NANOTECHNOLOGY 1

EDITORS
Prof Dr. Mustafa ERSÖZ
Dr. Arzum IŞITAN
Meltem BALABAN

Denizli 2018

~1~
NANOTECHNOLOGY 1
EDITORS
Prof Dr. Mustafa ERSÖZ
Dr. Arzum IŞITAN
Meltem BALABAN
(0258. 296 41 37 aisitan@pau.edu.tr)

ISBN 978-975-6992-77-7
1st Edition – October 2018

All rights reserved.

~2~
This book is an output of “Universal Nanotechnology Skills Crea-
tion and Motivation Development) / UNINANO” as numbered
2016-1-TR01-KA203-034520 supported by Turkish National Agency
under Erasmus+ Key Action 2 Strategic Partnership in the field of
Higher Education (KA203).

“Funded by the Erasmus+ Program of the European Union.

However, European Commission and Turkish National Agency can-
not be held responsi-ble for any use which may be made of the in-
formation contained therein”

~3~
CONTENTS

PREFACE 7
UNINANO PROJECT 8

SECTION 1 INTRODUCTION TO NANOTECHNOLOGY 9

1.1 MACRO, MICRO, NANO 11
1.1.1 Production Methods in Development of Technology and the Importance of Material 11
1.1.2 Importance of Size in Material Characterization 13
1.1.3 Macro Structures 14
1.1.4 Micro Structures 15
1.1.5 Nano Structures 17
1.2 The HISTORY of NANOTECHNOLOGY 19
1.2.1 Historical Development of Nanotechnology 19
1.3 DEVELOPMENT of NANOTECHNOLOGY 31
1.3.1 Nanotechnology in Material and Production 31
1.3.2 Nanotechnology in Electronics and Information Technologies 33
1.3.3 Nanotechnology in Medical Applications 35
1.3.4 Energy, Environment and Nanotechnology 37
1.3.5 Textile and Nanotechnology 39
1.3.6 Food Industry and Nanotechnology 42
1.4 NANOMETROLOGY 47
1.4.1 The Nanometer (nm) 48
1.4.2 The Nanogram (ng) 49
1.4.3 Current Nanoscale Measurement Studıes 51
1.5 IMPACT of NANOTECHNOLOGY 58
1.5.1 The impact of nanotechnology 58
1.5.2 How can nanotechnologies change our lives in the future? 62
1.5.3 The economic and social impact of nanotechnology 63
1.5.4 Nanotechnology Future today 64
1.5.6 Nano impact today 66

SECTION 2 PRODUCTION 71
2.1 EMULSION 73
2.1.1 Microemulsion 73
2.1.2 Microemulsion Types 76
2.2 PRECIPITATION 81
2.2.1 Chemical Precipitation 81
2.3 SONICATION 86
2.3.1 Sonication 86
2.3.2 Bubble Formation Mechanism 88
2.3.3 Synthesis Mechanism of Nanoparticles 90
2.4 ECO-FRIENDLY SYNTHESIS (GREEN CHEMISTRY) 93
2.4.1 Historical Overview 93
2.4.2 Principles of “Green” Synthesis 94
2.4.3 Methods 95
2.4.4 Application Examples 95
2.5 SOL - GEL METHOD 100

~4~
2.5.1 Sol - Gel Method Production Stages 101
2.5.2 Sol-Gel Material Components 102
2.5.3 3. Structures Created in Sol-Gel Method 104
2.5.4 Coating with Sol – Gel Method 105
2.5.5 Advantages of the Sol-Gel Method 106
2.5.6. Disadvantages of The Sol-Gel Method 106
2.6 PHYSICAL VAPOR DEPOSITION METHOD (PVD) 109
2.6.1 Sputter Technique 110
2.7 CHEMICAL VAPOR DEPOSITION METHOD (CVD) 114
2.8 LITOGRAPHY 118
2.8.1 Historical Development 118
2.8.2 Photoresists 120
2.8.3 Nanolithography 122

SECTION 3 NANOMATERIALS 127

3.1 NATURAL NANOPARTICLES 129
3.1.1 Natural Nanoparticles 129
3.1.2 Natural Nanoparticles in the Atmosphere 131
3.1.3 Natural Nanoparticles in the Hydrosphere 137
3.1.4 Mechanisms for the formation of natural nanoparticles (NNPs) 139
3.2 METAL and ALLOY NANOPARTICLES 152
3.2.1 Production Methods in Development of Technology and the Importance of Material 152
3.2.2 Biosynthesis of Metal NPs 154
3.2.3 Metals used in NP synthesis 155
3.2.4 Uses of Metal NPs 155
3.2.5 Alloy NPs 156
3.2.6 Arrangement of metal atoms in alloy NPs 156
3.2.7 Uses of Alloy NPs 157
3.3 NATURAL POLIMERIC NANOPARTICLES 163
3.3.1 Natural Polymers 164
3.3.2 Polysaccharides 164
3.3.3 Chitosan 164
3.3.4 Dextran 166
3.3.5 Alginate 167
3.3.6 Proteins 168
3.3.7 Collagen 169
3.3.8 Gelatin 170
3.3.9 Albumin 171
3.3.10 Synthetic Polymers 172
3.3.11 Lactide and Glycolide Copolymers 173
3.3.12 Poli(ɛ-Caprolactons) 174
3.3.13 Polyanhydride 174
3.3.14 Dendrimers 175
3.4 CERAMIC NANOPARTICLES 179
3.4.1 Conventional Sintering Method 181
3.4.2 Advanced Sintering Method 181
3.4.3 Usage areas of nano sized ceramic materials 182
3.5 MAGNETIC NANOPARTICLES 185

~5~
3.6 CONDUCTOR AND SEMICONDUCTOR NANOMATERIALS 191
3.6.1 Conductors 192
3.6.2 Semiconductors 193
3.6.3 Insulators 195
3.6.4 Conductor and semiconductor nanostructures 195
3.7 QUANTUM DOTS 201
3.7.1 Synthesis of Quantum Dot Structures 202
3.7.2 Application Fields of Quantum Dot Structures 203
3.8 CORE SHELL 209
3.8.1 Preparation and Importance of Core Shell Structure 209
3.9 CARBON-BASED NANOMATERIALS 217
3.9.1 Carbon nanoballs 219
3.9.2 Carbon nanotubes 220
3.9.3 Carbon nanorods 222
3.9.4 Carbon nanorings 222
3.10 GRAPHENE 225
3.11 THIN FILMSThİn Fİlms 233
3.12 NANOPARTICLE SHAPES 237
3.12.1 Factors affecting the shape control of nanoparticles 239
3.13 SURFACE MODIFICATION of NANOMATERIALS 246
3.13.1 Surface Modification of Nanoparticles 246
3.13.2 Surface Modification Mechanism of Nanoparticles 247
QUESTIONS 253

~6~
PREFACE
Nanotechnology, which is the fundamental technology of the industrial revolu-
tion of 21st century, is the science of controlling matter at atomic and molecular
levels. At its simplest meaning and depending on scientific determinations and
experiences, as a consequence of its contribution to environment, energy, mate-
rials strength and proper consumption, the share of nanotechnology in preser-
ving the world’s livability is very clear.
Today, the high value-added technology is vital for business lines that require
intense competition such as military, medical, automotive, textile applications.
In recent years, nanotechnological investigations have brought a significant
progress in especially materials science and many new products or process ta-
king place in our lives..
In general, nanotechnology education is conducted in post-graduate level and
the number of nanotechnology education programs within master’s and doctoral
programs increase constantly in many Universities. However, nanotechnology
education is very limited at undergraduate level in many natural sciences and
engineering programmes.
The books aimed at natural sciences and engineering undergaraduate students
as well as young students provide a complete review of all relevant aspects from
the nanotechnology and applications perspectives. The books provide practice-
based knowledge at undergraduate level through creating awareness of this
subject area and also support visual and e-learning in degree schemes that rela-
te to nanotechnology materials.
The Book 1 is devoted to provide a theoretical description of the basic principles
and fundamental properties of nanotechnology.
The Book 2 is devoted to presenting the characterisation techniques, micros-
copy, spectroscopy and application of nanotechnology for environmental, health
and safety issues.
We would like to thank very much to all researchers and authors who contribu-
ted to this two parts. We are deeply grateful to Erasmus+ Programme for fun-
ding the Universal Nanotechnology Skills Creation and Motivation Develop-
ment” KA203- Strategic Partnerships Project; 2016-1-TR01-KA203-034520 “
and the publication of these books.

Prof. Dr. Mustafa Ersoz, Editor

~7~
UNINANO PROJECT
You are reading Nanotechnology 1 book which is the one of the outputs of “Univer-
sal Nanotechnology Skills Creation and Motivation Development / UNINANO”
Project as numbered 2016-1-TR01-KA203-034520 supported by Turkish National
Agency under Erasmus+ Key Action 2 Strategic Partnership in the field of Higher
Education (KA203).
In UNINANO Project, Pamukkale University as coordinator and beneficiary institu-
tion, Selçuk University and Afyon Kocatepe University from Turkey, Bruno Kessler
Foundation and Cosvitec from Italy, Cluj-Napoca University from Romania, and
CCS from Greece have taken part.
To increase awareness of nanotechnology which is one of Turkey's 2023 strategic
goals has been the main objective of UNINANO Project. In line with this main ob-
jective, written and visual educational materials have been prepared, and aimed to
contribute to the advancement of nanotechnology knowledge by students and inst-
ructors using these materials. For this purpose, two course books have been prepa-
red in both printed and electronic versions, in both Turkish and English:
 Nanotechnology 1: Fundamentals of Nanotechnology
 Nanotechnology 2: Characterization and Applications

The electronic versions of the books are available on the www.pau.edu.tr/uninano

project website. Additionally, the answers of the questions at the end of the book,
also located on the web page can be accessed from e-learning materials.

With the happiness of completing our project;

We would like to thank to the Presidency of Turkey's National Agency for support of
our project.
We would like to thank to Rector of the Pamukkale University and Project Manager
Prof. Dr. Hüseyin BAĞ for his valuable support during two years.
We would like to thank to Prof. Dr. Mustafa Ersöz who worked scientific edito-
ralship of the book, and Meltem Balaban who worked in the book chapters' organi-
zation and book chapter authoring. As well as, we would like to thank to Dr. Zeha
Yakar, Dr. Cumhur Gökhan Ünlü, and Dr. Volkan Onar, the other project team
members of Pamukkale University, for their book chapters' authoring.
For their valuable effort and authoring, we would like to thank to all authors: Dr.
Arzu Yakar from Afyon Kocatepe University; Dr. Gratiela Dana Boca from Cluj-
Napoca University; Dr. Mustafa Ersöz, Dr. Gülşin Arslan, Dr. Yasemin Öztekin, Dr.
Serpil Edebali, Dr. İmren Hatay Patır, Dr. Canan Başlak, Dr. Emre Aslan and Dr.
İdris Sargın from Selçuk University.
We would like to thank to Ali Gökçe who prepared the UNINANO logo, Aydın Uçar
who prepared the cover design of the book, Can Kaya who helped in the book's ty-
pographic,and the students of Pamukkale University Technology Faculty who cont-
ributed to the project activities and meetings together with.

Dr. Arzum Işıtan

Project Coordinator
www.pau.edu.tr/uninano
https://www.facebook.com/UninanoPAU/
https://instagram.com/uninano_pau
https://twitter.com/Uninano_PAU

~8~
SECTION 1
INTRODUCTION
TO
NANOTECHNOLOGY

~9~
~ 10 ~
1.1 MACRO, MICRO, NANO
Dr. Arzum IŞITAN
aisitan@pau.edu.tr
PAMUKKALE UNIVERSITY
INTRODUCTION
In the broadest sense, the term "technology" is defined as "application informa-
tion covering the construction methods, tools, instrument and equipment used in
an industry, and their ways of use" [1].It can also be defined as all of the
equipment, all the information pertaining to these devices, developed by human-
kind in order to facilitate life, speed up production, change existing structures
and conduct research.
This definition is expressed as nanotechnology if it is applied to a dimension that
is defined as one billionth of meter. How did this adventure that can change from
meter to millimeter, millimeter to micrometers, micrometers to nanometers had
started?
1m 103 mm 106 µm 109 nm
Keywords: Macro, Micro, Nano
Abbrevisions: Meter (m), Milimeter (mm), Nanometer (nm)

1.1.1 Production Methods in Development of Technology

and the Importance of Material
The adventure had started with the discovery of fire. With the discovery of fire,
the most basic requirement for mine melting, casting and shaping was obtained
in addition to fundamental needs. Wood, stone and metal processing has become
increasingly easier. Although some casting methods have never changed for
about 6000 years, today scientists and engineers are constantly working on deve-
loping new production techniques and new materials for faster, more economical
and more convenient production.
From past to present, technology has always been used as a combination of both
artist elegance and engineering skills. These have all been achieved with the
same way as the queen's embroidered necklaces or royal crowns. However, as it
is well known, wars and weapons developed for those have a major role in the
development of technology. Light and sharp swords, light armors and large can-
nonballs have changed the fate of both nations and of technology.

~ 11 ~
The needs that increase with population have advanced technology further from
water-powered mills to flour factories, single-floor stone houses to skyscrapers,
from winding wheels to textile factory, carts to automobiles, boats to transatlan-
tic liners, stone bridges to suspended bridges that connect continents. Because
not only these structures, but also the tools and machinery necessary to realize
these structures were developed. By bringing together different materials, com-
posite materials that are completely different than the ones that formed them
have been produced. Or the existing materials have been improved with new
production and thermal techniques. Materials were processed at macro, micro
and nano levels, and as a result of all these developments, while telegraph was
an effective communication at the beginning of the century, telephones and mo-
bile phones have revolutionized communication. The transition from radio to
television, computer to tablet, air-land-railway transportation to interplanetary
space vehicles has become even faster.

At first, humankind met the needs from natural materials like stone, ceramics
and wood and built their structures with these; however, with the discovery of
bronze production, humankind paved a new and fast path.

~ 12 ~
Discovery of steel and its functionality had formed the foundation of industrial
revolution. The discovery of today’s light metals such as aluminum and tita-
nium, is very new in comparison to others and it is being used only for two cen-
turies. These metals were followed by the discovery of polymers. Although
composites are being used as building materials since ancient times, they have
become popular technological materials for the past 50-60 years.
Different properties can be obtained for the same material with different produc-
tion methods, and the properties of the materials can be changed through thermal
processes applied after production. The properties are characterized by color and
brightness in terms of macro scale, while in micro scale, the particles affect all
mechanical, physical and chemical properties and in the nano scale they repre-
sent atomic dimensions.
As a result of the collaborations of engineering technologies with the fundamen-
tal physics, chemistry and biology sciences, it became possible to analyze cha-
racteristics of organic and inorganic materials more thoroughly, they were better
understood and developed faster. The development of production and analysis
technologies has led to tremendous progress in many areas from medical appli-
cations to the furniture sector.

1.1.2. Importance of Size in Material Characterization

Nano materials/nano objects are materials that have one or more nano-sized
external dimensions [2,3].The nano scale is the last step of the material before
the atom. If all three dimensions of the material are less than 100 nm, such mate-
rials are called nanoparticles, quantum dots, nanoshells, nanorings and nanocap-
sules; if only two dimensions are less than 100 nm, they are called nanotube,
nanowire and fiber; if only one dimension is less than 100 nm, it is called thin
film, layer and coating [4].

Optical, mechanical, electrical and color properties of the same material in mac-
ro/micro and nano size may be different or even the opposite of other scales
[4].Some properties that do not occur in macro size may appear in nano size.
The main reason for this is the increased surface area/volume ratio with decrea-
sed material size and the non-continuous dimensions in nano-scale compared to
macro dimensions [5,6,7].As the surface area/volume ratio increases, materials
with low molecular weight can be formed [6,7].

~ 13 ~
  Human hair: 10-4 m, Red blood cell: 10-6 m, DNA: 10-8 m, Carbon nano-
tube: 3.10-9 m, Sİ atom: 10-10 m
 Human nail grows 1 mm per second.

1.1.3 Macro Structures

Macro structures are defined as visually observable and easily measurable sys-
tems. Standards have been developed to determine the physical and chemical
properties of parts or equipment with macro size. If the materials are structural
load-carrying elements, the mechanical properties that define the behavior of the
material under the load become very important. The priorities according to the
material selection and characterization can be listed as follows:

a) Durability
b) Wear resistance
c) Corrosion resistance
d) High/low temperature resistance
e) Ability to be shaped
f) Compatibility with assembly techniques
g) Appearance/brightness
h) Biocompatibility

The properties expected from the parts of a machine tool are different than the
properties desired for a photocopy machine or a washing machine. The proper-
ties of the glass used in the windows differ from the glass of a fish glass. Altho-
ugh both are ceramic, the properties expected from porcelain plates in our homes
are different than a flower pot and all these properties are expressed in macro
sense.
~ 14 ~
The reason for the use of platinum and titanium instead of stainless steel, which
was initially used as prosthetic material, is due to their higher biocompatibility.

1.1.4 Micro Structures

Micro structures are systems that can’t be seen by eye, and can only be characte-
rized with microscope. The size and shape of the particles forming the micro-
sized metallic materials and the type and thickness of the coatings on the mate-
rial are very influential on the mechanical properties. However, macro and micro
properties of the same material are basically the same.

In addition to the advantages of micro sizes in material technology, miniature

systems are being developed to obtain desired properties in macro scales. These
~ 15 ~
systems are being developed to obtain desired properties in macro scales. These
systems are called microelectromechanical systems (MEMS)/micro systems
technology (MST)/micromachines [9,10].These are miniature embedded systems
that contain one or more pieces of micro machine or structure.

Micro components make a system smaller, faster, more reliable, cheaper and let
them have more complex functions. In the most general sense, MEMS microst-
ructures are systems that are consisted of microsensors, microactuators and mic-
roelectronic components onto a silicon chip [9]. Microsensors detect changes in
the system environment by measuring mechanical, thermal, magnetic, chemical
or electromagnetic information or phenomena [9].

https://www.hysitron.com/applications/semiconductor-electronics/mems
http://internetofthingsagenda.techtarget.com/definition/micro-electromechanical-systems-MEMS
Google 17/05/2017

Sensor is a device that measures information and provides an electrical output

signal in response to the measured parameter. They can conduct mechanical,
thermal, chemical, magnetic and electrical measurements. A transducer is a de-
vice that converts a signal or energy into another form. The actuator is a device
that converts the received electrical signal into a process.

The most prominent feature of MEMS technology is the miniature dimensions.

Although MEMS technology is in miniature dimensions, it allows us to get the
desired tasks and targeted efficiencies at macroscopic levels also in miniature
dimensions [8].MEMS or micro technology is a rapidly evolving technology and
has a great potential to reshape the life standards of the future. By using this
technology [8,9]

 it is possible to reduce microsystem size by integrating micro-electronic

circuits or mechanical structures on the same integrated structure,

 one-piece integration and production of devices with very low cost.

The most advantageous potential material for MEMS is silicon because of its
physical and commercial properties. Microprocessing is especially specially

~ 16 ~
developed for the production of basic microelectromechanical devices such as
miniature sensors and actuators. Micro processing of silicon is the most mature
form of micro-processing technologies and allows for the production of MEMS
that have sub-millimeter size [10]. Silicon micro-processing is forming a mic-
roscopic mechanical part from a silicon substrate or a silicon bottom layer.

Uses of MEMS technology [8]

 biomedical sensors, miniature biochemical analytical instruments, pace-

makers, catheters, drug delivery systems,
 motor and drive control, automotive safety/brake/suspension systems,
 fiber optic components,
 low power and high density mass data storage systems,
 control of wireless electronic, aerodynamic and hydrodynamic systems,
 integrated fluid systems for miniature propulsion and combustion control,
 early detection systems against biological and chemical threats,
 electromechanical signal processing for small and low voltage fluctua-
tions.
 night vision systems

Micro-optoelectromechanical systems (MOEMS) are also a subset of the MST

and they form specialized technology fields by using miniature optical, electro-
nic and mechanical combinations with MEMS [8].

1.1.5 Nano Structures

Nano structures are atomic or nano-scaled systems and they are obtained by
using one or more mechanical, physical, chemical and thermal processes. For
example, two fluids that have droplet sizes of 0.1-1.0 µm form a thermodynami-
cally instable emulsion by completely dispersing within each other, and they get
separated in time due to gravity; however, emulsion that have droplet sizes smal-
ler than 100 nm form microemulsion that are thermodynamically stable, time-
independent, not affected by processes such as agitation and they have transpa-
rent appearance, and they allow for water-oil combination. In addition to nano-
particle synthesis, this method is used for paint, textile coating, cosmetics and
pharmaceutical areas.

Nanostructures obtained by very different production methods are used in many

different areas such as drug delivery, self-cleaning fabrics, flexible and highly
durable materials, and nano-sized machine production.

~ 17 ~
References
[1] www.tdk.gov.tr
[2] Bruus, H. “INTRODUCTION to Nanotechnology”, Lecture Notes,
Technical University of Denmark, spring 2004.
[3] Ramsden, J. “Essentials of Nanotechnology”, Ventus Publishing ApS,
2009.
[4] Filipponi, L. and Sutherland, D. “Nanotechnologies: Principles, Appli-
cations, Implications and Hand-on Activities”, Edited: by the European
Commision NMP Programme, 2012, European Union, Luxemburg.
[5] Nouailhat, A. “An INTRODUCTION to Nanoscience and Nanotechno-
logy”, John Wilwy and Sons Inc, Hoboken, USA, 2007.
[6] “Springer Handbook of Nanotechnology”, Editor: Brahat Brushan,
Springer, 2006.
[7] Hornyak, GL, Moore, JJ, Tibbals, HF, Dutta, J. “Fundamentals of Nano-
technology”, CRC Press, 2008.
[8] “An INTRODUCTION to MEMS”, PROME Faraday Partnership, Lo-
ughborough University, 2002.
[9] Maluf, N, Williams, K. “An INTRODUCTION to Microelectromecha-
nical System Engineering”, ARTECH HOUSE INC., Norwood, 2004.
[10] Varadan, VK, Vinoy, KJ, Jose, KA. “RF MEMS and Their Applicati-
ons”, John Wiley& Sons Ltd, England, 2003.

~ 18 ~
1.2 The HISTORY of NANOTECHNOLOGY

Dr. Zeha YAKAR

zyakar@pau.edu.tr
PAMUKKALE UNIVERSITY
INTRODUCTION
Stainless fabrics, unscratchable surfaces, color changing paints, anti-aging cos-
metic products and more... Nanotechnology, which has been described as the
comprehension, control and modification of functional materials at 1-100 nano-
meter briefly, takes attention with nanotechnology products and which we are
frequently encountered on advertising panels and televisions, is regarded as a
new technology revolution. In this chapter, the historical development of nano-
technology, which is included in our lives today quickly, will be discussed.

1.2.1 Historical Development of Nanotechnology

In fact, the use of nanotechnological products, which has an older history than
expected, dates back to ancient history. When we examine the histor-ical deve-
lopment in this regard, the Lycurgus Cup is considered as one of the greatest
successes of the glass industry of antiquity used by the Ro-mans in the 4th cen-
tury. The most important feature of this Cup which is still exhibited in the Bri-
tish Museum and is at an age of 1600 is the color change. The secret of the Cup
which is green when it is illuminated in the front and is red when it is illumina-
ted from back has been uncovered in 1990.

The Lycurgus Cup at the British Museum; illuminated in front (left) and back
(right)
(This image is published on https://twitter.com/britishmuseum/status/829336475548471296 and retrieved from
Google Images.)

~ 19 ~
Research has shown that the cup contains soda-lime glass and that there is 1%
gold and silver and 0.5% manganese in this glass. The researchers then assumed
that the unusual color change and spreading effect of glass was provided by col-
loidal gold. With the advances on research techniques in later years, scientists
discovered that gold and silver particles were found on the cup’s glass using
electron microscopes and radiographs, ranging from 50 to 100 nanometers in
size, one thousand times thinner than a hair and one thousand times smaller than
common salt.(Tolochko, 2009). In his work on plasmon published in the 2007
Scientific American, H.A. Atwater described these color changes by plasmon
stimulation of metal nanoparti-cles. This color-changing cup made by glass mas-
ters in the ancient Roman period using nanoparticles is one of the first examples
of nanotechnology.

Rose window on the north facade of Notre Dame Cathedral

(This image is published on https://www.alamy.com/stock-photo/north-rose-window-notre-dame-
cathedral.html and retrieved from Google Images.)

Another example of the nanotechnology known in the history is the stained glass
window which was frequently used in the European cathedrals be-tween the 6th
and 15th centuries and which lasted until today. These win-dows have dazzling
colors thanks to nanoparticles of gold chloride and other metal oxides and chlo-
rides. It was revealed that between 9th and 17th centuries, the living, shiny and
bright ceramic glazes used in the world of Islam and later in Europe contained
silver, copper or other metallic nano-particles (Tolochko, 2009).

~ 20 ~
Carbon nanotubes and cementite nanowires have also been used in the construc-
tion of the Damascus swords, which are known for their sharp-ness, flexibility
and durability in the 13th and 18th centuries (Reibold, Pau-fler, Levin, Koch-
mann, Pätzke and Meyer, 2006; Tolochko, 2009).

Damascus Sword Known for its sharpness, flexibility and durability

(This image is published on Google images and retrieved from Google Images at 17/05/2017.)

When the history of science is examined, it is seen that the use of nano-particles
with sizes ranging from 1 to 100 nm, which is the core of nano-technology used
in glass coloring since ancient times, has been a research topic only since the
middle of the 19th century. In fact, Michael Faraday (1857) took the greatest
step in the development of nanotechnology with his systematic studies of the
properties of metal colloids, especially gold colloids. Faraday has prepared aqu-
eous colloidal blends containing less than 100 nm of gold nanoparticles and has
determined that these blends have exceptional optical and electrical properties.
Faraday has compared the optical and electrical properties of gold-colloidal
mixtures to those of very fine gold leaves and found that they have different
properties. This difference is related to the granular structure of the colloidal
gold (Baalousha, How, Valsami-Jones and Lead, 2014). It was not possible to
determine and control the size distribution of the gold particles during the nine-
teenth century when this remarkable invention was made. Richard Zsigmondy,
who received the Nobel Prize in Chemistry for the first time in 1925, measured
the dimensions of nanoparticles such as gold colloids and used the nanoparticles
concept for the first time (Baalousha et al., 2014; Hulla, Sahu and Hayes, 2015).

~ 21 ~
 Richard A. Zsigmondy, the first person to use the nanometer concept
(This image is published on https://www.stampcommunity.org/topic.asp?TOPIC_ID=6541&whichpage=7 and
retrieved from Google Images.)

Richard Feynman is accepted as the idea father of modern nanotechnolo-gy.

Richard Feynman, who has been awarded the Nobel Prize in physics in 1965,
said in his speech "There is plenty of room at the bottom" at the meeting of the
American Physical Society in Caltech on December 29, 1959 as an idea without
the use of nanotechnology word that it is possible that atomic and molecular
sizes could be manufactured by developing special measurement and production
methods in nanoscale. In his speech, Feynman said that in small dimensions,
laws like gravity would decline and weaker micro-level forces like Van der
Waals would become more important.

Richard Feynman, the mastermind of nanotechnology

(This image is published on https://www.atomicheritage.org/profile/richard-feynman and retrieved from
Google Images.)

~ 22 ~
Feynman believes that adolescents will be a driving force in the scientific deve-
lopment, and in this important speech, he has announced two prob-lems to rese-
archers and promised to give $ 1,000 a prize when the problem has been solved.
One of the problems was the construction of a nanomo-tor. The problem was
solved immediately in 1960 with the construction of a cube-shaped engine with
an edge length of 1/64 inch (0.3 mm). The sec-ond problem was that all Encyc-
lopedia Britannica had to be reduced in size to write on top of a nail. This prob-
lem was solved in 1985 by Tom Newman, a graduate of Stanford University. He
wrote the first page of Charles Dickens' "The Story of Two Cities" with electron
beams on the top of the nail and received the second $ 1,000 prize. Today, the
"Feynman Award" is given by the Foresight Institute to science enthusiasts who
have made advances in the name of nanotechnology in memory of Feynman
(Keiper, 2003).

Approximately 15 years after Feynman's speech, the nanotechnology term was

first used by Norio Taniguchi in 1974. Using the focused ion beam technique,
atomic layer deposition and other methods, Taniguchi used the term nanotechno-
logy (nano-technology) to describe the processes of forming semiconductor
structures with nanometric precision. Nanotechnology has been characterized
by processes of processing, separation, joining, and deformation of materials by
a major atom or mole-cule (Keiper, 2003; Hulla, Sahu and Hayes, 2015).

Norio Taniguchi used the term nanotechnology for the first time
(This image is published on http://www.nanotechnologyresearchfoundation.org/nanohistory.html and retrie-
ved from Google Images.)

Another important person in the history of nanotechnology is Eric Drexler,who

has the first doctoral degree in molecular nanotechnology from the Massachu-
setts Institute of Technology (MIT). He became famous and was known with his
~ 23 ~
books titled "Engines of Creation: The Coming Era of the Nanotechnology" and
"Nanosystems: Molecular,Machinery,Manufacturing and Computation" publis-
hed in 1986.

Eric Drexler, the first person in the world had a doctorate in molecular nano-
technology
(This image is published on http://www.thenanoage.com and retrieved from Google Images.)

In his books, Drexler noted that nanorobots could exist, using biological systems
to make devices at the molecular level, and tried to reveal the effects of this
technology. In addition, he established the Foresight Insti-tute, a California-
based, non-profit organization that tries to educate socie-ty about both the poten-
tial benefits and risks of nanotechnology. In addi-tion, "Engines of Creation:
The Coming Era of the Nanotechnology" is the first nanotechnology book pub-
lished (Keiper, 2003).

An important breakthrough in the development of nanotechnology is the scan-

ning tunneling microscope (STM) invented by Gerd Binnig and Hein-rich Roh-
rer in 1981 in IBM's Zurich research lab.

STM is a powerful microscope that does not require special light, special lens, or
electron source for radiation, high resolving power that shows the three-
dimensional structure of the surface of objects small enough to be imaged by
conventional microscopes or powerful electron microscopes. It is widely used in
both industrial and basic research to obtain atomic scale metal surface images.
Binnig and Rohrer were awarded the Nobel Prize for Physics in 1986 for this
invention (Filippino and Sutherland, 2013). In 1986 Gerd Binnig, Calvin Quate
and Christoph Gerber developed the first atomic force microscope (AFM).

~ 24 ~
 Gerd Binning and Heinrich Rohrer invent the Scanning Tunneling Microscope
(This image is published on http://www.nobelprize.org and retrieved from Google Images.)

The first commercial AFM was put on the market in 1989. Today, AFM is one
of the most advanced tools in nanoscale imaging, measurement and material
processing and is used to solve processing and material problems in a wide vari-
ety of technologies that affect the tele-communications, biological, chemical,
automotive, aerospace and energy industries. The AFM not only resembles sur-
face imaging at atomic resolu-tion but also measures infinitesimal forces at the

nano-newton scale (Flippino and Sutherland, 2013).

Gerd Binnig, Calvin Quate and Christoph Gerber, invented Atomic Force Mic-
roscope
(This image is published on http://www.kavliprize.org and retrieved from Google Images.)

In 1985, Richard E. Smalley, Harold W. Kroto and Robert F. Curl discovered a new
form of hard carbon element after diamond and graphite, consisting of 60 carbon atoms
(C60). In fact, the first article on C60 was published by Eiji Osawa at Toyohashi Univer-

~ 25 ~
sity in 1970. In Osawa's article, he suggested that carbon may have a cage structure like
ball. However, the publication is not recognized worldwide because it is Japanese. On
the other hand, the studies published by Smalley, Kroto and Curl in Nature magazine in

1985 received great interest in the scientific world and won the 1996 Nobel Prize for
Chemistry (Erkoç, 2012).

The similarity of the C60 molecule with the football and the Geodetic Dome
(a- This image is published on http://www.gcsescience.com/a38-buckminsterfullerene.htm and retrieved from
Google Images. b- This image is published on http://thenanoage.com/buckminsterfullerene.htm and retrieved
from Google Images.)

As a famous architect, Buckminster Fuller is very similar to the geodetic dome

design, carbon molecules consisting of this new form of carbon element, which
is composed of sixty carbon atoms, are called "Buckminsterfullerene". Also
known as "Buckyballs", which resemble footballs, these structures are stronger
than steel, lighter in weight, and have an electrical and heat-permeable structure

~ 26 ~
at a nanometer scale especially in drug delivery and nanotechnology applications
(Flippino and Sutherland, 2013). Following this discovery, in 1991, the Japanese
NEC company announced that its researchers Sumio Iijiman found carbon nano-
tubes. Carbon nanotubes have a stretched shape of the C60 molecule and have
similarly important properties; 100 times stronger than steel, and the weight is
about 6 times the weight of steel (Baalousha, How, Valsami-Jones and Lead,
2014). Carbon nanotubes are used extensively in transistors and fuel cells, on
large TV screens, and in ultra-sensitive sensors due to their unique electrical
properties and extraordinarily thin nanoscale dimensions (Erkoç, 2012).

Sumio Iijima, the first person to find carbon nanotubes

(This image is published on http:// www.meijo-u.ac.jp/english/news/detail.html?id=xhFEUY and retrieved
from Google Images)

At the beginning of the 21st century, very important advances were made in the
use of nanotechnology in fields such as medicine, biotechnology, computer
technology, aviation, energy use, space studies, materials and manufacturing.

In 1999, the National Nanotechnology Initiative, the first official govern-ment

program to promote the speed of nanotechnology research, devel-opment and
commercialization, was launched in the United States. In 2001, nanotechnology
studies included the European Union Framework Programme as a priority area.
Japan is one of the countries that invest in nanotechnology in Asian countries.
Japan is the second country in the world to support the largest number of R & D
~ 27 ~
studies in the field of nano-technology after the United States. Among Asian
countries, China and Korea stand out among the countries that follow Japan.
While most of the work carried out in China are concentrating on semiconductor
manufactur-ing techniques and nano-technology based electronic devices, Korea
con-ducts research on microelectronic applications and microelectromechanical
systems (MEMS) (Roco, 2011). Turkey, who wants to participate in the nano-
technology revolution started in the middle of the 20th century by providing
support to sectors especially such as paint-coating, technical textile, chemical
materials, automotive, construction sector, materials and polymer composite, has
increased its investment in researches made in this area (Körözlü, 2016). In the
future, as nanotechnology will play a major role in the discovery of new compo-
nents and in the development of exist-ing technologies, it is inevitable that the
indispensable place of this tech-nology loft will remain for many years.

Summary
Nanoparticles, which are the foundation stone of these products, started to be
investigated only in the middle of the 19th century, though today's products of
nanotechnology based on the past are very common. The greatest step in the
development of nanotechnology was made by Michael Faraday in 1857, prepa-
ring aqueous colloidal blends containing small gold nanoparticles and examining
the optical and electrical properties of these blends. The size of the nanoparticles
was first measured by Richard Zsig-mondy in 1925 and the nanometer concept
was used for the first time. Richard Feynman (1959), who said that it would be
possible to manufac-ture atomic and molecular sizes by developing special mea-
surement and production methods at the nanoscale, and that there could be many
new discoveries on this scale is considered as the mastermind of the nano-
technology. The first scientist to use the term nanotechnology was Norio Ta-
niguchi (1974). Taniguchi has stated that nanotechnology consists of processes
of processing, separation, joining and deformation of materials by a major atom
or a molecule. Eric Drexler is another important name that made nanotechnology
popular.

Drexler has tried to educate society on the potential benefits and risks of nano-
technology with publications. One of the important inventions that helped nano-
technology evolve is the Scanning Tunneling Microscope, invented by Gerd
Binnig and Heinrich Rohrer (1981); And the other is the atomic force microsco-
pe developed by Gerd Binnig, Calvin Quate and Christoph Gerber (1986). A
~ 28 ~
new form of a carbon atom which is made of 60 carbon atoms (C60), 1 nanome-
ter in size, and is stronger than steel, lighter in plastic and lighter in electricity
and heat-permeable, was discov-ered in 1985 by Richard E. Smalley, Harold W.
Kroto and Robert F. Curl.

C60 is mainly used for drug release and nanotechnology applications. Carbon
nanotubes with similarly important properties with a stretched shape of the C60
molecule were discovered in 1991 by Sumio Iijima.

Carbon nanotubes are often used in ultra-sensitive sensors in transistors and fuel
cells, large TV screens, due to their electrical properties and their fine structure.
These rapid developments recorded in nanotechnology will enable the future to
emerge lighter materials with lower error levels and unmatched durability, and
these lightweight materials will bring revolution-ary innovations for many of the
existing industrial processes.

~ 29 ~
References
Atwater, H.A. (2007). The Promise of Plasmonics. Scientific American, 296(4),
56-63.
Baalousha,M., How, W., Valsami-Jones, E. ve Lead, J.R. (2014). Overview of
Environmental Nanoscience. In Lead, J.R., Valsami-Jones, E. (Eds.), Nanosci-
ence and the Environment. Elsevier, Amsterdam, Netherlands.
Erkoç, Ş. (2012) Nanobilim ve Nanoteknoloji, ODTÜ Geliştirme Vakfı Yayıncı-
lık ve İletişim A.Ş., Çankaya-Ankara.
Filipponi, L. ve Sutherland, D. (2012). Nanotechnologies: Principles, Applicati-
ons, Implications and Hands-on Activities. European Union, Luxemburg, 2012.
doi:10.2777/76945.
Erişim: https://ec.europa.eu/research/industrial_technologies/pdf/nano-hands-on-
activities_en.pdf
Hulla, J.E., Sahu, S.C. ve Hayes, A.W. (2015). Nanotechnology: History and
Future. Human Experimental Toxicology, 34(12), 1318-1321.
Keiper, A. (2003). The Nanotechnology Revolution. A journal of Technology
and Society, 1(2), 17-34.
Körözlü, N. (2016). Bilim ve teknolojinin geleceği nanoteknoloji. Ayrıntı Dergi-
si, 4(39), 27-30.
Reibold, M., Paufler, P., Levin, A. A., Kochmann, W., Pätzke, N. ve Meyer, D.
C. (2006). Materials: Carbon nanotubes in an ancient Damascus sabre. Nature,
444,(7117), p. 286. doi:10.1038/444286a
Roco, M.C. (2011). The Long View of Nanotechnology Development: The Na-
tional Nanotechnology Initiative at 10 Years. Journal of Nanoparticle Research,
13, 427-445.
Taniguchi, N. (1974) On the Basic Concept of Nanotechnology. Proceedings of
the International Conference on Production Engineering, Tokyo, 18-23.
Tolochko, N.K. (2009). History of Nanotechnology. In: Kharkin, V., Bai, C.,
Awadelkarim, O.O, Kapitsa, S. (Eds.), Nanoscience and Nanotechnology.
UNESCO, Oxford, UK, EOLSS, Encyclopedia for Life Support Systems.

~ 30 ~
1.3 DEVELOPMENT of NANOTECHNOLOGY
Dr. Zeha Yakar
zyakar@pau.edu.tr
PAMUKKALE UNIVERSITY

INTRODUCTION
Nanotechnology, the key technology of the 21st century, presents us with the
latest applications for diagnosing and treating diseases, monitoring and protec-
ting the environment, generating and storing energy, improving crop production
and food quality, and building complex structures. In this section, latest deve-
lopments and application fields of nanotechnology, which has become an impor-
tant part of our life, will be explained.

1.3.1 Nanotechnology in Material and Production

Today, more durable, longer-lasting, cheaper, lighter and smaller devices with
higher quality can be developed with the use of nanotechnology. These develo-
ped products stand out with their less material and energy requirement, cheaper
expenses and easy shipping, more functionality and ease of use (Ramsden, 2011;
Lines, 2008).

Nanoparticles, with their sizes between 1-100 nm and the significant improve-
ments they provide in the functionality of metal, ceramic, polymeric or composi-
te systems, form the basis of not only nano-sized materials but also nanotechno-
logy as well. Nanomaterials are now being used for the development of many
products that we use in our daily life. Skiing materials made of waterproof nano-
fibers and tennis balls produced by using clay based polymer nanocomposites
are two of the best examples of such products. These products, developed with
nanotechnology, are relatively more durable, longer-lasting and lighter.

~ 31 ~
 Structure of tennis balls produced with nanotechnology.
(This image is published on http://nano--tech.blogspot.com.tr/p/leisure.html and retrieved from Google Ima-
ges.).

Increased surface area and quantum effects are two of the most important pro-
perties that differentiate nanoparticle-enhanced materials from other materials.
For a particle of 30 nm, the atom ratio on the surface is 5%, whereas, this ratio
goes as high as 20% for a size of 10 nm. Therefore, nanoparticles have higher
surface/volume ratio than large particles. This situation makes nanoparticles
more sensitive than large particles in terms of reactivity, resistance, rigidity and
electrical properties. In addition, as the size of the materials decreases in nano-
scale, their quantum effects can impact and change the optical, electrical and
magnetic properties of the material.
As these properties of nanoparticles are revealed, significant developments have
emerged about using nanoparticles in production and materials. Nanoparticles
are especially being widely used for coating, surfaces and functional structures.
Self-cleaning surfaces and glasses are the best examples. These materials, coated
using titanium dioxide with high activation, have non-water retentive and anti-
bacterial properties. The synthetic material produced using polymer composites,
which are sensitive to touch, and enhanced with nickel nanoparticles, which can
rapidly and repeatedly recover themselves at the room temperature, is another
example. After this synthetic material is cut, it can restore itself back to its origi-
nal form within about 30 minutes by slightly combining the cut pieces together.
Such advancements are expected to lead to the development of self-repairing
smart prostheses (Servick, 2012).

~ 32 ~
 Self-assembly synthetic material produced with nanotechnology.
(This image is published on http://news.stanford.edu/news/2012/november/healing-plastic-skin-111112.html
and retrieved from Google Images.)

Clothes that have properties such as waterproof, self-cleaning, protection against

sunlight or anti-static can be manufactured by coating the fabrics with nanopar-
ticles. In addition, clothes are protected against bacteria since the nanoparticles
are being used in ventilation filters or washing machines.

1.3.2 Nanotechnology in Electronics and Information Tech-

nologies
Nanotechnology, which aims to produce high-performance and economic mate-
rials and devices, had and still have great contributions to the advancements in
the fields of electronics and information technologies. Faster, smaller and more
portable systems that can manage and store larger and more information are
developed with the use of nanotechnology. The best example of this is the basic
switches, or transistors, that activate all modern computers that have an impor-
tant role in the development of computer technology. Transistors are electrical
circuits components that regulates a voltage or current source and another volta-
ge or current source. Transistors form the basis of all electronic devices that we
use every single day, such as computers, smart phones and televisions.

At the beginning of the century, a typical transistor size was between 130 nm
and 250 nm, however, in 2016, a research team working at Lawrence Berkeley
National Laboratory had managed to make 1 nanometer transistor by using “car-

~ 33 ~
bon nanotubes” and “molybdenum disulfide (MoS2).This is the smallest transis-
tor ever produced (Desai et al., 2016).

The smallest transistor in the world is produced by using carbon nanotubes and molyb-
denum disulfide, which are alternatives to silicon.
(This image is published on http://www.techtimes.com/articles/181282/20161007/worlds-smallest-transistor-
built-using-carbon-nanotubes-and-engine-lubricant.htm and retrieved from Google Images.)

The electrical properties of carbon nanotubes, which have a thickness of a mil-

lionth of a millimeter and became popular in recent years, can be very different
and advantageous compared to semiconductors such as silicon.IBM, the largest
information technologies company in the world, is aware of the potential of this
material and defined carbon nanotubes as the “foundation of the future beyond
silicon”. Instead of millions of electrons, information can be processed with the
movement of a single electron in nano-sized transistors. As a result, it is possible
to achieve significant energy-saving. In addition, since it is very small, billions
of transistors can be fit into an area of one centimeter square. Therefore, compu-
ters can operate faster and efficiency can be further increased. In short, smaller,
faster and better transistors mean whole memory of the computers can be stored
inside a single tiny chip. With the production of nano-scaled electrical circuit
components, computers manufactured with nanotechnology are expected to be
smaller, faster, have greater capacity with less energy consumption than those
produced by using today’s technology.

~ 34 ~
1.3.3 Nanotechnology in Medical Applications

Nano-scaled materials and nano electronic biosensors are used to diagnose, mo-
nitor, follow-up and prevent the diseases in nanomedicine, which is the applica-
tion of nanotechnology in medicine. Today, many diseases from diabetes, cancer
to Parkinson and Alzheimer’s are threatening human life and accurate diagnosis
is of crucial importance in order to provide the correct treatment. Nanosensors
and nanoparticles produced with nanotechnology play an important role in the
correct diagnosis and timely treatment.

Drug delivery is one of the most important applications of nanotechnology in

medicine and many studies are being conducted on these applications. By injec-
ting the drugs that are loaded with nanoparticles, it is possible to detect diseased
cells, such as cancer cells, via these nanoparticles. Nanoparticles deliver the
drugs they carry to the diseased cells and they help the body to destroy these
cells without harming healthy cells. The best example of this application is the
Chemotherapy drugs that are loaded into nanoparticles for the cancer treatment.

Drug delivery is one of the most important fields of nanotechnology in medicine.

(This image is published on http://www.inovatifkimyadergisi.com/tag/nano-ilaclar and retrieved from Google
Images.)

Another important implementation of nanotechnology in medicine is the use of

quantum dots for the diagnosis and treatment of tumors in the human body. Alt-
hough this is still a developing technique, it is a promising approach for the can-
cer treatment.

~ 35 ~
Cancer diagnosis can be performed by detecting the location of cancerous tissues
by using iron oxide nanoparticles, which have magnetic properties. First, special
antibodies marked with iron oxide nanoparticles that are developed against the
tumor being sought for are injected to the body. If the sought tumor cannot be
found in the body, marked antibodies attach to the antigens on the tumor surface.
Tumors can be detected with the MRI device using the magnetic signals emitted
from the iron oxide particles present in the antibodies that are gathered in the
cancerous tissue. Even a very small tumor tissue in the body can be detected
(Nikalje, 2015).

In addition, the nano-vaccine field is rapidly developing with the recent emer-
gence of new nanotechnology tools and more information on polymeric drug
delivery. Nano-vaccines, developed by a group of scientists, are consisted of
synthetic polymer nanoparticles that contain tumor proteins recognizable by the
immune system, and they help people to fight cancer (Luo et. Al., 2017).

Nanoparticle vaccinations that will be used for the treatment of many diseases in
the future (This image is published on https://id-ea.org/researchers-explore-new-class-of-synthetic-
vaccines/ and retrieved from Google Images.)

Another application is Buckyballs fullerene, a nanomaterial that is used for the

reduction of inflammation during allergic reactions and for the involvement of
free radicals that occur during these reactions. In addition, nanoshells are used to
destroy cancer cells that are heated with infrared rays without damaging the he-
althy cells. The use of aluminosilicate nanoparticles with water absorption pro-
perties in trauma patients is very useful. Because of these properties, aluminosi-
licate nanoparticles cause faster clotting and reduce bleeding. Nanotechnology
can also be used to kill microorganisms. The wound can be purged from micro-

~ 36 ~
bes with silver nanoparticles. Some nanoparticles are used to treat infections.
Nitric oxide gas inserted wound creams can be given as an example. When these
creams applied on the wound, these nanoparticles release the nitric oxide gas
they carry and destroy the bacteria (Adnan, 2010).

1.3.4 Energy, Environment and Nanotechnology

In addition to efficient energy use, storage and generation, nanotechnology is

also being used to detect and clean the environmental pollutants. Nanotechno-
logy has different applications from providing clean potable water, increasing air
quality, developing new energy resources and removing hazardous and toxic
substances away from our environments and nanotechnology will definitely help
to create a sustainable environment.

Nanotechnological applications will be effective in the creation of a sustainable envi-

ronment.
(This image is published on http://nanoday.com/single/1013/benefits-of-nanotechnology-applications-in-
different-fields and retrieved from Google Images.)

~ 37 ~
Today, natural resources are running out at a high rate due to ever-increasing
energy-fuel consumption. As a result, the search for alternative energy sources

has increased in recent years and developed countries have allocated important
financial support for the research, especially on alternative energy sources. The
most important ones are the studies on Hydrogen energy. One of these studies is
about a generator powered by light and cleans the air while generating hydrogen
fuel. With the nanoparticles present in the catalyst of the device, hydrogen fuel is
produced as the dirty air is cleaned (Verbruggen et al., 2017).
A light-powered generator that generates hydrogen fuel and cleans the air.
(http://www.inovacaotecnologica.com.br/noticias/noticia.php?artigo=ar-poluido-usado-produzir-combustivel-
limpo&id=010115170515#.WbEYzNSLQsY and retrieved from Google Images.)

It is possible to store this produced hydrogen gas as fuel and hydrogen buses are
the best example of this. However, in order to spread the use of this energy, first
it is necessary to store hydrogen in high density and in a safe way. However,
storing high density hydrogen is a difficult and expensive task. Today, scientists
showed that hydrogen can be stored at very high capacities in carbon nanotubes
and molecules that are functionalized by transition elements (Pt, Pd, Ti, V
etc).Hydrogen-powered automobiles can become more common with this disco-
very and this will lead to environmentally friendly fuel consumption. This way,
solution can be found for clean air and alternative energy need.

Another important development in energy industry occurred in the studies for

battery life. Scientists used highly conductive nanowires, which are thousands
time thinner than human hair, in the batteries to increase the battery life. These
wires create a large surface area, therefore, provide a larger storage capacity; this
way, more electrons can be transferred. However, studies showed that these
wires are very fragile and cannot be re-charged many times. A group of researc-

~ 38 ~
hers coated nanowires inside a manganese dioxide and plexiglass-gel electrode
compound to eliminate this problem. The safety and durability of this mixture
are revealed through testing over more than 200.000 cycles. As a result of tests,
batteries didn’t lose capacity and used nanowires didn’t break down (Thai,
Chandran, Dutta, Li and Penner, 2016).This study is expected to prolong the life
of commercial batteries significantly. With such developments, smart phones,
computers, cars and other battery-powered vehicles may not need their batteries
replaced.

Quality of potable water can be increased by using nanoparticles.

(This image is published on https://www.cnbc.com/2015/11/12/light-work-getting-clean-water-with-
nanotech.html and retrieved from Google Images.)

Applications in water treatment processes are another important implementation

of nanotechnology. Nanomaterials such as nanomembranes, carbon nanotubes,
nanoclays and aluminum fibers are being used for water treatment applications.
These materials are cheap, portable and easily cleanable systems. Nanofilters
can clean the precipitates, chemical wastes, charged particles, bacteria and other
pathogens such as virus from the water. In addition, they can also clean toxic
trace elements like arsenic and viscous liquid contamination such as oil (OECD,
2004).

1.3.5 Textile and Nanotechnology

Today, integrating different properties in nanometer dimensions to the materials

used in textile industry leads to very important developments and it is expected
to continue. The most common application of nanotechnology is anti-stain and
anti-wrinkle products and products that are resistant to liquid spills. Scientists
have developed titanium dioxide nanolayer particles that react with sunlight to
destroy dirt and other organic materials, and they have allowed the fabric to stay
~ 39 ~
clean by coating this layer with cotton. Nanoparticles like clay, metal oxide,
carbon black, and graphite nanofibers and carbon nanotubes are being used to
improve the physical properties of textile products such as increasing their mec-
hanical resistance and enhancing their conductivity and antistatic behavior. The
most commonly used materials for nano-scaled filling materials are carbon na-
nofibers and carbon black nanoparticles with high chemical resistance and elect-
rical conductivity. Carbon nanofibers increase the tensile strength of composite
fibers and carbon black nanoparticles increase abrasion resistance and durability.
In addition, composite fibers reinforced with clay nanoparticles that have electri-
cal, thermal, chemical resistance and ultraviolet blocking properties exhibit fla-
me retardant, anti-ultraviolet and abrasion resistance properties (OECD, 2004).

In recent years, one of the important developments in the textile industry is self-
cleaning fabrics. A group of scientists found that when a textile product coated
with copper and silver-based nanoparticles, it became self-cleaning as a result of
being exposed to sunlight or any other form of light (Anderson et al., 2016).

Thin, flexible and light filaments that can generate and store electricity
from the sun and can be used as textiles.
(This image is published on http://www.nanowerk.com/nanotechnology-news/newsid=45064.php and
retrieved from Google Images.)

Another important development in textile is the thin, flexible and light filaments
of copper strips that can be woven as textile and can generate and store electri-
city from sunlight. These filaments, developed through nanotechnology, have
solar cells on one side and energy storing plates on the other side. In the future,
our mobile phones will be able to be recharged with the clothes made from fab-
~ 40 ~
rics woven with these filaments. Maybe we will get to monitor our heart beat,
body temperature and blood sugar regularly with our clothes (Li et al., 2016).

Uniforms produced with nanotechnology will provide convenience for soldiers.

(This image is published on http://www.fibre2fashion.com/industry-article/3046/military-
uniform?page=6 and retrieved from Google Images.)

These developments in the textile sector have provided positive contributions to

the defense industry and will continue to do so. In addition to superior protection
capabilities of intelligent uniforms and intelligent materials being developed by
nanotechnology, the fact that they have much more durability, longevity, lig-
htweight and resistance than conventional materials will increase their use in
military. In the future, the uniforms will gain new dimensions with flexible and
washable nanosensors integrated into the fabrics, such as generating energy,
sensing the body temperature and warning the soldier to allow the necessary
intervention to be performed, and detecting chemical and biological agents. In
addition, widespread use of all-seasons, durable, light and long-lasting clothes,
boots etc., will also contribute to the country's economy in financial terms (Ba-
yındır, 2017).

~ 41 ~
1.3.6 Food Industry and Nanotechnology

Nanotechnology applications in food industry are fairly new. The capability to

use nanotechnology is expected to allow food companies to design and manufac-
ture cheaper, safer, and more durable and more nutritious products. It is also
projected that food companies will use less water and chemicals in the prepara-
tion and production of these foods. A food company has placed nanosensors that
warn the user in food packaging. When the food inside the package is contami-
nated or started to degenerate, the nanosensor changes color and this warns the
consumer. In addition, scientists have developed a portable nanosensor that de-
tects pathogens and toxins found in food. This way it will be possible to control
the food during farm, slaughterhouse, transport or packaging processes, and this
will increase the food safety.

Packages produced with nanotechnology will reduce food waste.

(This image is published on
http://m.meatpoultry.com/articles/news_home/Business/2017/06/Nanotechnology_offers_benefits.aspx?ID={
4D25222A-B878-4896-8BD4-79828A445D81 and retrieved from Google Images.)

Some food companies have produced plastics containing clay-based nanopartic-

les. These nanoparticles in the plastics prevent oxygen, carbon dioxide, and
damp, and this allows food and meat to remain fresh (Mongillo, 2007).In addi-
tion, scientists have developed clay nanotubes that will protect people from food
poisoning by inhibiting rotting and bacterial growth. Normally the permeability
of the packages allows water vapor and oxygen circulation, causing ethylene
accumulation around the food, and this accelerates the degradation and decay of
food. Polyethylene films with hollow clay nanotubes are the most common plas-

~ 42 ~
tic compounds. It is shown that the nanotubes contained in these polyethylene
films inhibit the formation of ethylene gas around the food by preventing water
vapor and oxygen intake, and it is determined that foods are protected for a lon-
ger period (Lavars, 2017).

There are nanotechnology applications on functional foods that can respond

to the needs of the body.
(This image is published on https://www.linkedin.com/pulse/nanotechnology-food-satisha-
naraharimurthy and retrieved from Google Images.)

In addition to these applications, nanotechnology also has effective applications

on the development of nutritious and functional foods that can respond to the
needs of the body and effectively deliver nutrients to the body. Scientists are
currently trying to produce on-demand foods that are stand still in the body and
get activated when needed and have nanocapsules embedded in it. Another deve-
lopment in the food processing is nanoparticles that increase the absorption of
nutrients (Mongillo, 2007).In the food industry, new nanotechnology applicati-
ons are emerging every day.

~ 43 ~
Summary

The applications of nanotechnology, the most important technological development

of the 21st century, start from science fields such as chemistry, physics and biology
and extend to different fields from from health, engineering, food and electronic
applications. Nanotechnology is an emerging technology and applications are
increasing day by day. Materials at the nano scale are lighter, more durable and
programmable materials, and they require less material use in manufacturing and
less energy consumption at the production stage. One of the best examples of this
application is the production of nano-scale electrical circuit components. The
circuit components in the nanometer range are produced with less energy consump-
tion, and the computers in which these circuit components are used will be smaller,
faster and with greater capacity. Nanotechnology applications will also contribute
to the sustainable environment. Hydrogen-powered automobiles will consume less
fuel and will cause less environment pollution, thus lead to eco-friendly fuel con-
sumption. In addition clean water can also be obtained by using nanoparticles that
can clean up such as water sediments, chemical wastes, charged particles, bacteria
and other pathogens like viruses. It will also be possible to prevent food waste
through packaging produced by nanotechnology. Another important application of
nanotechnology is stain-resistant, non-shrinking, liquid spill resistant and self-
cleaning fabrics. Today, nanotechnology is frequently used in medicine. Nanoscale
materials and nanoelectronic biosensors are used for a variety of purposes such as
diagnosing, monitoring, treating and preventing diseases. Every day, a new appli-
cation of nanotechnology that makes life easier emerges and the number of such
applications will continue to increase.

~ 44 ~
References

Adnan, A. (2010). Application of Nanotechnology in Medicine. Biotech Articles,

https://www.biotecharticles.com/Nanotechnology-Article/Application-of-
Nanotechnology-in-Medicine-216.html
Anderson, S.R., Mohammadtaheri, M., Kumar, D., O’Mullane, A.P., Field, M.F.,
Ramanathan, R. ve Bansal, V. (2016). Robust Nanostructured Silver and Copper
Fabrics with Localized Surface Plasmon Resonance Property for Effective Visible
Light Induced Reductive Catalysis. Advanced Materials Interfaces, 3(6), 1-39.
DOI: 10.1002/admi.201500632
Bayındır, M. (2007). Nanoteknoloji Hayatımızda. Bilim ve Ütopya, 152, 12-18.
Li, C., Islam, Md.M., Moore, J., Sleppy, J., Morrison, C., Konstantinov, K., Dou,
S.X., Renduchintala, C. ve Thomas, J. (2016). Wearable energy-smart ribbons for
synchronous energy harvest and storage. Nature Communications, 7: 13319. DOI:
10.1038/ncomms13319
Desai, S.B., Madhvapathy, S.R., Sachid, A.B., Llinas, J.P., Wang, Q., Ahn, G.H.,
Pitner, G., Kim, M.J., Bokor, J., Hu, C., Wong, H.S.P ve Javey, A. (2016). MoS2
transistors with 1-nanometer gate lengths. Science, 354 (6308), 99-102
DOI:10.1126/science.aah4698
Lavars, N. (2017, August 22). Clay-nanotube film keeps foods fresher for longer.
http://newatlas.com/clay-nanotube-film-food/51003/
Lines M.G. (2008). Nanomaterials for Practical Functional Uses, Journal of Alloys
and Compounds, 449, 242-245.
Luo, M., Wang, H., Wang, Z., Cai, H., Lu, Z., Li, Y., Du, M., Huang, G., Wang,
C., Chen, X., Porembka, M.R., Lea, J., Frankel, A.E., Fu, Y.X., Chen, Z.J. ve Gao,
J. (2017). A STING-Activating Nanovaccine for Cancer Immunotherapy, Nature
Nanotechnology, 12, 648–654 (2017) DOI:10.1038/nnano.2017.52
Mongillo, J. F. Nanotechnology 101. Westport: Greenwood Publishing Group;
2007.
Thai, M.L, Chandran, G.T., Dutta, R.K., Li, X. Penner. R.M. (2016). 100k Cycles
and Beyond: Extraordinary Cycle Stability for MnO2Nanowires Imparted by a Gel
Electrolyte. ACS Energy Letters, 1(1), 57-63 DOI: 10.1021/acsenergylett.6b00029

~ 45 ~
Nikalje, A.P. (2015). Nanotechnology and its Applications in Medicine, Medicinal
Chemistry, 5(2), 81-89. DOI: 10.4172/2161-0444.1000247
OECD, (2004). Nanotechnology: Emerging safety issues? ENV/JM (2004)32,
quoted in Small Sizes That Matter: Opportunities and Risks of Nanotechnologies.
Allianz Report in co-operation with the OECD International Futures Programme.
http://www.oecd.org/dataoecd/32/1/44108334.pdf
Ramsden J. (2011). Nanotechnology: An INTRODUCTION, (ISBN: 978-0-08-
096447-8) Elsevier, 2011.
Verbruggen, S.W., Van Hal, M., Bosserez, T., Rongé, J., Hauchecorne, B., Mar-
tens, J.A. ve Lenaerts, S. (2017). Inside Back Cover: Harvesting Hydrogen Gas
from Air Pollutants with an Unbiased Gas Phase Photoelectrochemical Cell
(ChemSusChem 7/2017). ChemSusChem, 10 (7): 1640.DOI: 1002/cssc.201700485
Servick, K. (2012, November 11). Stanford’s touch-sensitive plastic skin heals
itself. http://news.stanford.edu/news/2012/november/healing-plastic-skin-
111112.html

~ 46 ~
1.4 NANOMETROLOGY
Meltem BALABAN
mltm.blbn@gmail.com
PAMUKKALE UNIVERSITY

INTRODUCTION
Metrology is defined as "the science of measurement, embracing both experi-
mental and theoretical determinations at any level of uncertainty in any field of
science and technology" by the International Bureau of Weights and Measures
(BIPM).1

Nanometrology is a part of metrology and it deals with measurements at the

nanoscale. ISO (International Organization for Standardization) definition of the
term nanoscale2 is:
“Size range from approximately 1 nm to 100 nm”, nm(nanometer) being the unit
of length at nanoscale.

Nanotechnology operates at nanoscale. At nanoscale, size is important due to

both miniaturization of technology and changing properties of materials. For
example, at nanoscale metals become harder, ceramics become softer, chemical
resistance increases, weight is reduced, new electrical and biological properties
occur. Laws of physics change at nanoscale, too.

Nanometrology is actually the “science” of nanoscale level measurement, taking

into account the definition of metrology above. It relies on both experimental
and theoretical studies concerned with nanoscale domain measurement. Studying
matter at the level of atoms and molecules, which are structures sized as bil-
lionths of a meter (nanometers) or less, requires nanometrology.

Table 1.4.1 shows SI base quantities and their respective units of measurement.

Keywords: Metrology, Nanometrology, Nano Scale, BIPM (Bureau Internatio-

nal des Poids et Mesures)

~ 47 ~
Table 1.4.1 SI base quantities and respective units of measurement
Base Quantity Name and Symbol of SI Unit of Measurement
Length Meter(m)
Mass Kilogram(kg)
Time, Duration Second(s)
Electric current Ampere(A)
Thermodynamic Temperature Kelvin(K)
Amount of substance Mole(mol)
Luminious Intensity Candela(cd)

SI prefixes, referring to powers of 10, are shown in Table 1.4.2.

Table 1.4.2 SI prefixes expressed in powers of 10

Factor Name Symbol Factor Name Symbol
101 deka Da 10-1 deci d
102 hekto H 10-2 centi c
103 kilo K 10-3 milli m
106 mega M 10-6 micro µ
109 giga G 10-9 nano n
1012 tera T 10-12 pico p
1015 peta P 10-15 femto f
1018 exa E 10-18 atto a
1021 zetta Z 10-21 zepto z
1024 yotta Y 10-24 yocto y

1.4.1 The Nanometer (nm)

The nano prefix comes from a Greek word nanos, and it means dwarf. As stated
in other parts of this book, the nanometer(nm), the unit of length at nanoscale, is
equivalent to 10-9 meters(m). The prefix "nano" means one-billionth, or 10-9 in
the International System of Units (abbreviated SI from French: Le Système In-
ternational d'Unités). Since the prefix "nano" means one-billionth, one nanome-
ter is one-billionth of a meter.

~ 48 ~
3 atoms which are lined up are approximately 1 nm long. A single human hair is
about 80,000 nanometer (nm) wide, a red blood cell is approximately 7,000 nm
wide, a DNA molecule 2-2.5 nm or a water molecule is 0.24 nm. The diameter
of an atom is 0.1-0.5 nm. The wavelength range of visible light is 400-700 nm.
The single-layer(one-atom) thickness of graphene is 0.345 nm. The hydrogen
atom is about 0.1 nm. A virus may be about 100 nm.

Figure 1.4.1 shows some natural and manmade things’ dimension measurements
in nanometers and the relative scaling of the micro-sized and the nano-sized

matters:

Figure 1.4.1 The Scale of Things - Nanometers and More.

(Source: Office of Science, U.S. Department of Energy)

1.4.2 The Nanogram (ng)

The nanogram is the unit of mass at nanoscale. It is equivalent to 10-9 grams(g).

The number of atoms in 1 ng of an element can be calculated by:

~ 49 ~
 6,022 10
10

6,022x1023 in the above formula is Avogadro’s number*. Table 4.3 shows the
number of atoms in 1 ng of some well-known elements. Avogadro sayısıdır. Tab-
lo 1.4.3’te bazı elementlerin 1 ng’ındaki atom sayısı gösterilmiştir.

Table1.4.3 Number of atoms in 1 ng of some elements

Element Molar Mass No. of atoms in 1 ng
(gr/mol)
Hydrogen 1,0079 597.479.908.721.103,00
Helium 4,0026 150.452.206.066.057,00
Carbon 12,0107 50.138.626.391.467,60
Oxygen 15,9994 37.638.911.459.179,70
Calcium 40,0780 15.025.699.885.223,80
Iron 55,8500 10.782.452.999.104,70
Copper 63,5460 9.476.599.628.615,49
Silver 107,8700 5.582.645.777.324,56
Gold 196,9700 3.057.318.373.356,35
Lead 207,1900 2.906.510.931.994,79
Mercury 200,5900 3.002.143.676.155,34

As can be seen from the table above, even a very small quantity like 1 ng of an
element has trillions of atoms in it.

Some of the instruments used for nanoscale measurement are listed below:
• Scanning Electron Microscopes(SEM),
• Transmission Electron Microscopes(TEM),
• Field Ion Microscopes(FIM),
• Scanning Tunneling Microscopes(STM),
• Atomic Force Microscopes(AFM).

All of the above instruments are used for seeing at nanoscale, so that nanometric
measurements can be accomplished.

~ 50 ~
1.4.3 Current Nanoscale Measurement Studıes
Measurements on Thın Fılms
A thin film is a layer of material. Its thickness ranges from fractions of a nano-
meter (monolayer) to several micrometers. The controlled synthesis of materials
as thin films (a process referred to as deposition) is a fundamental step in many
applications. The characterisation of these films and coatings is an important
branch of nanometrology, with a large variety of measurement problems and
tasks. Sample applications of thin films are:
• semiconductors and dielectrics,
• optical components,
• wear resistant coatings, and
• solar cells.

Typical nanoscale measurement requirements regarding thin films are listed

below:
• Thickness and density of the thin film,
• Morphology of the thin film outer surface,
• The thickness, roughness and density of the individual sublayers for
multilayer films,
• Chemical compositions of the individual layers,
• Uniformity of the individual layers,
• Surface quality and material of the substrate,
• Functional properties of the film (e.g., adhesion strength, hardness, fric-
tion coefficient, wear resistance).

A universal technique for thickness measurements at the nanoscale does not

exist. Every measurement task requires a dedicated analysis to identify and se-
lect the most appropriate measurement method adjusted to the specific problem.

Measurements on Structured Surfaces

Samples with structured surface features are classified as being at nanoscale if
the smallest feature size, the critical dimension, is less than 100 nm. Such struc-
tures are nowadays part of many industrial devices and applications including:

• Semiconductors and integrated circuits,

• Micro-electro-mechanical systems,
~ 51 ~
 • Biomedical devices, and
• Optical devices.

Typical parameters to be measured within this field are height, width, angle,
pitch (of periodic structures) and diameter (of e.g., particles).

The measurement quantities dealt with in this section are dimensional. The sizes
of the structures or features define the physical behaviour of the whole system –
even the material properties may change, if the structures are smaller than a cer-
tain limit.

Measurements on Engıneered Nanopartıcles

Nanoparticles are ultra-small particles that have one dimension less than or equal
to 100 nanometers. The properties of many conventional materials change when
formed from nanoparticles. This is typically because nanoparticles have a greater
surface area per weight than larger particles which causes them to be more reac-
tive to some other molecules.

Nanoparticles engineered for shape, size, and surface properties possess special
functionalities including catalytic behavior, improved strength, enhanced ther-
mal and electrical conductivity, and controlled release of host molecules. These
advanced properties make engineered nanoparticles usable in applications in
biomedicine, nanoenergetic materials, and functional nanocomposites.

Nanoparticle-sizing is an important area of study in nanometrology. It’s neces-

sary to measure how big the particles are. Counting the number of particles in a
specific substrate and through the use of an Equivalent Diameter (the diameter
of a perfectly spherical particle which would create the same fluctuation of scat-
tered light intensity, sedimentation time responses, etc.), and finding average
sizing values is a typical measurement approach of metrology for engineered
nanoparticles.

Measurements on Nanobiotechnology
At nanoscale, proteins take the specific shapes necessary to conduct their functi-
ons. It is also the scale that holds the width of DNA molecules and viruses, and
the thickness of the membrane forming the wall of cells. Nanotechnology and

~ 52 ~
biotechnology are closely related, in consequence of these facts. Some applicati-
ons of nanobiotechnology are
 magnetic nanoparticles used to destroy cancer cells,
 surface modification and coatings at the nanoscale to tailor biological
responses to materials used in e.g., implants
 pharmaceuticals where the nanoscale structure and chemical composi-
tion are tailored for efficient delivery of the drug to its target
 better food packaging and storage materials, prolonging the shelf life of
fresh food.

The metrology field is focused on physical measurements (e.g., mass, time,

length). A particular issue is the measurements in biology and medicine that are
dealing with amount of substance. An example is the amount of nanoparticles
binded to Magnetic biosensors for in-vitro diagnostics. Another example is the
surface roughness on the nanometre scale which plays an important role for the
tribological aspects (friction, lubrication and wear) of medical implants. Nanobi-
otechnology deals with coatings and thin films, structured surfaces, and partic-
les, and therefore dimensional analysis methods mentioned in the previous secti-
ons are relevant for nanobiotechnology, too.

Natıonal Metrology Instıtutes

Member institutions of European Association of Metrology Institutes-
EURAMET) are listed in the Table 1.4.4.

Table 1.4.4 Member metrology institutions of EURAMET

Country Organization
Germany Physikalisch-Technische Bundesanstalt (PTB)
United States National Institute of Standards and Technology
(NIST)
Albania General Directorate of Metrology (DPM)
Australia National Measurement Institute(NMIA)
Austria Bundesamt für Eich- und Vermessungswesen
(BEV)
Belgium Quality and Safety Department, Ministry of Eco-
nomic Affairs (SMD)
Bosnia Herzegovina Institute of Metrology of Bosnia and Herzegovina

~ 53 ~
 (IMBIH)
Bulgaria Bulgarian Institute for Metrology (BIM)
Croatia Croatian Metrology Institute (HMI)
Czechoslovakia Czech Metrology Institute/Ceský metrologický
institut (CMI)
China National Institute of Metrology of the People’s
Republic of China (NIM)
Denmark Danish Fundamental Metrology Ltd (DFM)
Estonia Central Office of Metrology (AS METROSERT)
Finland Mittatekniikan Keskus, Centre for Metrology and
Accreditation (MIKES)
France Laboratoire National de Métrologie et d'Essais
(LNE)
India Indian Institute of Legal Metrology
Netherlands VSL Dutch Metrology Institute (VSL)
United Kingdom National Physical Laboratory (NPL)
Spain Centro Español de Metrología (CEM)
Sweden RISE Research Institutes of Sweden AB (RISE)
Switzerland Federal Institute of Metrology (METAS)
Ireland NSAI National Metrology Laboratory (NSAI
NML)
Italy National Institute of Metrological Research
(INRIM)
Japan National Metrology Institute of Japan(NMIJ)
Montenegro Bureau of Metrology (BMM)
Letonia Latvian Metrology Bureau (LATMB)
Lithuania Centre for Physical Sciences and Technology:
Metrology Department (FTMC)
Luxemburg Bureau luxembourgeois de métrologie (ILNAS)
Hungary Government Office of the Capital City Budapest
(BKFH)
Malta Malta Competition and Consumer Affairs Autho-
rity - Standards and Metrology Institute (MCCAA-
SMI)
Macedonia Bureau of Metrology, Ministry of Economy
(BOM)
~ 54 ~
Egypt National Institute of Standards (NIS) of Egypt
Norway Norwegian Metrology Service, Justervesenet (JV)
Poland Central Office of Measures (GUM)
Portugal Instituto Português da Qualidade (IPQ)
Romania National Institute of Metrology (INM)
Serbia Directorate of Measures and Precious Metals
(DMDM)
Slovakia Slovak Institute of Metrology/Slovenský Metrolo-
gický Ústav (SMU)
Slovenia Metrology Institute of the Republic of Slovenia
(MIRS)
Taiwan National Measurement Laboratory(NMI)
Turkey National Metrology Institute/TÜBITAK Ulusal
Metroloji Enstitüsü (UME)

1.4.4 Difficulties Encountered in Nanometrology

Error margin of nanoscale dimensional metrology must be below 1nm. Most
frequently encountered difficulties in nanoscale measurements, currently, are:
 Calibration of sensors whose resolution is under 1nm (which are used,
for example, in measurements of electron and ray beams),
 Contamination that is frequently encountered in characterisation/grading
laboratories,
 Measurement of large amounts of nanomaterials such as carbon nanotu-
bes,
 Sample preparation for nanoscale imaging devices (for which high-
vacuum environment must be provided).

1.4.5 Improvement Areas for Nanometrology

Some of the current improvement areas for nanometrology are given in the fol-
lowing paragraphs. Difficulties in the below-mentioned improvement areas can
be overcome by primarily understanding and studying well the happenings that
occur at the nanoscale:
 Development/calibration of methods for measurement at nanoscale,
 Development/improvement of new instruments for measurement at na-
noscale,
 Establishment/sustainability of an infrastructure guaranteeing reliable
nanoscale measurement results of nanomaterials and nanoproducts (This
challenge is heavily dependent on the appropriate theoretical, experi-

~ 55 ~
 mental, and applicable establishment of the first two challenges mentio-
ned above. In order to realize this challenge, global co-operation of na-
notechnology research and development (R&D) studies and works sho-
uld be motivated, followed through, and sustainably consolidated.),
 Establishment of new reference materials and standards,
 Determination/Measurement of new unique nanoscale characteristics,
 Studies on portability/transferability of micro-scale technologies to na-
noscale,
 Studies related to uncertainties in nanoscale dimensional metrology.

Conclusion
Nanometrology is a part of metrology and it deals with measurements at the
nanoscale. Nanoscale is “Size range from approximately 1 nm to 100 nm”,
nm(nanometer) being the unit of length at nanoscale. Properties of nanomaterials
change at nanoscale. For example, at nanoscale metals become harder, ceramics
become softer, chemical resistance increases, weight is reduced, and new and
unique electrical and biological properties occur. Nanometrology is required for
studying matter at the level of atoms and molecules, which are structures sized
as billionths of a meter (nanometers) or less. Nano scaling studies began app-
roximately 20 years ago. Nanoscale measurements must be correct, sensitive,
and reliable, in order to achieve sound process control in nano-production.
Nanometrology is extensively used in medical products, pharmaceuticals, elect-
ronics, automotive, and forestry sectors. Its usage areas will broaden, covering
unexpected sectors, too, as long as further sectors’ studies are conducted at na-
noscale.

Don’t forget:

“It is not possible to produce

an object that cannot be mea-
sured.”

~ 56 ~
References
1. Bureau International des Poids et Mesures(BIPM)-International Bureau
of Weights and Measures web bağlantısı, https://www.bipm.org
2. National Institute of Standards and Technology (NIST) web site,
https://www.nist.gov/
3. ISO/TS 27687:2008, Nanotechnologies – Terminology and definitions
for nano-objects –nanoparticle, nanofibre and nanoplate, 2008.
4. IEEE Nanotechnology Council (NTC) web bağlantısı,
http://sites.ieee.org/nanotech/
5. Fritz Allhoff, Patrick Lin, and Daniel Moore, What is Nanotechnology
and Why Does it Matter:From Science to Ethics (Malden, MA:Wiley-
Blackwell, 2010), pp. 153-169.
6. Bhat, J. S. A. (2003).Heralding a new future-nanotechnology?Current
Science, 85(2), 147-154
7. Introductory Guide to Nanometrology, Co-Nanomet, Coordination of
Nanometrology in Europe, Edited by Poul-Erik Hansen, Gert Roebben
8. European Nanometrology 2020, Co-Nanomet, Coordination of Nano-
metrology in Europe
9. Vassilios Constantoudis, Kostas Poulios, Manolis Chatzigeorgiou, Ge-
orge Papavieros, Computational nanometrology of nanostructures: the
challenge of spatial complexity, Conference Paper, 18th International
Congress of Metrology, January 2017
10. http://www.sme.org

~ 57 ~
1.5 IMPACT of NANOTECHNOLOGY
Dr. Gratiela Dana BOCA
bocagratiela@yahoo.com
UNIVERSITATEA TEHNICA DIN CLUJ-NAPOCA

INTRODUCTION
Nanotechnologies represent engineering on a very small scale. They can be app-
lied in many areas, such as: health and medicine, information and communica-
tion technology and energy and the environment. Nanotechnologies are currently
considered "emerging technologies" that can revolutionize a large number of
application domains. Nanotechnologies can have some revolutionary implicati-
ons for our society in terms of applications or tools that can be accomplished.
Nanotechnology is impacting businesses and will offer new and improved pro-
ducts and processes and will allow companies to innovate and enter with new
generation products on a new global market.

1.5.1 The impact of nanotechnology

As a preamble to the nanotechnology impact the diagram below ( Figure 1.5.1)

illustrating the complexity domain of nanotechnology, technologies and areas of
application.

EDUCATION TECHNOLOGICAL
TRANSFER
SOCIETY

APPLICATION OF NANOTECHNOLGY

HEALTH IT&C ENERGY TRANSPORT

- MEDICINE
- FARMACY ENVIRONMENT SECURITY

Figure 1.5.1. Nanotechnology impact

~ 58 ~
Nano Impact aims to play an important role in disseminating knowledge about
nanomaterials in human and environmental systems. It focuses on four main
areas:

Human nanotoxicology – including the interactions between nanomaterials and

biological systems (nano-bio interactions) at the cellular and organism level,
mechanisms of disease development and in vitro and in vivo toxicity screening
strategies

Nano-eco toxicology – nano-bio interactions and effects on organism and

ecosystem health

Exposure – release of nanomaterials throughout the life cycles of products and

applications, the fate and behavior of nanomaterials in a variety of settings and
the development and application of analytical methods to quantify and
characterize the nanomaterials in environmental and biological media

Risk and life cycle assessment – human and environmental risk assessment,
and development of life cycle assessment methods and use of life cycle
perspectives.

The risk posed by nanomaterials is poorly understood because of a lack of

detailed data, the novelty of the area and the potential novel behaviors of
nanomaterials. But they are important emerging contaminants, so to protect
health and ensure the long-term sustainability of the technology, these risks need
to be understood, quantified and reduced.

Nanotechnology becamme a daily ineed in the future with positive impact in

our life. The impact of nanotechnolgy can be identify in different fields from
our life and economical sectors. The benefits and applications are presented in
Table
1.5.1.

~ 59 ~
 Table 1.5.1. Nanotechnology Applications
Applications and
Benefits
Uses
cntrolled manufacturing
Advanced faster electronics, processes, economical and
new material high output with low cost.
Manufacturing
development

CO2 reduction, lighter mate-

nanocomposites, rials, move to less fuel con-
advanced sensors, sumption cost savings, imp-
Aerospace faster electronics for roved functionality of mate-
data processing rials, minimising risk, flexi-
bility and new systems
nanoparticles for higher crop yields, reduction
removing contamina- in the use of pesticides and
Agriculture tion, moisture sen- improved water manage-
sors, detection of ment
pathogens
lubricant / hydraulic
CO2 reduction, lighter mate-
additives, nanopartic-
Automotive les in catalytic con- rials, move to less fuel con-
verters, fuel cells, sumption
hydrogen storage
Chemical reduction of waste and CO2
fuel cells, nanopartic-
Industries les as catalysts reduction

Construction thermal insulation, lower energy needs, CO2

Energy storage reduction
devices
clear sunscreens, UV protection, enhanced
Cosmetics beauty care products, delivery of medicated skin
cosmeceuticals, nut- products
raceuticals
Creative changing effects, bioinspired product deve-
advanced display lopment
Industries
systems
advanced display
technologies with providing faster, smaller and
Electronics conductive nanoma- enhanced hand held devices
terials, quantum
computing, data

~ 60 ~
 storage, printable and
flexible electronics,
magnetic
nanoparticles for data
storage
Air and water filtra-
tion, waste and water
treatment, hazour-
Environment dous materials dispo- CO2 reduction and clean-up
sal, in-building
Environmental
systems, remediation
improved barrier
properties and heat- tracking, quality monitoring
Food
resistance, anti- and anti-counterfeiting,
and microbial and anti- provides enhanced informa-
fungal packaging, tion on product and is envi-
drink packing smart
ronmentally friendlly
sensing, biodegradab-
le packaging
Nanoparticulate drug
delivery, Nanosilver better patient care and un-
Healthcare dressings, derstanding of biological
processes
Fluorescent biologi-
cal labels
energy storage devi- environmentally friendly
Low Carbon ces
with the goal to reduce CO2
Technologies
production

anti-fouling coatings, sronger and lightweight

Materials nanotube polymers, materials, functionalised
printed electronics materials

employee monitoring, ad-

vancing imaging,
Safety PPE equipment,
better testing,
stronger materials
new characterisation met-
hods

~ 61 ~
 stain-resistant fabrics,
self cleaning and
anti-bacterial
hospital garments, emer-
coatings, protection
and detection, gency clothing and PPE,
Textiles
healthcare, new wea- fashion on demand
rable textiles
incorporating solar
cells, sensors and self
cleaning properties
Source: Adaptation after http://workshop-nano.wikispaces.com/Nano

1.5.2 How can nanotechnologies change our lives in the fu-

ture?

Nanotechnologies have played an important role in producing smaller, more

efficient and multifunctional devices.
In the future, our lives could change through many technological innovations
such as:
● Introducing medications that can be activated and controlled from the outside
of the human body into the circulatory system;
● They could collect data and send them to the physician to modify treatment
(teranostics);
● Nano-sized devices for transporting drugs and targeting cancer cells;
● Tattoos on the skin to monitor salt levels and other metabolites and to alert
athletes or diabetics;
● Footwear or clothing with sensors to collect data during training;
● Integrated energy collector systems (in textiles, footwear, etc.) to collect solar
and mechanical energy to charge electronic devices;
● Flexible and transparent solar panels integrated into windows, ceramic tiles,
etc., with high efficiency conversion of solar energy;
● Surfaces and textiles to remove nitrogen oxides and other smog gases from
the urban atmosphere.
● Smart food packaging with sensors to detect the way it is used to transport
the product, for detection of contamination, which are:
 fitted with tracking system;
 communication to warn;
 manufacturer and trader.
~ 62 ~
1.5.3 The economic and social impact of nanotechnology

Nanotechnology has a large number and variety of applications in many diffe-

rent sectors. Potentially, nanotechnology could lead to a more efficient and sus-
tainable use of resources and maybe have a beneficial impact for the vast majo-
rity of people around the world.
However, as all the technologies that exist, it could have a negative impact on
society in what concerns aspects of:
1. confidentiality;
2. division of society;
3. communication risks.

Confidentiality: The potential for abuse is present and the limits of the type of
information that can be captured must be clearly defined by society, through the
legislative system.

Divide society: As with previous technologies such as IT, nanotechnology could

has the effect of widening the gap between the rich and the poor, or more preci-
sely the developed world in developing. Many of the precious metals and mine-
rals that new nano materials are going to replace, and thus reduce dependence on
non-renewable, are exploited in developing countries. Loss of these incomes,
without a strategy of replacing them, will have a negative impact on the eco-
nomy and development of these countries. To respond to these potential effects,
strategies in nanotechnology must be approached differently in different count-
ries, depending on the needs of those countries.

Communication: Accepting new advances in nanotechnology and, in particular,

its effects on the scale broad, it can only be achieved through communication
and dialogue between scientists, industry, governments and society in general.
This has often been ignored and led to misinformation and misunderstanding on
the risks and benefits associated with new advances. The need for communica-
tion was recognized by governments, research and industry funding agencies and
these institutions have now initiatives to actively exploit the dialogue with scien-
tists and citizens interested through.

~ 63 ~
1.5.4 Nanotechnology Future today
The 21st century It is also called manufacturing technology. It is a multidiscipli-
nary field that combines the great scientific achievements in physics, chemistry,
biology, mathematics and materials science in the construction of atoms and
nanoscale molecules of materials with artificial intelligence. Nanotechnology is
a collective term for technological developments at nanoscale. The nanometric
structures are not only very small, reaching even to the atomic scale, but they
possess some totally unique and unexpected properties, compared to the same
substance taken at the macroscopic level.

Time
2025 Bionic
.
Photo- lentil
. invisible
voltaic cloths
.
cells
2016
.
3D
2000
Television
WHAT
IS
Nanotechnology impact
NEXT?

Nano impact evolution between 2011-2015:

• Nanomaterials to replace current materials, for example polymers;
• Nanoparticle-based target drugs become a standard tool (for therapeutic purpo-
ses, increasing performance);
• Intelligent probes (which illuminate when they reach their target) are basically
used for in-vivo diagnostics;
• Nano tools (such as optical tweezers) are used inside cells while retaining cell
integrity and activity;

~ 64 ~
• Nanoprobes are widely used for different applications in diverse sectors, inclu-
ding households;
• Integrated DNA-based circuits for the purpose of specific diagnostics in the
current practice of hospitals;
• Biochips in vitro tests replace animal tests for different applications (eg in
pharmacy, cosmetics);
• Biosensors for single molecule detection based on nano devices are commerci-
ally available;
• Auto assembly is widely implemented as a technique for developing materials
and devices;
• Chips based on bimolecular as active elements are manufactured on a commer-
cial scale;
• Nanoelectronic chips are manufactured on a commercial scale using DNA or
peptides.

Nano impact evolution between 2016-2020:

• The fundamental processes of the cell cycle are widely known;
• Human organs can be developed in vitro due to nano bio technological advan-
ces;
• Bio molecular engines are used in nano and Microsystems;
• The general public uses biochips for personal purposes;
• Artificial systems have self-reputation skills.

Nano impact evolution between 2020-2025:

Nano machines for therapy and diagnosis inside the body are commonly used;
the researchers are trying to improve their vision. It's not about correcting vision
defects, but about a lens that you can see. For example, you are in an unknown
city and need to get to a destination quickly. In this case, the contact lens will
turn on, and over the landscape you see as a rule will show all kinds of indicators
that will allow you to focus. The difference between a regular contact lens and a
contact lens with display is that the latter have electrical connections and LED
array.

~ 65 ~
 Inteligent lens
(This is a featured Picture on Google images,https://gadgetreport.ro/gadget/tehnologie-sf-devine-realitate-
cum-arata-lentilele-de-contact-inteligente-video/)

1.5.6 Nano impact today

a) Nanotubes
The most difficult problem faced by scientists when they proposed building a
space elevator was linked to the material that would be most appropriate to meet
such a high demand. A Japanese researcher discovered in 1991 a novel combi-
nation of carbon, which he called the 'tube nano' and which proved to be breath-
taking. The space elevator will be designed to send space to the satellites. Ulti-
mately, it would make it a tourist attraction, offering the curious to travel in spa-
ce.

Space elevator
(This is a featured Picture on Google images)

~ 66 ~
 b) Nokia Morph The Phone To Be Transformed
Thanks to nanotechnology, which tends to generate seemingly magical functio-
nality in common devices, Nokia has succeeded in bringing together in a fasci-
nating device a series of technologies that will be available for mobile
equipment over the next decade. Baptized Morph, the prototype created by No-
kia can change its shape in a variety of ways, from bracelet to regular phone or
office desk. It is transparent, has a surface capable of cleaning itself and the as-
sembly can detect and even use power sources nearby. Exposed at the Modern
Art Museum in New York, Morph is a concept that aims to demonstrate the
extreme flexibility of mobile devices that our near future holds for us.

Nokia Morph
( Picture taken from Google http://www.dreambloggers.com/5068/nokia-morph-nano-technology-phone-
future-of-mobile-phones-features-specs/)

c) Nano Robots Doctors in 30 Years

How would we be able to swallow a tiny doctor who could travel through blood
to any sick cell of his body?
The nanodoctor would be good at all: to provide medication, to remove tumors,
to analyze and to "put the shoulder" on the reconstruction of accidentally destro-
yed tissues. Today are very little effective due to precautions. When we make an
antibiotic for killing bacteria, we must make sure that it does not kill our body's
cells.
A nanorobot, able to administer poison only to the bacteria we are targeting,
would greatly simplify things. Diseases can be diagnosed before the person feels
~ 67 ~
the first inconvenience, which would further simplify their treatment. Human
organs that suffer wear damage such as liver, kidneys and brain may be helped
to recover damaged cells.
Nano robots will be able to place cells exactly at the "disaster" site and then,
after they multiply - turning into a tissue identical to the one to be replaced, the
robots will stop the process to avoid the appearance of tumors. So complex we
will have in only 30 years.

Nano robots
(This is a featured Picture on Google images http://www.groupin.pk/blog/nanotechnology-a-daily-need-in-the-
future/)

d) Nano Spaces
The lotus plant is immune to maculation (smear, dirt), there is no dirty lotus. It is
an intelligent light-spreading plant that has a high energy efficiency. Every drip-
ping drip drives dust and dirt after it. The concept were used as a start-up on
auto products. The development of nano -spaces which it can be applied in the
nanotechnological facilities for cars, car service, show-rooms, industrial and
production halls and underground parking.

Lotus effect
(Picture taken from Google https://biomimeticdesign.wordpress.com/2008/08/27/lotus-effect-efecto-lotus/)

~ 68 ~
THE FUTURE IS NANO!

The term “nanotechnology” has been evolved around couple of years. Nano-
technology is actually the technology of building electronic circuits and devices
of size smaller than 100 nanometers. It is shortened to word “Nanotech”. Almost
every industry is using that advanced technology as they produce a large quan-
tity of products at a very cheap price. It has opened a new dimension for compa-
nies and entrepreneurs. It is impacting businesses and keeps on introducing new,
cheap and improved products and processes. Nanotechnology gives a full chance
to companies to innovate and enter new market.
Nanotechnology will affect every aspect of our lives, from the medicines we use,
to the food we consume and the energy supplies we require, the cars we drive,
the buildings we live in, and the clothes we wear. Nanotechnology will helps us
in achieving a better and safer life
If these short-term uses of nanotechnology seem impressive, the long-term capa-
bilities are tedious. NASA's Advanced Concept Institute (ICA) has been specifi-
cally designed to promote visionary research into space technologies that will
take between 10 and 40 years to be frustrated like:
- the use of a large number of molecular microscopic machines to produce any
object by assembling it with an atom;
-have 100 times the tensile strength of steel, but only one-eighth of weight; -they
are 40 times stronger than graphite fibers;
-have a higher conductivity than copper;
-can be both conductors and semiconductors, depending on atomization;
-there are excellent thermal conductors.

~ 69 ~
References

http://nanotechinnove.blogspot.ro/
http://www.groupin.pk/blog/nanotechnology-a-daily-need-in-the-future/
http://www.nanopro.biz/index.php?option=com_content&view=article&id=53&
Itemid=16

~ 70 ~
SECTION 2
PRODUCTION

~ 71 ~
~ 72 ~
2.1 EMULSION

Dr. Arzu YAKAR

ayakar@pau.edu.tr
AFYON KOCATEPE UNIVERSITY

INTRODUCTION
Emulsion methods is one of the liquid-phase nanoparticle preparation tech-
niques. An emulsion is the complete mixture of two liquids. Ordinary emulsions
are instable in terms thermodynamics and the droplets that have average sizes of
0.1 - 1.0 microns grow with the gravitational effect and two phases separate
from each other again. Emulsions have a blurry appearance. However, micro-
emulsions are defined as thermodynamically stable emulsions. Their properties
are time-independent and they are not affected by production steps such as agita-
tion process. Their average drop sizes are smaller than 100 nm. Microemulsions,
contrary to emulsions, appear transparent as they don’t refract the light due to
their extremely small droplet sizes despite the fact that they contain high amo-
unts of water and oil. Their superior properties enabled microemulsion method
to be used widely in nanoparticle production.

2.1.1 Microemulsion

There is a wide variety of methods in nanoparticle synthesis. Microemulsion is

one of the liquid-phase synthesis methods. The emulsion, which is the basis of
the method, is consisted of oil (nonpolar phase) and water (polar phase). These
two phases are immiscible and they separate back into two phases when they are
mixed with an external force. In order these two phases to mix, an energy that
can enable water-oil mixture is required instead of water-water and oil-oil inte-
raction. Intermediate surface tension occurs in the presence of two phases. App-
roximately 3.0-5.0 x 10-2 N force per unit length (m) is required to remove the
intermediate surface tension between water and oil surfaces (Bourrel and
Schechter, 1988). Surfactants consisted of organic molecules that have hydrophi-
lic head and lipophilic tail (Figure 2.1.1) are used to overcome this force. Hyd-
rophilic part of surfactant is consisted of non-ionic or ionic groups. These groups
are bonded to the hydrophobic long-chain hydrocarbons with covalent bonding.

~ 73 ~
 Figure 2.1.1. Surfactants
(The image is published on https://en.wikipedia.org/wiki/Surfactant and retrieved from Google Images.)
Yüzey aktif maddeler

There are four types of surfactants; anionic (eg; dioctyl sodium sulfosuccinate
(DOSS), commercial name PENTEX® 99), cationic (eg; cetyl trimethyl amo-
nium bromide, CATB), non-ionic (eg; sorbitan alkyl esters, commercial name
Span®) and dual groups with both anion and cation group (eg; amonium sulfo-
betaine). Therefore, emulsions are consisted of at least three components; oil,
water and surfactant.

In the presence of enough surfactants in the medium, surfactant decreases the

intermediate surface tension between water and oil molecule and creates an in-
termediate surface between water and oil (Gelbart and Benshau, 1996). If a very
small amount of suitable surfactant is added into water-oil medium and agitated,
a liquid medium called continuous phase, in which emulsion is formed, where
droplets of one phase is dispersed in the other phase that has a surface covered
with surfactant (Figure 2.1.2). These emulsions have blurry appearances and
droplets inside are approximately 0.1-1.0 micron in size.
~ 74 ~
 Figure 2.1.2. Emulsion formation
(This image is published onhttp://www.physics.emory.edu/faculty/weeks//lab/emulsion/ and retrieved
from Google Images.)

The most important part of emulsion formation process is to decide which phase
will be the continuous phase. The surfactant to be selected will be of great im-
portance for this purpose. If the surfactant is hydrophilic, it will be emulsified
inside continuous water phase with oil droplets. In the contrary case when lipop-
hilic surfactant is used, water droplets will be formed in continuous oil phase
(Bancroft, 1913).

Although emulsions are kinetically stable, they cannot remain stable thermody-
namically for a long time. As the surfactant dissolves in a phase, droplets come
together again. Thus, medium returns to separate water and oil phase (Gelbert
and BenShau, 1996). If a surfactant that has a balanced hydrophilic and lipophi-
lic properties is used at the right concentration, a different oil and water system
is produced. This new system is called microemulsions (Figure 2.1.3) and they
have different properties than emulsions. Droplet sizes of microemulsions vary
between 5 nm and 50 nm. They are stable in terms of kinetics and thermodyna-
mics, and they have low viscosity. Microemulsions are homogeneous macrosco-
pically and heterogeneous microscopically and different structures such as la-
mel, cylinder and sponge-like are observed. In addition, intermediate surface
tension is much lower than 10-6 mN/m.

~ 75 ~
 Figure 2.1.3. Microemulsion drops
(This image is published on http://www.enviroquestgpt.co.uk/content/micro-emulsion.html and retrieved from
Google Images.) Mikroemülsiyon damlaları

2.1.2 Microemulsion Types

Systematic examination and understanding of phase behaviors of emulsions or

mircoemulsion like liquid crystal phases and their related systems carry great
importance. Winsor (1948) had recommended a classification diagram for liquid
formulations that contain oil, water and surfactants. Systems have four different
types based on equilibrium phase (Figure 2.1.4) (Hloucha, 2015; Paroor, 2012).
In Winsor I type oil/water (O/W) microemulsion, the inner phase consisted of oil
droplets that are covered by surfactants are dispersed inside continuous water
phase. As the surfactant dissolves in the water phase, water phase is rich in terms
of surfactant and oil phase is poor in surfactants. In Winsor II type, water/oil
(W/O) microemulsion is consisted of water droplets dispersed in continuous oil
phase, which is known as inverse-micelle. Oil phase is rich in surfactant,
however, water phase is poor. In Winsor III microemulsions, there is excess
water phase at the bottom, excess oil phase at top and there is surfactant dissol-
ved in two continuous phases in the intermediate region that is in balanced
between these two phases. This is the microemulsion type that contains three
different phases; oil/water (O/W), water/oil (W/O) and water+oil+surfactant
(W+O+S). In Winsor IV type microemulsion, it appears like a single phase con-
taining water+oil+surfactant since the phase borders are not clear in macroscopic
level.

~ 76 ~
Figure 2.1.4. Winsor type microemulsion Type I: O/(W+S), Type II: W/(O+S),
Type III: O/(W+O+S)/W, Type IV: W+O+S
(This image is published on https//fr.wikipedia.org/wiki/Type_Winsor and retrieved from Google Images.)

Fish diagram is used to determine the type of microemulsion (Figure 2.1.5). In

this graphic, total surfactant concentration is on the x-axis, and settings parame-
ter (such as temperature, surfactant mixture or salt concentration) is on the y-axis
and Winsor type systems are attained over the graphic.

Figure 2.1.5. Fish phase diagram used for microemulsions

~ 77 ~
In case of high total surfactant concentrations and narrow setting parameter va-
lues, Winsor IV type single phase emulsions are formed. This region is called
tail region. In conditions lower than the lowest surfactant concentration, Winsor
type I, II and III emulsions are obtain that has 2 and 3 phases.

Generally, microemulsions are consisted of lipophilic phase, hydrophilic phase,

surfactant and second surfactant (Zielińska-Jurek, 2012). In order for micro-
emulsions to have low intermediate surface tension and good solubility, they
must be well-formulized. For a good formulation, parameters of oil/surfactant
and surfactant/second surfactant ratio, surfactant, second surfactant, aqeous and
oil phase concentration and nature, pH, temperature and polarity hydrophili-
city/lipophilicity must be determined (Malik, 2012). In addition to these factors,
suitability of surfactant and second surfactant is very important for the micro-
emulsion wanted to be obtained. Triple phase diagrams are used to study the
phase behaviors of microemulsions that contain water, oil and surfactant at cons-
tant pressure and temperature (Figure 2.1.6) (Malik, 2012; Paroor, 2012). Each
corner of the phase diagram corresponds to the 100% concentration of its com-
ponent. When four components are used, one corner on the pseudo-triple phase
shows a double mixture of surfactant+second surfactant.

Figure 2.1.6. Microemulsion three-phase diagram

(This image is published on http://www.pharmatutor.org/articles/formulation-characterization-of-
microemulsion-based-gel-antifungal-drug?page=2 and retrieved from Google Images.)

~ 78 ~
Generally, water/oil (W/O) microemulsions are preferred for the attainment of
nanoparticles. Water emulsion in oil (W/O) is obtained by the dispersion of
water inside a hydrocarbon-based continuous phase. In this region, surfactant
produces clusters known as inverse micelle (Malik, 2012). Central nuclei of
these inverse micelles start to separate with the addition of polar or ionic com-
ponent. This way, organic or inorganic materials disperse regularly inside the
oil. These systems are dynamic. Micelles frequently collide in random Brownian
motion. Collisions enable micelle contents to be exchanged and mix the inorga-
nic reagents inside them. This exchange process forms the basis of nanoparticle
synthesis that allows different reagents dissolved in different micelle solutions to
react after agitation. Micelles that provide suitable conditions for controlled nuc-
leation and growth can be defined as nanoreactors. After the growth step, surfac-
tant prevents nanoparticles from clustering (Lopez-Quintela, 2003).

Only a limited number of organic nanoparticles can be prepared by using oil

microemulsions dispersed in continuous water phase, which is also called micro-
emulsion polymerization (Lopez-Quintela, 2003; Malik, 2012; Hloucha, 2015).
This technique could not be further developed due to the difficulties in separa-
tion of phases. Polymeric nanoparticles can be obtained with the use of polyme-
rization reactions in O/W emulsions that enable the dispersion of hydrophobic
nanoparticles with sizes of 10-40 nm inside water. Rapid polymerization is one
of the most important advantages of this method.

Summary
Microemulsions are emulsions that are formed by spontaneous mixture of two
liquid phases under certain conditions. Although they are homogeneous in macro
scale, they are heterogeneous in micro scale. Tension between phases is quite
low. Since the formed droplets are smaller that visible wave length, these micro-
emulsions appear transparent. They are stable in terms of kinetics and ther-
modynamics. A wide variety of nanomaterials can be prepared by using solely
microemulsion method or in conjunction with other methods. Microemulsions
are a unique class of colloidal systems with their high degree of inter-phase dis-
persion, very small sized droplets and ability to control the chemical reaction. In
addition to nanoparticle synthesis, microemulsion method is also used for reco-
very of oil, fuel additive, paint, textile coating, cosmetics and pharmaceutical
areas.

~ 79 ~
References

Bourrel, M. ve Schechter, R. S. (1998). Microemulsions and Related Systems:

Formulation, Solvency, and Physical Properties (Surfactant Science Se-
ries, Vol. 30) Marcel Dekker Inc., New York and Basel, pp. 483.
Hloucha, M. (2015). Microemulsions, Ullmann's Academy, Encyclopedia of
Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Wein-
heim, Germany.
Lo´pez-Quintela, M.A. (2003). Synthesis of nanomaterials in microemulsions:
formation mechanisms and growth control. Current Opinion in Colloid
and Interface Science, 8, 137–144.
Malik, M.A., Wani, M.Y. ve Hashim, M.A. (2012). Microemulsion method: A
novel route to synthesize organic and inorganic nanomaterials. Arabian
Journal of Chemistry, 5, 397–417.
Paroor, H.M. (2012). Microemulsion: Prediction of the Phase diagram with a
modifed Helfrich free energy, Doctor of Philosophy in Natural Sciences,
Max Planck Institute for Polymer Research Mainz, Germany and Johan-
nes Gutenberg University, Mainz, Germany.
Winsor, P.A. (1948). Hydrotropy, solubilisation and related emulsication proces-
ses. Transactions of the Faraday Society, 44, 376-398.
Zielińska-Jurek, A., Reszczyńska, J., Grabowska, E. ve Zaleska, A. (2012). Na-
noparticles Preparation Using Microemulsion Systems, Microemulsions -
An INTRODUCTION to Properties and Applications, Dr. Reza Najjar
(Ed.), ISBN: 978-953-51-0247-2, InTech, Available from:
http://www.intechopen.com/books/microemulsions-an-
INTRODUCTION-to-properties-and- applications/nanoparticles-
preparation-using-microemulsion-systems

~ 80 ~
2.2 PRECIPITATION

Dr. Arzu YAKAR

ayakar@pau.edu.tr
AFYON KOCATEPE UNIVERSITY

INTRODUCTION
Superior magnetic, optical, conductivity and durability properties of nanomateri-
als allow them to be used in many industrial areas. Industry’s interest in these
material also led to a diversity in production methods. There are two main app-
roaches in nanomaterial synthesis; one of them is production by starting from
atom or molecule (bottom-top), another one is breaking large particles into smal-
ler structures (top-bottom). In general, production methods of nanomaterials can
be classified in three: solid phase methods, liquid phase methods and gas phase
methods. Coprecipitation method is widely used in the industry as one of the
liquid phase methods.

2.2.1 Chemical Precipitation

The most critical point of precipitation method is to synthesize the nanomaterial

in situ and to study in the same liquid medium. This prevents physical changes
and the aggregation of small crystals. Synthesis contains the reaction in the
compound substance dissolved in the solution. Additive substance is added into
the main solution before the precipitation reaction. Surfactant is used to preserve
the separation between the formed particles. The resulting nanocrystal is separa-
ted via centrifuge, washed and dried with vacuum (Rajput, 2015).

Chemical precipitation is one of the most suitable liquid phase synthesis met-
hods. Because the starting materials can be mixed in atomic level and they can
synthesize metal-oxide and ceramic nanoparticles that have complete composi-
tion through chemical precipitation method. Figure 2.2.1 shows the basic steps
of chemical precipitation.

~ 81 ~
Figure 2.2.1. Flowchart of chemical precipitation process (Nuraje and Su, 2013;
Cox, 2014; Zhong et al 2012)

First, main solutions consisted of starting materials such as metal oxides (eg.
Li2O3), metal salts (eg. FeCl2, AgNO3) and organimetallic compounds (eg.
Fe(Ac)2) or hydrates of these (eg. FeCl2•6H2O), are prepared by dissolving these
starting materials in a suitable solution (Zhong et al 2012). Widely used soluti-
ons are deionized water, ethanol, methanol and acidic solutions. Then, prepared
solutions are directly mixed or one solution is added onto other one drop by
drop. Although high reaction temperature is not needed, hours of vigorous agita-
tion is required in order for starting materials to react. For many nanomaterials,
this synthesis process is conducted in room temperature or a little bit higher
temperatures. Precipitation of the dissolved substance from the solution can oc-
cur due to the low solubility. Two precipitation processes take place in chemical
precipitation synthesis. In the first process, reaction products precipitate after the
reaction is completed as shown in the below reaction because they have lower
solubility in the solution;

~ 82 ~
MgCl2 (aq) + 2 AgNO3 (aq)  2 AgCl (s)↓ + Mg(NO3)2 (aq)

In the second process, when the reaction products dissolve in the main solution,
a precipitator (insoluble) is added into the solution to precipitate the reaction
products (Zhong et al 2012). Precipitator mixes with the main solution, however,
it does not dissolve the reaction products which cause the precipitation of the
reaction products in the main solution-precipitator mixture. Second process is a
form of coprecipitation, and since the solubility here is depended on pH, precipi-
tation is sensitive towards pH (Zhong et al 2012). Certain pH level forces the
reaction products into precipitation. Generally, metal salts require basic or weak
acidic environments (Macingova and Luptakova, 2012). The popular precipita-
tion agents used, such as NH4OH, NaOH and Na2CO3, for the precipitation are
basic materials. There are no strict rules about the addition time of precipitators
into the system, however, precipitator is recommended to be added drop by drop
in oder for the convenient control of the pH level. Before the separation of the
precipitates, conditioning (maturing) period with waiting time from several ho-
urs to several days is required to obtain cleaner and bulk particles. Precipitates
like metal hydroxides and metal complexes are often separated from the solution
by centrifuge or filtering methods. Precipitates are subject to washout process
several times by using deionized water, pure alcohol or other solvers in order to
attain highly pure nanomaterials and to remove impurities. Precursor compound
powders are obtained after drying for a sufficient amount of time at temperatures
higher than 100°C or by freeze drying. Nanoparticle powders with desired crys-
tal structures are obtained by applying thermal processing methods, such as tem-
pering, sintering and calcination, to precursor compound powders for several
hours at high temperatures (Macingova and Luptakova, 2012; Lateef and Nazi,
2016).

A chemical precipitation method is consisted of three main stages; chemical

reaction, nucleation and crystal growth. Chemical precipitation kinetic is gene-
rally not a controlled process in terms of solid-phase nucleation and growth.
Therefore, solid materials attained through chemical precipitation have larger
particle size distribution and uncontrolled particle morphology due to agglome-
ration. In order to obtain nanoparticles with narrow particle size distribution,
some certain conditions, such as supersaturation, homogeneous concentration

~ 83 ~
distribution across the whole reactor and single growth time for all particles, are
required (Macingova and Luptakova, 2012; Lateef and Nazi, 2016).

Another solution method widely used in the synthesis of multicomponent oxide

ceramics is the “coprecipitation” that produces two or more simultaneous undis-
solved precipitates (Lateef and Nazi, 2016). Precursors used in this method are
generally inorganic salts such as nitrate, chloride and sulphate. A homogeneous
solution is created by dissolving these precursor compounds in water or another
suitable solver medium. These salts are separated from the solution in the forms
of hydroxides, aqueous oxides or oxalates with the use of pH tracking or vapori-
zation process. Crystal growth and agglomeration processes are affected by pa-
rameters like salt concentration, temperature, true pH and pH change rate. After
the precipitation process, solid mass is collected, washed and dried slowly by
heating the solver medium up to boiling point. Washout and drying procedures
applied for coprecipitated hydroxides affect the agglomeration degree in the
final powder. Generally, calcination step is required to the convert hydroxide
into crystal oxides. In majority of double, triple and quadruple systems, a crys-
tallization step, which would be performed via calcination or hydrothermal pro-
cedure in high pressure autoclaves, may be required. Homogeneity of constituent
distribution, relatively low reaction temperature, weak agglomerated particles,
regular particle size and low costs are some of the most important advantages of
the precipitation method. However, coprecipitation reactions are highly sensitive
against environmental conditions. In addition, these reactions are not suitable for
the systems that have amphoteric properties (Lateef and Nazi, 2016).

Summary
To summarize, chemical precipitation is consisted of two steps; chemical synt-
hesis inside a liquid and solid state thermal processing. While first step determi-
nes the chemical composition and pre-crystal structures of the nanomaterials,
second step affects the final crusyal structures and phase morphologies. Chemi-
cal composition is the most fundamental property that affects the performance
and structure of nanomaterials. Therefore, mixing the starting material with a
constant molar ratio during the synthesis process is the most important step.
Generally, precipitated precursor powders are poorly arranged and have poor
crystallinity. In addition, they exhibit large sizes and particle size distribution.
Many chemical reactions, including dehydration, that take place during the

~ 84 ~
thermal processing contribute to the regulation of properties such as crystallinity,
crystal size, size distribution and phase transformation.
References
Cox S.C. (2014). Mimicking Bone - Chemical and Physical Challenges. The
Warwick Research Journal, 2, 82-101.
Lateef A. ve Nazi R. (2016). Science and Applications of Tailored Nanostructu-
res Part 12: Metal Nanocomposites: Synthesis, Characterization and Their
Applications, One Central Press (OCP), 240-256.
Macingova, E. ve Luptakova, A., (2012). Recovery of Metals from Acid Mine
Drainage. Chemical Engineering Transactions, 28, 109-114.
Nuraje, N. ve Su, K. (2013). Perovskite Ferroelectric Nanomaterials. Nanoscale,
5, 8752-8780.
Rajput N., (2015). Methods of Preparation of Nanoparticles, A Review. Interna-
tional Journal of Advances in Engineering & Technology, 7, 1806-1811.
Zhong W.H., Maguire R.G., Dang V.T., Shatkin J.A., Gross G.M. ve Richey
M.C. (2012). Nanoscience and Nanomaterials; Synthesis, Manufacturing
and Industry Impacts, DEStech Publications, Inc., Lancester, Pennsylva-
nia, U.S.A.

~ 85 ~
2.3 SONICATION

Dr. Arzu YAKAR

ayakar@aku.edu.tr
AFYON KOCATEPE UNIVERSITY
INTRODUCTION
Nanomaterials are inevitable parts of human life. New technologies and methods
are constantly being developed for the synthesis of these materials. In addition to
the conventional chemical reactions, emerging new methods can also be used to
control particle sizes and particle size distribution of the nanomaterials used for
energy conversions and biological applications. Ultrasonic synthesis, one of the
synthesis method of nanomaterials, is an emerging technology that has an impor-
tant potential for the production of large scale functional materials.

2.3.1 Sonication

Most of the living creatures use sound waves to communicate. Sound pass thro-
ugh an elastic medium as longitudinal waves in a series of compression and rare-
faction cycles (Figure 2.3.1). This stimulates the medium, such as liquid, to cau-
se replacement parallel to the direction of the wave (Ashokkumar, 2016). Frequ-
ency and acoustic amplitude are the most important properties that characterize
the pressure wave (sound wave).

Figure 2.3.1. Sound wave

(http://www.mediacollege.com/audio/01/sound-waves.html ,
This image is published on https://www.flickr.com/photos/mitopencourseware/3042950125 and retrieved from
Google Images.)
~ 86 ~
Sound waves can be classified in different frequency ranges depending on their
form and purpose. Frequencies lower than 20 Hertz (Hz) are called subsonic
waves. Human ear cannot hear this sound. Sometimes infra-sound (subsonic)
waves can be felt as shock waves like during earthquakes. 20 Hz-20 kHz is the
hearing range of human ear. Frequencies higher than 20 kHz are called ultraso-
und. Based on the applied frequency, ultrasound use can be classified in two
(Kuijpers, 2004);
- Low intensity, high frequency ultrasound (2-500 MHz, 0,1-0,5 W/cm2)
- High intensity, low frequency power ultrasound (20-900 kHz, <10 W/cm2)

First ultrasound type is used for medical diagnosis. This type of ultrasound is not
used for reactions. On the contrary, power ultrasound uses its energy to form
cavitations that contain bubble formation, growth and fluctuation (Kuijpers,
2004).

Generally, mechanical vibrations produced by sound waves are used in many

applications such as quality control of food and other material, medical diagno-
sis, cleaning of small and large equipment, extraction and emulsification in
pharmaceutical field (Ashokkumar, 2016).

Interaction of sound waves with water leads to some events. Especially as the
ultrasound passes through a liquid medium, it strongly interacts with small gas
bubbles present in the liquid. The interaction between gas bubbles and ultraso-
und leads to a phenomenon known as acoustic cavitation (Suslick, 1999).

In comparison to conventional energy sources, ultrasonic effect allows highly

extraordinary reaction conditions otherwise not achievable by other methods,
such as extremely high temperature and pressure in liquids. When liquids are
exposed to ultrasound, compressed acoustic waves with changing amplitudes
create bubbles and these bubbles vibrate. These bubbles are formed in the “nega-
tive” pressure period of rarefaction phase of the sound wave (Figure 2.3.2). Vib-
rating bubbles can effectively accumulate ultrasonic energy by growing up to a
certain size. Under correct conditions, this bubble grows and then collapses. The
intense energy accumulated inside the bubble (with heating and cooling ratio
>1010 K/s) is then rapidly released with the collapse. Exploding collapse of the
bubbles can cause extreme temperatures (5000 K) and pressures (1000 bar).
These hot spots can lead to irreversible changes (Bang and Suslick, 2010).
~ 87 ~
 Figure 2.3.2. Representation of sound wave phases
(This image is published on http://www.morkoamerica.com/cavitation.html and retrieved from Google Ima-
ges.)

2.3.2 Bubble Formation Mechanism

Ultrasound waves in a liquid cause molecules to vibrate around their present

locations. The distance between molecules reduced during the positive pressure
cycle, and increases during the negative pressure cycle. In the presence of high
enough intensity, the critical distance between the molecules is exceeded during
the negative pressure period and a cavity forms (Kuijpers, 2004; Ashokkumar,
2016). Due to the presence of dissolved gases and nuclei such as solid foreign
bodies, these cavities are formed under significantly lower sound pressure than
expected (Kuijpers, 2004). After the formation of a cavity, a critical sound pres-
sure must be exceeded for the exploding growth of this bubble. This exploding
growth is monitored by implosive collapse (Figure 2.3.3). The bubble content is
adiabatically heated during this collape; this leads to local short-lived hot spots
inside the liquid. Depending on certain conditions, pressure and temperature
inside the bubble can increase up to 200 bar and 5000 K, respectively (Leong,
2011; Kuijpers, 2004).

~ 88 ~
 Figure 2.3.3. Formation and collapse of bubble
(This image is published on http://www.morkoamerica.com/cavitation.html and retrieved from Google Ima-
ges.)

Resulting high temperature and pressure levels cause a series of chemical reacti-
ons in and around the bubble. Extreme conditions convert acoustic energy into
luminous energy which has a very short emission life (Figure 2.3.4). This inte-
resting physics phenomenon, known as sonoluminescence, was first observed in
1930s (Bang and Suslick, 2010).

Figure 2.3.4. Conversion of acoustic energy into light energy

(This image is published on http://www.ecowaterchc.com/solution/cavitation-basics/ and retrieved from Goog-
le Images.)

Free radicals are formed with the sonolysis of water as a result of ultrasonic
irradiation of the aqueous liquids. Primary sonolysis products in water are H* ve
OH* radicals. These radicals either come back together to return their original
forms or combine to produce H2 ve H2O2. They may produce HO2* radical by
reacting with O2. These strong oxidizing and reducing substances are used for
various sonochemical reactions in aqueous solutions (Leong, 2011).

~ 89 ~
2.3.3 Synthesis Mechanism of Nanoparticles

The fundamental mechanism in the production of metal or metal compounds is

the heat released from the cavitation bubbles. In order to produce metal and me-
tal oxides, volatile metal complexes are used in organic solutions and metal salts
in aqueous solution. These two methodologies have completely different mecha-
nisms for the production of functional nanoparticles. Some researchers used
volatile coordination compounds that contain zerovalent metal atoms to produce
metal nanoparticles (Leong, 2011; Ashokkumar, 2016). Cavitation bubbles
expand during the rarefaction cycle of the sound wave and volatile compounds
vaporize inside the bubble. Fe(CO)5 dissolved in octanol used for Fe nanopartic-
le production diffuses into the bubble and degrades during the collapse of the
bubbles due to the high temperature conditions that lead to the formation of Fe
nanoparticles. Produced material has amorphous structure and they exhibit high
catalytic activity in comparison to its commercial counterparts (Leong, 2011).

While metal nanoparticle formation takes place in the hot regions of the cavita-
tion bubbles in organic solutions, they are produced either in bubble/solution
intermediate phase or in the bulk solution in aqueous solutions. Produced H
atoms may act as reducing agents. When dissolved metal ion containing aqueous
solution is exposed to sound waves, H atoms produced inside the bubbles are
diffused into the bulk and react with metal ions to produce metal atoms that can
agglomerate for metal nanoparticle production (Ashokkumar, 2016).

Ultrasonic synthesis of polymer nanoparticles has numerous advantages over

conventional polymerization process (Kuijpers, 2004; Ashokkumar, 2016). Inc-
reased rate, particle size control, polymerization without initiator and single mo-
lecule weight distribution are some of the most important advantages. Mecha-
nism of ultrasonic polymerization process includes both physical and chemical
forces produced during acoustic cavitation (Figure 2.3.5). Initially generated
shear forces and hairline forces on the interface help the production of nanome-
ter-sized monomeric emulsion drops in aqueous phase. Primary and secondary
radicals produced in the cavitation bubbles are diffused into the monomer drops
that initiate the polymerization, thus, each monomer droplet is converted into a
polymer particle. Surfactants added to the medium are used to make monomer

~ 90 ~
drops stable. Reaction mechanism of ultrasonic polymerization is discovered by
Bradley and Grieser (Bradley and Grieser, 2002).

Figure 2.3.5. Physical forces that bubbles are exposed to

(This image is published on
https://upload.wikimedia.org/wikipedia/commons/thumb/5/59/Superheating.svg/1280px-Superheating.svg.png
and retrieved from Google Images.)

SUMMARY

Chemical outcomes of acoustic cavitation is very extensive, Bubble collapse in

the liquids creates unique high-energy conditions to trigger chemical reactions in
otherwise cold liquids. Benefits of sonochemistry are researched and a wide
variety of important applications with exciting potentials are developed for the
synthesis of extraordinary inorganic and biomedical materials. Development of
effective drugs for the disease treatment by using ultrasound is a commonly used
area with health benefits. Another emerging area is the use of ultrasound to pro-
vide new food substances and studies are especially focused on the production of
new dairy products.

~ 91 ~
References
Ashokkumar, M. (2016). Ultrasonic Synthesis of Functional Materials, Springer
International Publishing.
Bang, J.H. ve Suslick, K.S. (2010). Applications of Ultrasound to the Synthesis
of Nanostructured Materials. Advanced Materials, 22, 1039–1059.
Bradley, M. ve Grieser, F. (2002. Emulsion Polymerization Synthesis of Catio-
nic Polymer Latex in an Ultrasonic Field. Journal of Colloid and Interface
Science, 251, 78–84.
Kuijpers, M.W.A. (2004). Ultrasound-induced polymer reaction engineering in
high-pressure fluids, Technische Universiteit Eindhoven.
Leong, T., Ashokkumar, M. ve Kentish, S. (2011). The Fundamentals of Power
Ultrasound, Acoustics Australia, 39, 54-63.
Suslick, K.S., Didenko, Y., Fang, M.M., Hyeon, T., Kolbeck, K.J., McNamara,
W.B., Mdleleni, M.M. ve Wong, M. (1999). Acoustic cavitation and its
chemical consequences. Philosophical Transactions of the Royal Society
A, 357, 335-353.

~ 92 ~
2.4 ECO-FRIENDLY SYNTHESIS (GREEN
CHEMISTRY)

Dr. Serpil EDEBALİ

serpicetin@gmail.com
Dr. Yasemin ÖZTEKİN
yoztekin@gmail.com
Dr. Gülşin ARSLAN
garslan@selcuk.edu.tr
Dr. Mustafa ERSÖZ
mersoz@selcuk.edu.tr
SELÇUK UNIVERSITY

INTRODUCTION
Investments on nanotechnological research and applications are growing every-
day, thus, increases the concentration of nanostructures in the nature as a result.
Although we have very limited information about the impacts and risks of na-
nostructures on the environment and human health, they are already incorporated
into the compounds of various commercial products [Andreotti et al., 2015].
Nanomaterials change the properties of any material with their characteristics
that make them appealing, such as surface chemistry, surface area, size, shape
and functionalization. Therefore, in recent years, scientists are working on diffe-
rent methods for the synthesis of nanoparticles. However, since the chemicals
used in conventional synthesis methods are known to have adverse effects on
lively life, Green Chemistry method is preferred for the synthesis of nanopartic-
les. This way, nanoparticles can be intracellularly or extracellularly synthesized
from extracts and metal ions that are acquired from yeast, fungal bacterias or
plants, which have extensive application fields.

2.4.1 Historical Overview

The process had started in mid 20th century by establishing environmental pro-
tection rules, environmental regulations and environmental awareness rules and
became official with the formation of Environmental Protection Agency (EPA)
in 1970. Scientists, who are concerned with the future, shifted from pollution
elimination to pollution prevention with these initiatives and the office of “Pollu-
tion Prevention and Toxic Substances” was formed in 1988 within EPA. Initiati-
ves of EPA continued with their contribution to “Green Chemistry: Theory and

~ 93 ~
Application” authored by Paul Anastas and John C. Warner in 1998. In 2001 and
2005, Knowles, Noyori, Sharpless, and Chauvin Grubbs, Schrock received No-
bel Prize, respectively. These Nobel Prizes reinforced the importance of researc-
hes in “Green Chemistry” field and helped scientists to raise a higher awareness
that the future of chemistry must be more “green”.

2.4.2 Principles of “Green” Synthesis

12 principles of Green Chemistry, as mentioned in “Green Chemistry: Theory
and Application” book by Anastas and Warner, can be listed as follows [Anastas
and Warner, 1998].
● Waste prevention: It is better to prevent waste than to treat or clean up
waste after it has been created.
● Atom economy: Synthetic methods should be designed to maximize
the incorporation of all materials used in the process into the final pro-
duct.
● Less hazardous chemical synthes: Wherever practicable, synthetic
methods should be designed to use and generate substances that possess
little or no toxicity to human health and the environment.
● Designing safer chemicals: Chemical products should be designed to
affect their desired function while minimizing their toxicity.
● Safer solvents and auxiliaries: The use of auxiliary substances (e.g.,
solvents, separation agents, etc.) should be made unnecessary wherever
possible and innocuous when used.
● Design for energy efficiency: Energy requirements of chemical proces-
ses should be recognized for their environmental and economic impacts
and should be minimized. If possible, synthetic methods should be con-
ducted at ambient temperature and pressure.
● Use of renewable raw materials: A raw material should be renewable
rather than depleting whenever technically and economically practicab-
le.
● Reduce derivatives: Unnecessary derivatization (use of blocking gro-
ups, protection/ deprotection, temporary modification of physi-
cal/chemical processes) should be minimized or avoided if possible, be-
cause such steps require additional reagents and can generate waste.
● Catalysis: Catalytic reagents (as selective as possible) are superior to
stoichiometric reagents.
● Design for degradation: Chemical products should be designed so that
~ 94 ~
 at the end of their function they break down into innocuous degradation
products and do not persist in the environment.
● Real-time analysis for pollution prevention: Analytical methodolo-
gies need to be further developed to allow for real-time, in-process mo-
nitoring and control prior to the formation of hazardous substances.
● Inherently safer chemistry for accident prevention: Substances and
the form of a substance used in a chemical process should be chosen to
minimize the potential for chemical accidents, including releases,
explosions, and fires.

2.4.3 Methods

Synthesis of nanoparticles can be achieved through many physical and chemical

methods (electrochemical reduction etc.) [Bar et al., 2009]. Despite being suc-
cessfully synthesized by different methods, environmental friendly, inexpensive,
biocompatible methods are being studied in recent years due to the high cost of
the methods, and environmental and biological risks of the hazardous chemicals
used. Nanoparticles prepared by eco-friendly synthesis and other biological met-
hods are simple in application, they are economic, compatible with biomedical
and pharmacological applications and convenient for commercial production
[Flippo et al., 2010].
Nanoparticles can be synthesized by using living organisms or chemicals such as
plant extracts, microbes, fungi, yeast, algae, virus etc. [Bar et al., 2009, Kasthuri
et al., 2009, Philip et al., 2010, Dubey et al., 2010].
In order for a synthesis method or a material to be environmentally friendly, it
needs to have a safe, single reaction step, not produce any waste, use renewable
raw materials, have acceptable environmental hazard, 100% efficient and the
resulting nanoparticle must be easily separated from the reaction medium.

2.4.4 Application Examples

Below listed success examples of environmentally friendly studies show how
green chemistry affects a wide range of fields from pharmacology to household
goods and offers a way to a better world. In addition to the examples, during the
transition of environmentally friendly studies from research to practical stage,
2005 Nobel Prize in Chemistry was rewarded to the discovery of a catalytic

~ 95 ~
chemical process called metathesis that has a wide applicability in chemistry
industry. The process has the potential of using significantly less energy and
reduces the greenhouse gas emissions for many important processes. In addition,
this is a system that is stable under normal temperatures and pressures can be
used with environmentally friendly solvents and produces less hazardous waste.
In 2012, Presidential Green Chemistry Challenge Award was given to a study on
a catalyst technology to break down natural oils and recombine the fragments
into novel, high-performance green chemicals. This study was translated into
practice with the production of special chemicals for many areas of use such as
high concentration cold water detergents that provide better cleaning with redu-
ced energy costs.
Computer Chips
Many chemicals, large amount of water and energy are needed for the manufac-
turing of computer chips. In a previously conducted study, the ratio of chemical
and fossil fuels required to manufacture one computer chip was found to be
630:1. It means that in order to manufacture one chip, it is necessary to use sour-
ce materials 630 times as much of the chip's weight. To compare, this ratio is 2:1
for an automobile. Feather-based printed circuit boards, which can work twice as
fast as conventional circuit boards, are produced by using light and mechanical
and thermal stress resistant fibers made out of protein and keratin found in feat-
hers. Although this technology is still being used for commercial purposes, con-
ducted studies led to the discovery of other use areas for feathers as source mate-
rial, including biofuel.
Medicine
In the pharmaceuticals industry, new methods to develop drugs with fewer side
effects and to use processes that produce less toxic wastes are being sought.
A safe, highly efficient active pharmaceutical ingredient that produces less waste
is developed by enzymatic methods with environmentally friendly biocatalysts
for use in Type 2 diabetes. Although high amounts of hazardous reagents and
toxic waste are involved in the formation of multistage conventional prescription
for the treatment of high cholesterol, with the green synthesis that uses synthetic
enzyme and low-cost raw materials, wastes and hazardous substances are redu-
ced and low-cost drugs that meet consumer needs are offered.

~ 96 ~
Biodegradable Plastics
Instead of using petroleum-derived plastics for water bottles and yoghurt contai-
ners, environmentally friendly production is enabled with the use of microorga-
nisms that transforms corn starch into a resin that is as strong as plastics. Studies
to obtain biodegradable raw materials from bio-waste are ongoing.
Starch-based and calcium carbonate augmented biodegradable market bags that
are burst and tear-resistant, waterproof, printable and flexible can be manufactu-
red. Using these bags, which can be completely decomposed in water, CO2 and
biomass, in industrial compost system instead of commercial plastic bags will
significantly reduce household waste very soon.
Paint
When oil-based alkyd paints are dried, they cause large amounts of volatile
compound to evaporate and lead to more environmental impact, however, new
paints using soy oil and sugar mixture instead of fuel-fossil-derived paint resin
are discovered and they reduce the hazardous volatile substance levels by 50%.
Water-based acrylic alkyd paints with low levels of volatile compounds can be
produced from recyclable soda bottle plastics (PET), acrylics and soy oil.

Results

EPA and ACS (American Chemistry Society) play an important role in suppor-
ting the research and education on pollution prevention and reduction of toxic
substances conducted by Green Chemistry Institute for the past thirty years.
Governments and scientific institutions around world have stated that application
of green chemistry and engineering will not only lead to a cleaner and more sus-
tainable world, but they will also do good in terms of positive social and econo-
mic impacts. Since 1996, the United Nations has been annually awarding the
Presidential Green Chemistry Challenge Award to reward and celebrate the sig-
nificant achievements in Green Chemistry. Success of green chemistry for a
better world is proved by its wide range of applications from medical products to
household goods.

~ 97 ~
Summary
 Since green chemistry has a low cost most of the time, pollution prevention
is cheaper than pollution reduction.
 If a valuable use can be found, waste is not a waste. However, it is more fa-
vorable to find a better process to eliminate the waste.
 Chemical accidents caused by human errors will be frequently encountered.
If the chemicals used are nontoxic, severity of the accidents will be signi-
ficantly reduced.
 A green and sustainable society cannot be built overnight: The journey is
long and uncertain.
 In an ideal chemistry factory, the waste free product is targeted. The better
a real factory uses its waste, the closer it is to its ideal, the greater is the
gain.
 Green chemistry can guide chemists in the design of both effective and safe
products.
 Green chemistry is part of a multidisciplinary approach directed at building
a sustainable society.
 Technological advancements should not come at the cost of health and
prosperity of future generations.
 Green chemistry may remove the necessity of choosing between techno-
logy and sustainability.
 Governments and scientific communities around the world agree that green
chemistry and engineering applications will not only lead to a cleaner and
more sustainable world, but they will also do good in terms of positive
social and economic impacts. These advantages encourage businesses and
governments to support the development of sustainable products and pro-
cesses.

~ 98 ~
References
Andreotti F., A.P. Mucha, C. Caetano, P. Rodrigues, C. Rocha Gomes C.M.R.
Almeida. (2015), Ecotoxicology and Environmental Safety, 120: p. 303-
309.

Bar H., Bhui D.Kr., G. P. Sahoo., Sarkar P., De S. P., Misra A., (2009), Green
synthesis of silver nanoparticles usıng lateks of Jatropha curcas, Colloids
and Surfaces A: Physicochem. Eng. Aspects 339, 134-139.

Dubey S. P., Lahtinen M., Sillanpaa M., (2010), Tansy fruit mediated greener
synthesis of silver and gold nanoparticles, Process Biochemistry 45, 1065-
1071.

Flippo E., Serra A., Buccolieri A., Manno D., (2010), Green synthesis of silver
nanoparticles with surose and maltose: Morphological and structural cha-
racterization, J. NonCrystalline Solids 356, 344-350.

Kasthuri J., Veerapandian S., Rajendiran N., (2009), Biological synthesis of silver
and gold nanoparticles using apiin as reducing agent, Colloids and Surfaces
B: Biointerfaces 68, 55–60.

Philip D., (2010), Green synthesis of gold and silver nanoparticles using Hibiscus
rosa sinensis, Physica E 42, 1417-1424.

~ 99 ~
2.5. SOL - GEL METHOD

Dr. Volkan ONAR

vonar@pau.edu.tr
PAMUKKALE UNIVERSITY

INTRODUCTION
Sol - Gel process is one of the liquid-phase synthesis methods, which is a bot-
tom-up approach, used in nanomaterial production. What makes liquid-phase
important is that it creates the most suitable medium to let materials affect each
other by coming together at a certain ratio. [21 and article]. Sol-Gel method, as
with other liquid-phase methods, is about forming a solid gel in a liquid phase
from a suspension consisted of solid metal salts by utilizing the effects of ca-
talyst agent and medium. “SOL” repre-sents a suspension consisted of liquid
and solid particles, while “GEL” represents the solid state of this suspension.

Sol-Gel method is a economic and low-temperature method for small scale pro-
duction of nanomaterials; it is easier than other nanomaterial production met-
hods and it can be performed under laboratory environments (at room temperatu-
re). Conversion of attained gel into glass was first used in 1970s. The method
gained immediate interest as it allowed for nanomaterial pro-duction with low
energy consumption. This interest kept growing in 1980s and used in glass
manufacturing by a German company.

Abundant variety of nanomaterials that can be produced by Sol-Gel meth-od,

size differences, purity rates and homogenous distributions made this method an
inevitable technique of technological and scientific studies. [5,8,9, article]. It is
most widely used for ceramic production.

Generally, the Sol-Gel process is based on hydrolysis and subsequent condensa-

tion (the process where two molecules combine together by removing a small
molecule, like a water molecule, they have inside) of metal oxide pre-initiators,
such as nitrate, sulphate etc., with or without catalysts, inside ethanol or water
based acidic or basic solution.
1
Condensation: The process where two molecules combine together by removing a
small molecule, like a water molecule, they have inside

~ 100 ~
Alkoxides present inside a water - alcohol solution are removed from the me-
dium through hydrolysis by pre-initiators (acidic or basic). Metal oxide bonds
are formed from the metal that remains in the structure after hydrol-ysis and they
create a mesh-like structure by growing to make the whole volume consisted of
Metal + Oxide + Metal, and then gel is formed. At-tained gel is left for aging
and porous gel (xerogel) or nanomaterial pro-duction by burning with high-
temperature processing is performed.
In the past, this method was used only for small amounts of nanomaterial pro-
duction, however, today this method is well-established in the industry and be-
came a standard procedure.
Keywords: Nanomaterial production method, sol-gel

2.5.1 Sol - Gel Method Production Stages

 Hydrolysis of pre-initiators
 Condensation
 Gelling
 Aging
 Drying
 High-temperature processing
The most important feature of this method is that it allow ceramic material pro-
duction at 8 oC–room temperature.

Figure 2.5.1. Hydrolysis and condensation mechanisms

Alkoxide groups inside the alcohol-water solution are gradually removed by

hydrolysis in the presence of acidic or basic catalyst and replace the hydroxyl
groups that will form the metal + oxygen + metal bonds.

~ 101 ~
 Figure 2.5.2. Schematic representation of Sol - Gel Method
(https://www.ttu.ee/public/m/.../Lecture12_Synthesis2.pdf)

Sol-gel process has a particular importance since all chemical reactions and all
starting and resulting materials can be controlled.

Products with different characteristic properties can be obtained under similar

experiment conditions. The reason is each step of Sol - Gel pro-cess causes dif-
ferent effects on final product to be produced. Therefore, product-specific pro-
cess steps are required for the desired final product with utmost attention in all
steps.

2.5.2 Sol-Gel Material Components

Sol-gel process involves the transition of the sol compound from a liquid “sol”
phase to solid “gel” phase. Inorganic sol and gels are directly pro-duced with
synthesis from chemical reagents that are generally dissolved in a liquid me-
dium. The reagent that contains a metal (M) cation in an inor-ganic sol or gel is
called pre-initiators. The chemical transformation of this structure is signifi-
cantly complex.

~ 102 ~
Conversion of sol into gel also involves very complex reactions on a mo-lecular
level. These reactions enable controlled distribution of dense col-loidal particles
inside the sol or allows agglomeration of these in the gel to be controlled.

The components used in Sol-Gel process can be classified as follows;

Pre-initiators
All soluble pre-initiator can be used in sol-gel process. These can be defined
under two main groups: Metal salts and alkoxides

a) Metal Salts
The general formula of metal salts is MmXn. Here, M metal, X an anionic
group, and m and n stoichiometric constants. AlCl3 can be given as an examp-
le for metal salts.

b) Metal Alkoxides
Alkoxides are expressed in M(OR)n general formula. Aluminum ethoxide
(Al(OC2H5)3) can be given as an metal alkoxide example.

Metal alkoxides actively participate in reactions. These compounds are highly

reactive in the presence of humidity, heat or light.

Table 2.5.1. Alkoxides

Alcohol
Alkoxide
R(OH)
Methanol (CH3OH) Methoxide
Ethanol (C2H5OH) Ethoxide
1 – Propanol (n – propanol) (C3H7OH) 1 – Propoxide (n – Propoxi-
de
2 – Propanol (iso – propanol) (C3H7OH) 2 – Propoxide (iso – pro-
poxide)
1 – Butanol (n- butanol) (C4H9OH) 1 – Buthoxide (n – buthoxi-
de)
2 – Butanol (C4H9OH) 2 – Buthoxide (sec – but-
hoxide)
2- Methyll propanol (iso –propanol) 2 – methyl propoxide (iso -
(C4H9OH) propoxide)

~ 103 ~
 Tertio buthoxide
2 – Methyll – prop –2– ol
(tertio – butanol ) (C4H9(OH))

Solvents
As metal salt and alkoxide pre-initiators used in the method vary depend-ing on
the type of the nanomaterial to be produced, solvent must be se-lected according
to the pre-initiator type. Pre-initiators must go into reac-tion inside the solvent
used. Therefore, if metal salts are used as pre-initiators, solvent must be water,
and if metal alkoxides are used, solvent must be alcohol [4, 6, 11, 14].

Catalysts
Catalysts used in Sol-Gel method are studied under to main categories. These
acidic catalysts and basic catalysts. Generally used catalysts are given in Figure
2.5.3.

Figure 2.5.3. Catalyst types

2.5.3 3. Structures Created in Sol-Gel Method

Sol-Gel method uses more suitable conditions for nanomaterial pro-duction in

comparison to other methods. Therefore, Sol-Gel method is used to produce
different products with various physical properties like fibers, films, monoliths
and particles.
~ 104 ~
 Production by Sol-Gel method continues to gain importance day by day in vari-
ous fields, such as catalysts, sensors used in chemistry, membranes, fibers, opti-
cal sensors, development of new materials for chemical devices, ceramic pro-
duction, and nuclear and electron-ics industries.

2.5.4 Coating with Sol – Gel Method

Dip Coating
In this process, material to be coated is dipped into the solution and pulled back
at a specified speed under controlled atmosphere and controlled temperature. A
thin film forms on the surface of the material to be coated. The thickness of this
film changes depending on the maximum pulling speed, viscosity of the liquid
and the content of the solid onside the liq-uid.

The next step is the condensation of the solvent and tempering after gel-ling in
order to obtain oxide coating.

Angle-based Dip Coating

In this method, thickness of the coating depends on the angle between the bot-
tom layer and the liquid surface; therefore, different layer thicknesses can be
achieved on the top and bottom sides of the bottom layer.

Spin Coating Process

This method is used to perform thin coating on flat surfaces. The ma-terial to be
converted into coating is dissolved or dispersed with a solvent. Dispersed coa-
ting material is accumulated on the bottom layer and then spinned until a smooth
layer is obtained.

Flow Coating Process

In this method, liquid coating material is poured onto the material to be coated.
Coating thickness depends on the inclination angle of the bottom layer, viscosity
and solvent vaporization rate. Advantage of the method is that it provides easy
coating for non-planar large surfaces.

~ 105 ~
2.5.5.Advantages of the Sol-Gel Method

 Sol-Gel method allows materials to form oxide compounds and enables

the production of organic or inorganic materials.
 Except for the condensation step, it allows material production at low
temperatures and prevents thermal degradation of the material.
 Highly pure materials can be produced.

 High-porosity materials and nanocrystals can be produced.

 Since each step can be controlled during the material production, partic-
le size, amount of pores, surface roughness of the material to be produ-
ced can be controlled
 As liquid starting materials are used, it provides shape variety in cera-
mıc material casting without melting the materials and allows the pro-
duction of thin film and fibers.
 This method is widely used in optical part manufacturing since the mate-
rials produced with this method have high optical quality.

2.5.6. Disadvantages of The Sol-Gel Method

 Pre-initiator materials are generally expensive and sensitive against hu-

midity. This situation causes errors in special applications like large sca-
le optical coatings.
 Method takes a lot of time due to its multi-stage structure.

 Aging and drying processes must be conducted very carefully and meti-
culously. Desired properties cannot be obtained because of the dimensi-
onal changes and strain fractures during aging and drying stages.
 Method does not allow for large scale production.

~ 106 ~
 Summary

Sol-Gel method is the most widely used liquid phase method. The method is low
cost and it allows nanomaterial production in laboratory conditions with a simple
setting. However, costs increase for large scale productions due to the multiple
stages involved. It allows for production of nanomaterials that have different sha-
pes and sizes. Nanomaterials with more homogeneous structures can be produced
in comparison to other methods. Shape and size of the produced material can be
changed by meticulous control of the process steps. In addition, even surfaces of
complex shapes can be coated with Sol-Gel method.

Sol-Gel method is an important and widely used technique for nanomaterial pro-
duction.

~ 107 ~
 References

1. Brinker C.J., Scherer G. W., “Sol- Gel Science – The Physics and Che-
mistry of Sol – Gel Processing”, Academic, New York,1989.
2. Znaidi L., “ Sol – Jel Deposited ZnO thin films: A review” , Materials
Science and Engineering B, 174, 18 – 30, 2010.
3. Morpurgo M., Teoli D., Palazzo B., et al, “Influence of Synthesis and
Processing Conditions on the Release Behavior and Stability of Sol–Gel
Derived Silica Xerogels Embedded With Bioactive Compounds”, Il
Farmaco, 60, 675–683, 2005.
4. Volkan M., Stokes D.L., Vo-Dinh T., “A Sol – Gel Derived AgCl Pho-
tochromic Coating on Glass for SERS Chemical Sensor Application”,
Sensors and Actuators B 106, pp. 660–667, 2005.
5. Jung S., Kim J.H., “Sintering Characteristics of TiO2 Nanoparticles by
Microwave Processing”, Korean J. Chem. Eng., 27(2), 645-650, 2010.
6. Bayrakçeken, A., ‘Platinum and Platinum-Ruthenıum Based Catalysts
on Various Carbon Supports Prepared by Different Methods for Pem
Fuel Cell Applications’ In Partial Fulfillment of the Requirements for
the Degree of Doctor of Philosophy in Chemical Engineering, 2008.
7. Mohammadi M.R., Fray D.J., “Sol–Gel Derived Nanocrystalline and
Mesoporous Barium Strontium Titanate Prepared at Room Temperatu-
re”, Particuology, 9, 235–242, 2011.
8. Damardji B., Khalaf H., Duclaux L., David B., “Preparation of TiO2-
Pillared Montmorillonite as Photocatalyst Part II Photocatalytic Degra-
dation of a Textile Azo Dye”, Applied Clay Science 45, 98–104, 2009.
9. JOHNSTON H.J,Grindrod E.J.,Dodds M.,Schimitschek, “Composite
nanostructured calcium silicate phase change materials for thermal buf-
fering in food packing”, Current Applied Physics 8,508-511, 2008.
10. Toygun Ş., Köneçoğlu G., Kalpaklı Y., “General Principles of Sol –
Gel”, Journal of Engineering and Natural Sciences, Sigma 31, 456 –
476, 2013.
11. https://www.ttu.ee/public/m/.../Lecture12_Synthesis2.pdf, web bağlantı-
sı

~ 108 ~
 2.6 PHYSICAL VAPOR DEPOSITION METHOD
(PVD)

Dr. Cumhur Gökhan ÜNLÜ

cunlu@pau.edu.tr
PAMUKKALE UNIVERSITY
INTRODUCTION
Today, nanoparticles can be produced by using many different meth-ods. Pro-
duction methods of nanoparticles can be examined under two main topics. These
are wet chemical synthesis and synthesis un-der gas phase environment. These
methods have various advantages and disadvantages over each other. Nanopar-
ticles to be produced in gas phase environment are either particles that are obtai-
ned by form-ing gas phase from a solid-form material in a vacuum environment
or thin film coatings. One of the most common techniques for synthesis in gas
phase environment is the physical vapor deposition (PVD) method.

PVD is a common method used in industry for thin production and coating in
high vacuum environments. This method is being used since 1800s and now, in
parallel with the development of nanotech-nology, it is used to produce nano-
scaled materials and perform coat-ings with nanometric thicknesses. PVD is a
thin film coating tech-nique that is commonly used in medicine, automotive
industry, metal processing industry and other industries. Physical vapor deposi-
tion method is defined as the accumulation of physically vaporized or ejected
particles on a substrate. These techniques have many types and most common
ones are sputter and vaporization methods. Nano-particles to be produced using
this method are obtained through sub-limation on a substrate or as powder in a
gas phase environment. The most important feature of this method is that it
enables controlled acquisition of particles in a vacuum environment without
requiring different solution mediums necessary for chemical reactions. This way,
particle crystallization, size and shape can be easily controlled. Parameters that
regulate the properties of the particles are pressure, gas flow and thermal heat
values of the production environment.

~ 109 ~
2.6.1 Sputter Technique

Sputter technique is based on the physical accumulation of atoms, which are

ejected from a target material by positive ions, on a sub-strate. In order to produ-
ce a material with this method, the environ-ment called vacuum chamber, where
the reaction will take place, is vacuumed by using a vacuum pump. Then, a cont-
rolled inert that gas does not react is used inside the vacuum chamber. This gas
is general-ly Argon (Ar). Ar atoms are ionized by colliding them with electrons
that are accelerated under a high electrical field. Ar atoms, which are now +
ions, move towards cathode inside the electrical field and they eject atoms from
the target material, which is placed in front of the cathode, by hitting the said
material. The process is concluded by the deposition of these atoms, which gain
kinetic energy as a result of this collision, on the substrate that is placed in front
of the anode (Figure 2.6.1). Depending on the target material that is wanted to be
grown, two different sputter processes can be performed, namely, DC and RF
voltage. DC sputter is used if the target material is a conducter and RF sputter
technique is used when the desired materi-al will be produced out of conductor
and semi-conductor targets.

Figure 2.6.1. Schematic view of sputter system

(https://en.wikipedia.org/wiki/Sputter_deposition)

In magnetron sputter technique, magnetic field is used to confine electrons that

are close to the target in order to control the amount of atoms wanted to be
grown and to eject atoms from a specific region of the target material (Figure
2.6.2). This way, Ar atoms ionized in these areas can eject atoms from the target
material.

~ 110 ~
 Figure 2.6.2. Target and magnets of a magnetron sputter system

Schematic view of a magnetron sputter system used to grow nanopar-ticles is

shown in Figure 2.6.3.

Sintering
Sputtering
furnace Deposition
chamber
chamber

Ar+He

Cu target

Atoms clusters

Pump

Figure 2.6.3. Schematic view of magnetron sputter system used to produce na-
noparticles

~ 111 ~
High resolution transmission electron microscopy (HRTEM) images of nanopar-
ticles with different types and properties obtained by this method are shown in
Figure 2.6.4.

a b c

2 nm

Figure 2.6.4. HRTEM images of a) Fe-Bi dumbbell-like, b)Fe-Mg core-shell, c)

Cu nanoparticles produced by magnetron sputter method

~ 112 ~
References

1) https://en.wikipedia.org/wiki/Sputter_deposition

2) C.Gokhan Unlu, Zi-An Li, M. Acet, and M. Farle, Gas-phase synthesis

of Fe-Bi metastable and dumbbell Particles, Cryst. Res. Technol., 1–
4 (2016)

3) C.Gökhan Ünlü, Mehmet Acet, Atakan Tekgül, Michael Farle, Şaban

Atakan, Jürgen Lindner, The Production of Cu nanoparticles on large
area graphene by sputtering and in-flight sintering, Cryst. Res. Tech-
nol., 52, 1700149, (2017)

~ 113 ~
 2.7 CHEMICAL VAPOR DEPOSITION METHOD
(CVD)

Dr. Cumhur Gökhan ÜNLÜ

cunlu@pau.edu.tr
PAMUKKALE UNIVERSITY

INTRODUCTION
Chemical Vapor Deposition Method (CVD) is a material production procedure
that is being used for many years in material science. In general, this method
allows obtaining a gas-phase material in solid form. This method is used for
surface coating of materials, which are generally named as thin film.

This method is based on the deposition of the material consisted of gases on

determined suitable substrate surfaces by going through chemical reaction with a
carrier gas under temperature and in mediums such as plasma. Although this
method is used to produce thin films on a material, it is also being used to obtain
high-purity bulk materials, powder materials, and, recently, nanomaterials. Na-
nometric material production can be conducted by controlling the necessary
parameters in the system like gas flow rate, deposition duration, pressure and
temperature. Especially in recent years, CVD has become one of the most im-
portant production techniques used to obtain carbon allotropes of artificial dia-
mond, graphene and carbon nanotubes. Wide variety of different materials can
be produced by CVD method.

Figure 2.7.1. Chemical vapor deposition method

(Karslioglu, R., (2007), Production of SnO2 Coatings by Chemical Vapor Deposition Method, Master Thesis,
Sakarya University, Institute of Science)
~ 114 ~
In CVD method, material or materials to be produced are put into the system in
gas form and are deposited on a substrate surface, which is a specified heated
catalyzer, as a chemical vapor. Chemical reaction occurs on hot surface or close
to it. Formed vapor creates a film layer on the substrate surface it is deposited.
Unwanted reaction products, that are produced as a result of the reaction, are
removed from the system as vapor. Steps of a basic CVD production methods
are as follows;
• A mixture of reactant gases, carrier gases and inert gases is sent into the
vacuum chambers, where the reaction will take place, in certain ratios
and flow rates,
• Gases that will react move on the substrates used as catalyzer,
• Reactants are absorbed from the substrate surface,
• Surface and reactants go into chemical reaction and a thin film is formed
on the surface.
• Inert products are removed from the vacuum chamber.

CVD method has many advantages. Produced thin films have a very
homogeneous distribution in terms of thickness and matter quantity. Another
advantage over other methods is the fact that many different materials can be
produced by this method. Produced materials can be obtained in significantly
pure forms. Deposition rate is very high in CVD method. Therefore, it doesn’t
require high vacuum values.

Figure 2.7.2 Chemical Vapor Deposition Method

~ 115 ~
There are different types of CVD methods that enable the production of materi-
als required for various application fields. These methods include hot wall reac-
tors, cold wall reactors, atmospheric pressure CVD, and low pressure CVD.
• Hot Wall CVD: In the system, the reactor walls, where the reaction ta-
kes place, are also heated during the heating of the substrates.
• Cold Wall CVD: This method is based on keeping the reactor walls,
where the reaction occurs, cold. IR-lamps are used inside the reactor for
the heating system.
• Atmospheric Pressure CVD (APCVD): Reaction occurs under atmosp-
heric pressure. Production method is significantly easy and rapid. Pro-
duction temperature is cold. Contamination is high.
• Low Pressure CVD (LPCVD): Reaction takes place under medium pres-
sure (30-250 Pa) and high temperature. High quality and purity products
are obtained. This method requires high temperature and production rate
is slow.

Generally, temperature requirement for CVD production is between 200 and

1600 oC. In addition, there are other CVD techniques like Plasma CVD, Laser
CVD, Hot Filament CVD.

Figure 2.7.3 Graphene production on Cu with Thermal CVD system

Materials wanted to be produced must be in gas form under room temperature

and this condition can be given as one of the disadvantages of the method. This
makes it difficult to produce many elements. In addition, most of the gases used
in CVD method are toxic and flammable. They are required to be disposed of
without damaging the nature and the environment. Therefore, an additional filte-
ring system is required. And some gases may be expensive.
~ 116 ~
References

1) Karslıoglu, R., (2007), Kimyasal Buhar Biriktirme Yöntemiyle SnO2

Kaplamaların Üretilmesi, Yüksek Li-sans Tezi, Sakarya UNIVERSITY,
Fen Bilimleri Enstitüsü

2) https://ultramet.com/chemical-vapor-deposition/

~ 117 ~
2.8 LITOGRAPHY

Dr.Serpil EDEBALİ
serpicetin@gmail.com
Dr.Mustafa ERSÖZ
mersoz@selcuk.edu.tr
SELÇUK UNIVERSITY

INTRODUCTION

Most of the top-down miniaturization methods starts with litography, which is

used to transfer the copies of a master mould onto the surface of solid material
like a silicon chip plate. The word litography is derived from “Lithos - stone +
graphein - to write” and called as “stone print” in the literature. In this chapter,
different forms of litography will be discussed in detail and their differences
from most of the miniaturization processes will be put forward.

2.8.1 Historical Development

Although many attempts had been made to copy using various resins under day
light, Nicéphore Niépce had managed to copy a worn down print onto an oil
paper placed on a glass plate that is coated with tar (asphalt) dissolved in laven-
dar oil (French, 1822). After 2-3 hours under sun light, it was observed that uns-
haded regions on the tar were more soluble and became more rigid than shaded
regions that can be washed with a mixture of turpentine and lavendar oil. Niép-
ce's recommended mixture corresponds to a negative-type photoresist. Five ye-
ars later, in 1827, a Parisian engraver Lamaitre managed to make a worn down
copy of a engraving piece of Cardinal d’Arnboise by using a strong acid on a
layer developed by Niépce. Latest copy represents the first mould transferred by
photolithography and chemical milling [Pfeiffer, 2010].
Actually, the word litography (means stone [lithos] and to write [graphein] in
Greek language) defines a process that was discovered by Aloys Senefelder in
1796. Senefelder found that when a stone (Bavarian limestone) is suitably inked
and processed with chemicals, an engraved image can be transferred onto paper.
The chemical processing of the stone pulls the ink to the area with image and

~ 118 ~
water to the area without image; therefore, these areas become lipophilic (hyd-
rophobic) and lipophobic (hydrophilic), respectively.
Niépce process became one of the most important studies in early development
of photography. In recent years, the photomasking performed subsequent toafter
chemical processing has opened the way for photolithography that is used for
integrated circuit production and miniaturization sciences. Not only until the
Second World War, method was further developed even 100 years after Niépce
and Lemaitre and first applications of printed circuit board had emerged. Con-
nections are made by soldering electronic parts on to a mould of “wires” produ-
ced by photoradiation of copper folio layer that is plaalced layer-by-layer on a
plastic plate. Starting from 1961, new methods are invented for transferring
many number of transistors onto a thin silicon slice by using photoetching pro-
cess. Today photolithograpy, x-ray lithography and charged particle lithography
all achieved sub-micron printing.
Lithography (or shaping) includes shapes of various components of integrated
circuit (IC), their sizes and a series of process steps to determine the location.
Current development in IC design is possible by shaping the small areas on the
chip plate by utilizing reduced chip sizes (miniaturization) and increased density
of transistors. Therefore, majority of IC design success is achieved by lithog-
raphy [Chou, 1996].
For lithography process, first a printed copy of the mould must be produced.
This called reticule or mask. The process is completed by transferring the design
on the mask onto the chip plate [Piner et al, 1999]. Transfer can take place with
a 1:1 ratio (i.e. without any reduction in the size), however, generally the size is
reduced, thus, mould is transferred to a small area on the chip plate. This is achi-
eved by using lenses that are suitable for mould reduction. Lithography has two
stages, and each of them has several steps:
1. In the first stage, mould is transferred to a photoresist layer on a chip plate.
Photoresist is mildly sensitive material and its properties change when exposed
to light with a certain wavelength. This process is called developing. The mould
formed in this step is temporary and it can be easily removed. This is particularly
important if the mould is not fully aligned with the chip plate or another mould
on the chip plate.
2. Mould is transferred from photoresist to chip mould. Exposed chip plate sur-
faces or layers accumulated on top of that can be etched (removal of material).
~ 119 ~
Dopant materials are added to the partitions of chip plate along the mould. This
is the final stage, and the removal of the formed moulds without damaging the
chip moulds underneath is a difficult process.
After mould is formed on the photoresist and chip plate surface is exposed (de-
veloping process), exposed chip plate surface is etched. It is possible to accumu-
late material on the exposed surface [Parikh, 2008].
Photolithography is the most widely used lithography method. In the IC in-
dustry, mould transfer from masks to thin films almost started with photolithog-
raphy. Correct recording and a series of exposure of successful moulds result in
complex, multi-layered ICs. This two-dimensional process has a limited toleran-
ce for non-planar topography; this also introduces a major limitation for non-IC
miniaturized systems that exhibit extreme topographies. Photolithography deve-
loped very rapidly and maintained a constant advanceement with its ability to
resolve even the tiniest properties. This ongoing improvement prevented the
adaptation of alternative high-resolution lithography techniques, such as x-ray
litography, for IC industry.

2.8.2 Photoresists
The use of photoresists in chip plate production had started in 1950s. This tech-
nology was adapted from photography industry. There are general purpose re-
sists and resists that are specific for special applications. These are generally
adjusted to a certain wavelength. Components of a photoresist are as follows:
1. Polymer - a light-sensitive polymer with properties that change when exposed
to light. The desired characteristic is generally a resolution that changes in a
certain solvent.
2. Solvent - solvent is used to thin the resist, thus, it can be applied onto chip
plate with spinning process. Solvent is generally removed by heating up to
100°C, a method known as soft roasting process.
3. Sensitizers - they are used to control the chemical reaction during exposure.
4. Additives - Various chemicals added to achieve certain processes like pain-
ting.
Photoresists general initiate the reaction with ultraviolet (UV) or visible light,
therefore they are called optical resists. In addition, there are special resists for
other radiation types like x-ray and e-beam.

~ 120 ~
 Figure 2.8.1. Schematic view of positive and negative resists

Generally, photoresists are classified in two groups:

1. Positive resists - These become more soluble when they are exposed to UV
rays.
2. Negative resists - These become less soluble when they are exposed to UV
rays.
Differences between these two types are shown on Figure 1. Photoresists di-
rectly transfers the mould from mask to the chip plate, therefore, mask protects
the resist lower than itself against exposure to UV rays. Remaining part of the

~ 121 ~
 resist, the exposed part, becomes more soluble and can be easily removed [Iva-
nisevic, 2001]. On the other hand, negative resists transfer the negative of the
mask mould onto the chip plate. This is a process similar to the negative process
of photography. For negative resists, the part protected by the mask is more so-
luble because it is not exposed to UV ray and radiation makes the remaining part
of the resist more rigid [Kim, 2008].

2.8.3 Nanolithography

Nanolithography is a branch of nanotechnology and it is related to the studies and

applications of nanoproduction of nanometer-sized structures, and it is the nanoco-
ating of at least one horizontal dimension between the sizes of an atom and 100
nm. Although it means small writing on stone, recently it is also used, in terms of
nanotechnology, for nanoproduction of groundbreaking semi-conductor integrated
circuits, nanoelectromechanical systems (NEMS) [Ruizab and Chen Christopher,
2007] or other applications that are related to other various scientific branches in
nanoresearch [Venugopal and Kim, 2013].

There are many lithography techniques where micro/nano coating is possible [Ste-
venson J. T. M. ve Gundlach, 2014]. These are;

• Photolithography: This is a conventional and classic technique and called optical

or UV lithography. A photolithography system is typically consisted of a light
source, a mask and an optical projection system. This technique uses the exposure
of photoresist to ultraviolet light in order to obtain desired mould. Photolithography
can produce integrated circuits and other internal computer parts. At the same time,
it can also be used to produce organic memory devices for the production of micro-
circuits (NEMs, MEMs) and array structure.

• X-ray Lithography: This method is an extension of photolithography. The only

difference is that this method uses x-rays instead of UV for as light source. In this
method, a mask is required since direct writing or moulding is not possible. X-ray
lithography is used for building block integrated micro fluid structures. This tech-
nique hasve application fields in the production of miniaturized devices such as
genetic and microchips, microelectrophoresis devices. In addition, it is used for the
production of flaming diffractive optical elements with the help of x-ray mask.

~ 122 ~
• Electron Beam Litography: This method is used for production of nano-scale
moulds. This technique uses an accelerated electron beam to focus on an electron-
sensitive resist in order to expose the material. This electron beam is scanned over
a resist, which has a several nanometers of layer-by-layer structure, to produce
desired consecutive moulds. The process involves the steps of preparation of a
resist like a polymethylmethacrylate (PMMA) by using spin method, removal of
any solvent and rigidification of a film as mentioned in photolithography. Desired
mould with high-resolution up to 10 nm in size by exposing the selected area to
high energy of the electron beam. Scanning electron microscope (SEM) can be
turned into electron beam lithography machine and used. Its application fields
include telecommunication, sensors, optical photobiology and phototherapy scien-
ces. 1D and 2D photonic crystals and silicon-insulated photonic wires can be obta-
ined with this method.

Alternative Nanolithographic Techniques:

◦ Micro-contact printing: This is a soft printing method. It allows for creating

moulds as self assembled monolayers of ink on masters such as polydimethylsi-
loxane (PDMS) sealing. It can be easily removed from the substrate during produc-
tion due to the low melting point of PDMS, a prepolymer. This technique is used in
fields like cell, DNA and protein shaping, microQRCode and MEMs, cell biology,
miniature mechanization and surface chemistry.

◦ Nano-stamp lithography: This is a process similar to soft lithography. In this

method, desired methods can be obtained by using a mold to process the photore-
sist by dilating it. The nano-stamp lithography is based on the modification of thin
polymer film; mechanical sealing deformation is achieved through a thermo-
mechanic or UV curing process by using a template containing nanomoulds (a
mould or seal). Low cost LED devices, polarizers, plasmonic devices and photonic
crystals can be produced in high efficiency with this technique. In addition, this
technology is also effective in the production of electronic devices such as MOS-
FE, O-TFT and single-electron memory. It has key applications in formatting of
magnetic medium for optical storage (EBR) and hard disc drives.

~ 123 ~
Conclusion

In this chapter, where different types of nanodevice production are explained and
differences between different lithography techniques are given, it can be seen that
nanolithography has a wide range of application fields. It is highlighted that lithog-
raphy techniques are effectively preferred especially for the production of different
types of sensors and other devices that contain nano-scaled components. In conclu-
sion, it is clear that nanolithography technology will be very helpful for the structu-
ring of nanoscience and technology of future.

~ 124 ~
References
Chou, S. Y. (1996). Nano imprint Lithography. J. Vac. Sci. Technol. B., , 14, 4129.

Ivanisevic, A. (2001). Dip-pen nanolithography on semiconductor surfaces. J. Am.

Chem. Soc. , 123, 7887-7889.

Kim, S. J. (2008). Development of Focused Ion Beam Machining Systems for

Fabricat‐
ing Three-dimensional Structures. Jpn. J. Appl. Phys., , 47(6), 5120-5122.

Parikh, D. (2008). Nanoscale Pattern Definition on Nonplanar Surfaces Using Ion

Beam Proximity Lithography and Conformal Plasma-Deposited Resist. J.
Microelec‐tromech. Syst. , 17.

Pfeiffer H. C., 2010. Direct write electron beam lithography: a historical overview,

Proc. SPIE, 7823, 782316.

Piner R.D., Zhu J., Xu F., Hong S., Mirkin, C. A. (1999). Dip-pen Nanolithog-
raphy.
Science. , 283 (5402), 661-663.

Ruizab S.A. ve Chen Christopher S., 2007. Microcontact printing: A tool to

pattern, Soft Matter, 3, 168-177.

Stevenson J. T. M. ve Gundlach A M, 2014.”The application of photolithography

to the
fabrication of microcircuits”,J.Physics E: Scientific Instruments, 19, 654-667.

Venugopal G. ve Kim S.-J., (2013). Advances in Micro/Nano Electromechanical

Systems and Fabrication Technologies: Nanolitography,
http://dx.doi.org/10.5772/55527.

~ 125 ~
~ 126 ~
SECTION 3
NANOMATERIALS

~ 127 ~
~ 128 ~
3.1 NATURAL NANOPARTICLES
Dr. Arzu YAKAR
ayakar@aku.edu.tr
AFYON KOCATEPE UNIVERSITY

INTRODUCTION
Nanotechnology is a branch of science that deals with materials that have sizes
of one billionth of a meter and works with materials that can be controlled at
atomic/molecular scale. A nanoparticle generally covers a size range of 1 to 100
nm and is the most fundamental component in the production of nanostructures.
In addition, they are larger that a simple molecule or atom that is regulated by
the rules of quantum mechanics, but significantly smaller than the objects that
are mentioned within the Newtonian law of motion. As particles get smaller,
they manifest different properties. For example, metallic nanoparticles have
physical and chemical properties desired in various industrial applications and
are different from bulk metals, such as low melting point, high surface Area,
specific optical properties and mechanical force. It can be seen in historical
artworks that especially the optical properties of nanoparticles have been known
for a long time and widely used in paintings and sculptures. Whereas a 20 nm
gold nanoparticle has the characteristic wine red, silver has yellowish gray, pla-
tinum and palladium have black colors (Figure 3.1.1). Natural nanoparticles can
be formed by one or more processes in the atmosphere, hydrosphere, lithosphere
and biosphere that cover the earth. Extraterrestrial processes that form the cos-
mic dusts are also part of these processes. In this section, general information of
natural nanoparticles will be given.

3.1.1 Natural Nanoparticles

Nanoparticles can be formed by chemical, photochemical, mechanical, thermal
and biological ways separately or with the combination of several natural pro-
cesses in the atmosphere, hydrosphere, lithosphere and biosphere that cover the
Earth. Extraterrestrial processes that form the cosmic dusts are also part of these
processes. The major natural sources of nanoparticles in the atmosphere are vol-
canic eruptions, desert surfaces, and dusts emitted from cosmic sources in the
solar system. Particulate matters, which can also be created by crashing of a
meteor passing through the atmosphere or the accumulation of cosmic dusts, are
carried up in the sky to different distances by volcanic eruptions, storms or air
~ 129 ~
currents formed by strong winds. Hurricanes carry large amounts of water from
the ocean surfaces to the atmosphere. Evaporation allows water, salt and algae to
release their spore contents, and other unicellular organisms. Due to these comp-
lex events, which occur simultaneously most of the time, the atmosphere is cons-
tantly filled with nanoparticles that cause various reactions that affect biosphere
at various altitudes and distances. At the same time, natural nanoparticles (NNP)
can be spontaneously created as a result of human-induced mining, waste water
production and other wastes created by industrial processes and during other
activities. A recent estimation conducted for NNP formation suggests that seve-
ral thousand teragrams (1 Tg = 1012 g) of NNP is created via only biochemical
processes (Sharma et al., 2015, Hochella et al. 2015).

Figure 3.1.1. Colors of silver (Ag) and gold (Au) nanoparticles with different
shapes and sizes
(http://sciencegeist.net/the-shape-of-things/ sayfasında yayınlanan bu fotoğraf Google görsellerinden alınmış-
tır.)

Gold and silver has been used as the foundational component of jewelry, metal
coins and color-leaded windows of cathedrals for centuries. Today, they also
became the focal points of nanomaterials and the gold-silver nano pair, which
are artificially attained as engineering materials, has numerous applications.
Silver nanoparticles are one of the most studied types due to their exclusive de-
tection, catalytic, optical and antimicrobial properties and being sensitive sensors
for the detection of various biomolecules and monitoring of biological conversi-
ons (Batley et al. 2013, Sharma et al. 2014, Sharma et al. 2015). Similarly, gold
nanoparticles are being used for the diagnosis and treatment of cancer, chemical
and biological imaging, catalysis and sensors (Saha et al. 2012). The constant
increase in the use of these gold and silver nanoparticles that are produced as
engineering materials, their release to the environment, and their potential im-

~ 130 ~
pact on ecological system due to release have caused concerns, however, toxic
properties of naturally formed nanoparticles have drawn relatively less interest.

3.1.2 Natural Nanoparticles in the Atmosphere

There are 3 fundamental sources for the natural nanoparticles in the atmosphere.
These are volcanic eruptions, desert and cosmic dusts.

1) Volcanic Eruptions
The ash released by volcanic eruptions has a complex structure consisted of
liquid/solid particles that are carried upwards by the hot gas flow and can reach
temperatures above 1400°C (Strambeanu et al. 2015, Juravle 2012). After the
eruption of the volcano, ash spreads to the atmosphere, gas temperature drops
and gas composition changes (Figure 3.1.2). Chemical reactions or electrostatic
interaction forces cause particles to accumulate in bulks. Content of volcanic gas
emissions change depending on kinetic conditions such as thermodynamic con-
ditions, pressure, temperature, reaction rate and the natural structure of the
magma.

Figure 3.1.2. Volcanic explosion

(The image is published on https://www.slideshare.net/PandeyAman/hw-homework-science-amanpptx-mmmm
and retrieved from Google Images.)

Basaltic magma is rich in terms of magnesium and iron, and poor in silica. In
addition, it has a reduced gas concentration containing mainly carbon dioxide
and sulfur dioxide and low viscosity. Generally, hydrogen sulfur (H2S) and hyd-

~ 131 ~
rogen chloride (HCl) are dominant in the gas emissions (Strambeanu et al. 2015,
Symond et al. 1994, 1988, Cadle et al. 1980, Chin et al., 1993). Hydrogen chlo-
ride is highly soluble in water. The water vapor in the upper layers of the at-
mosphere condensates above the ash particles and causes acid rains. These gases
are quickly moved away from the atmosphere with the acid rains occurring du-
ring the eruptions. Hydrosulphuric acid oxidized by ozone in the troposphere
also has the same effect. The concentration of hydrobromic acid is relatively low
(Strambeanu et al. 2015, McElroy et al. 1992, Bureau et al. 2000). In addition to
hydrosulphuric acid oxidization, hydrobromic acid also has significant contribu-
tion to the reduction of both ozone and diatomic oxygen concentrations. Volca-
noes are thought to be the source of the hydrofluoric acid in the atmosphere.
Therefore, there is very limited knowledge about its concentration in the at-
mosphere. In some cases where the hydrofluoric acid emissions are too high, it
has been reported that these emissions significantly pollute the plant cover and
cause animals and people to die. As with other halogen acids, hydrofluoric acid
also spreads around the volcano through acid rains. Therefore, excessive fluoride
ions can cause animal deaths in large areas even a long time after the eruption. If
the concentration goes above 250 ppm, it may cause plant intoxication, thus,
harming the plant cover (Strambeanu et al. 2015, Textor et al. 2003). Chemical
composition of the ash can be easily detected from the emissions of dormant
volcanoes. Dry fumaroles do not contain water, therefore they exceed critical
temperature of the water (374°C). It contains nitrogen gas (N2), carbon monoxi-
de gas (CO), hydrogen gas (H2), methane gas (CH4) and sodium chloride vapor
(NaCl), potassium chloride (KCl) and copper (II) oxide (CuO). Fumaroles pro-
duce halite (NaCl), sylvine (KCl) and tenorite (CuO) by accumulation on the
edges of the crater and during eruption or on the surfaces thrown in the form of
ash. Acid fumaroles contain hydrogen sulfur (H2S), sulfur dioxide (SO2), carbon
dioxide (CO2) and water vapor. Their critical temperature is close to that of
water. If acidity is not too high, acid fumaroles contain iron (II)/(III) chlorides
(FeCl2, FeCl3), copper (I)/(II) chlorides (CuCl, CuCl2) or iron oxides in the form
of magnetite (Fe2O3). In the presence of sulfur (especially in underwater fumaro-
les), iron exists in the forms of marcasite (white iron pyrite) and pyrite (FeS,
FeS2). Alkali fumaroles are produced from the reaction of ammonium chloride
(NH4Cl), ammonia hydroxide (NH4OH) and water vapor in the presence of am-
monia (NH3). Ammonia chloride takes the form of micrometer or sub-
micrometer particles. Temperatures of these fumaroles are 100-400°C. Eruptions
are natural volcanic vapor ventilations where hot water vapor and sulphur gases
~ 132 ~
are dominant. Fumaroles release sulfurous acid (H2SO3) and more stable sulfuric
acid (H2SO4) gases in the presence of sulfur, hydrogen sulfur (H2S)/sulfur dioxi-
de (SO2) and water vapor. Sulfurous arsenic, caused by the condensation of the
vapor, is defined as the solid of orpiment (As2S3), iron and copper pyrites, iron
sulfate (FeSO4) natural sulfur substances (Juravle, 2012).

2) Deserts
Other important sources of nanoparticles that are flown by air flows and dust
storms and carried to the atmosphere are the large deserts. Long range migration
of metal powders and human-induced pollutants over the continents has become
the focal point of recent studies. These studies revealed that approximately 50%
of the aerosols in the troposphere are desert-originated minerals. Chemical com-
position of very thin desert sand dust changes depending on the air currents and
anthroogenic activities (Strambeanu et al. 2015, Shi et al. 2005).
Analyses showed that the composition of the particulate substance, formed du-
ring the dust storm between China and South Korea (Figure 3.1.3), contained
high concentrations of silicon, aluminum, calcium and iron. In addition, heavy
metals (Hg and Cd) and poly(nuclear) aromatic hydrocarbons (PAH), which are
generally produced by coal combustion, are also detected in the stratosphere,
however, their sources are not known (Strambeanu et al. 2015, Xiaodan 2007,
Chun et al. 2008).
Analyses conducted around Xian city, which is located close to the huge at-
mospheric dust transfer from the Gobi desert, and the Hua mountain revealed the
presence of sulphide, nitrate and ammonium ions originating from anthropoge-
nic activities in addition to high concentrations of carbon and organic nitrogen
concentration, which are thought to be originating from microbiological activi-
ties in the atmosphere. These particles carried by the wind have sizes between 80
nm and 1000 nm.
In recent years, the types and behavior of Saharan aerosols have been extensi-
vely studied in the Sahel region, in some parts of the Atlantic Ocean and in So-
uthern Europe. The contribution of Sahara to the particulate matter (PM10) is
determined through the gravimetric analysis of Al, Si, Fe, Ti, non-sea originating
Ca, Na and K oxides (Strambeanu et al. 2015, Wang et al. 2012).

~ 133 ~
 Figure 3.1.3. Desert storm between Cape Verde Islands and Senegal
(The image is published on http://www.gmes-atmosphere.eu/news/dust_senegal/ and retrieved from Google
Images.)

An estimation about the ionic balance of the atmosphere suggests that the reacti-
ons containing anthropogenic acids and micro crystal particles may play an im-
portant role in the sedimentation of nanoparticle systems, and that they may
affect the intake of these by the cellular structures of living organisms (Strambe-
anu et al. 2015, Wang et al. 2012).
The results of other studies conducted during the fine particle transportation
between the Cape Verde Islands (Strambeanu et al. 2015, Wang et al. 2012) and
Sal Island (Figure 3.1.3) close to Senegal coasts caused by Harmattan (Figure
3.1.4) suggests (Strambeanu et al. 2015, Taylor 2002) that dust particle currents
in the main cloud are localized based on their masses. Estimations based on
Al2O3 concentration revealed that air opacity and O3 concentrations are decrea-
sed above 4.500 m. Same studies (Strambeanu et al. 2015, Marconi et al. 2013,
Goudie et al. 2001) detected nanoparticle compounds that are created as a result
of the reaction between anthropogenic aerosols, especially ammonium sulphate
(NH4HSO4), and their components. Samples collected at high altitudes are asso-
ciated with air masses traveling from North Africa deserts and coming from
Europe. As the nitrate concentration is not increased, this hypothesis is more
plausible than the hypothesis based on the large impact of local biomass com-
bustion emissions. At high altitudes, the old contamination layers from fossil
fuel combustions, possibly of North American origin, were encountered.

Harmattan is the name of the dust-

laden, dry wind that blows from the
shores of Western Africa coasts.
~ 134 ~
 Figure 3.1.4. Desert storm between Cape Verde Islands and Senegal
http://www.gmes-atmosphere.eu/news/dust_senegal/ sayfasında yayınlanan bu fotoğraf Google görsellerinden
alınmıştır.)

Geochemical indications of the dust particles, arising from the above mentioned
findings, are consistent with the previous results obtained from the area. Accor-
ding to these results, Si, Fe and Ti concentrations have not changed consistently
with the composition of the soil. However, concentrations of other elements,
such as Ca and S, have increased due to the industrial operations conducted in
the African deserts in the last decade (Strambeanu et al. 2015, Formenti 2003).

3) Cosmic Dusts
Total annual transportation of cosmic dusts (Figure 3.1.5) on the Earth is app-
roximately 40.000 tonnes. Majority of the cosmic dusts are originated from the
interplanetary dust cloud surrounding the Sun, star masses between Mars and
Jupiter or comets (Strambeanu et al. 2015, Zook 2001). Regardless of their sizes,
cosmic objects pass through the space on very high speeds, sometimes even
exceeding 150.000 km/hour. As they get closer to the Earth, they slow down due
to the friction in the atmosphere and this causes meteors to burn and characteris-
tically flare. Speeds of smaller particles also decrease due to the friction in the
atmoshpere, however, they reach the surface of the Earth without burning
(Strambeanu et al. 2015, Zook 2001).
Composition and size of interplanetary dusts are measured by using the satellites
in the space and infrared detection applications. Old and new studies revealed
that cosmic dust is consisted of micro particles, nano particles and their accumu-
lation. These dusts have irregular shapes and their porosity changes based on

~ 135 ~
whether the structure is spongy or compact. Their compositions, sizes and physi-
cochemical properties depend on their original source.

Figure 3.1.5. Kozmik Toz Bulutu

(https://www.nasa.gov/image-feature/goddard/2016/hubble-peers-into-the-storm sayfasında yayınlanan bu
fotoğraf Google görsellerinden alınmıştır.)

Interstellar dust clouds contain carbon monoxide, silicon carbide, amorphous

calcium silicate, water ice and poly(nuclear) aromatic hydrocarbons (PAH) or
other basic organic structure, whereas interstellar medium contains carbon and
silicon particles. On the other hand, comet dusts have different composition than
that of those originating from asteroid disruption. Comet dusts have similar
compositions to interstellar clouds, but the dusts originating from asteroid dis-
ruption have large amounts of silicon and iron (Strambeanu et al. 2015, Love et
al. 1992, Humphreys et al. 1972, Donald et al. 1999). In the comet dust samples
collected during recent space studies (Strambeanu et al. 2015, Donald et al.
2011) presence and ratios of different elements such as hydrogen, oxygen, car-
bon and nitrogen were discovered. Relations between these elements provide
information about the distance between the Sun and where the comets are for-
med, and the types of existing comets (e.g. ones closer to the Sun have higher
temperatures).

In addition, it was also revealed that cosmic dust contained organic matter comp-
lexes in the form of aromatic-aliphatic mixtures, which can be spontaneously
created in the universe. Computational chemistry studies on complex organic
molecules that form the basis of life have lead to the theory that these types of
molecules might be created by the nanoparticles orbiting around the Sun before
~ 136 ~
the Earth was formed (Strambeanu et al. 2015, Starkey 2013). Other studies
(Strambeanu et al. 2015, Gudipati et al. 2012) revealed that poly(nuclear) aroma-
tic hydrocarbons (PAH) are converted into amino acids and nucleotides via hyd-
rogenation, hydroxylation or partial oxidation under conditions similar to the
medium of stars. According to the recent estimations, it has been claimed that
more than 20% of the carbon compounds are based on PAH, that they were for-
med a little after the Big Bang and that they have played a role in the formation
of new stars and outer planets by spreading into the universe.
Studies conducted on the properties of nanoparticles provide very valuable in-
formation about the formation of planetary systems, source of organic matters
and water that produce the spontaneously growing systems that form the life,
and their roles.

3.1.3 Natural Nanoparticles in the Hydrosphere

Nanoparticles that are carried by natural water can be found everywhere. Very
small sizes ranging from 1 to 100 nanometers ensure that they are both highly
mobile and chemically reactive. Colloids and nanoparticles can be present in
numerous compositions and in different forms around us. Majority of colloids
are formed from biological degradation, low molecular weighted degradation
products (humic material) and from minerals produced during the chemical ab-
rasion of rocks, especially the oxides of iron (Fe), manganese (Mn) and alumi-
num (Al), and oxyhydroxides and aluminosilicates.

Figure 3.1.6. Rough formula of humic substance

(The image is published on http://karnet.up.wroc.pl/~weber/kwasy2.htm and retrieved from Google Images.)

The most studied sub class of natural organic matters is the humic substances
(HS). HS (Figure 3.1.6) can come together as irregular materials in a small por-

~ 137 ~
tion of nano size range (<5 nm) and as potentially larger structures (especially
mineral colloids) outside the nano range (Hartland et al. 2013, Tipping 2001).
Other natural organic substances found in natural waters include peptides, prote-
ins, peptidoglycans, polysaccharides and similar biomolecules. Polysaccharides
have fibrillary or cage-like configurations, however, proteins are generally glo-
bular and they degrade less than HS because of their differences. On the other
hand, HS generally reduce aggregation through charge and/or steric stabilization,
and such compounds have an effect to increase the sizes of nanoparticles and
colloids (Figure 3.1.7) via coagulation (Hartland et al. 2013, Buffle and Leppard
1995). In all environmental systems, metal oxides, especially iron and mangane-
se, are important nano-scaled phases that are capable of binding trace elements.
Nanoparticles and colloids typically have a negative electrostatic surface charge
in the neutral pH (~ pH 7) of natural waters. Thus, despite their original surface
potentials, almost all inorganic colloids in the natural waters have a negative
surface charge due to the HS surface coatings (Hartland et al. 2013, Tipping and
Higgins 1982). Similar charges between the particle surface, for example, nega-
tive and negative charges, allow nanoparticles and colloids to remain in a disper-
sed stable state in the water and form a suspension since similar charges repel
each other, whereas, surface charge differences of all particles, for example posi-
tive and negative charges, balance the opposite ions by forming a double layer
around the particle (Figure 3.1.8).

Figure 3.1.7. Grain size distribution of natural particles

(The image is published on
ttp://technique.eau.free.fr/index.php?coagulationfloculation=INTRODUCTIONCoagand retrieved from Goog-
le Images.)

~ 138 ~
 Figure 3.1.8. The stability of the colloidal system
(The image is published on http://www.silver-colloids.com/Tutorials/Intro/pcs7.html and retrieved from Goog-
le Images.)

In general, the mobility of nanoparticles in surface waters is limited only by their

colloidal stability. Similarly, nanoparticles can move smoothly in broken aqui-
fers. However, nanoparticles and colloid mobility is more limited since nanopar-
ticles are more likely to collide with soil particles in underground surface porous
media (e.g. Alluvial underground water aquifers). The number of collisions of
soil particle (Hartland et al. 2013, Tufenkji and Elimelech 2004, Nelson and
Ginn 2005) is determined by various events such as Brownian motion, shearing,
precipitation, inertia and hydrodynamic forces. Smaller particles move with a
largely random Brownian motion, this is especially true for nanoparticles. Vari-
ous retention mechanisms such as filtering, maximum holding time capacity of
the surface and charge heterogeneity on the soil surface can also be important for
the motion of nanoparticles and colloids in the porous medium.

3.1.4 Mechanisms for the formation of natural nanopartic-

les (NNPs)
All potential paths leading the classification and formation of NNPs are complex
and extensive. NNP formation occurs in all areas surrounding the world, chemi-
cal elements/species and wide range of mechanisms, processes and conditions.
~ 139 ~
Mentioned syntheses can take place with bottom-up approach starting from mo-
lecular/ionic species, such as iron hydride NNP formation from microbiological
activities or halogenure and aqueous sulphide NNP formation from the evapora-
tion of sea spray. Syntheses can take place with a top-down approach starting
from larger particles, such as nano-sized mineral particles produced via wind
erosion on the deserts or the formation of carbon nanoparticles through the com-
bustion of biomass (Sharma et al., 2015, Hochella et al. 2015, Wu et al. 2012,
Konishi et al. 2012).
Nano-sized objects in the world are formed in all areas involving troposphere,
hydrosphere that covers oceans, lakes, rivers, underground waters, lithosphere
that covers soil, rocks, magma etc., and the biosphere where all organisms live
including microorganisms and humans (Sharma et al., 2015, Hochella et al.
2015).
Basic processes that lead only to the formation of inorganic NNP (Figure 3.1.9);
- may only involve nucleation and growth of various inorganic phases in the
atmosphere, hydrosphere and even in the lithosphere as a result of inorganic
reactions or with the contribution of organic substances. Reactions in surface
waters and hydrothermal flues that contribute to the production of NNP can take
place with thermal, non-thermal and photochemical processes. Typical Fe(II)
formation in geochemical environment can ease the formation of iron hydride
nanoparticles that can be made stable via silicon ions (Sharma et al., 2015, Ko-
nishi et al. 2012). Other nanoparticles containing Mn, Cr, Cu, Ba and Pb can be
formed in cold carbon dioxide leakages.

Figure 3.1.9. An example for the formation of Ag NNP

~ 140 ~
(The image is published on
http://www.nature.com/nnano/journal/v11/n8/full/nnano.2016.93.html?WT.feed_name=subjects_nanotoxicolo
gy and retrieved from Google Images.)
Some of the mechanical processes affecting the NNP formation are mechanical
grinding of Earth’s crusts during earthquake, wind erosions in unforested and
non-planted soils and desert winds. In addition, mainly biomass combustion in
equatorial region of the world can be the best example for thermal processes.
Organisms, especially microorganisms, produce natural NP in the world. Biolo-
gical processes (or biomineralization) in the world can create several inorganic
nanomaterials like calcium phosphate, calcium carbonate, Fe and Si based na-
nominerals. Two processes are well understood and defined. One is the biologi-
cally induced mineralization (BIM), and the other one is biologically regulated
mineralization (BRM). In BIM process, aside from solid substrate attaching to
the bacteria or its the relation with bacteria cell, no other function specially cont-
rolled by microorganisms take place in the formation of nanoparticles. However,
nucleation and growth of the particles are controlled by microogranisms from
start to finish in the BRM process and nanominerals are generally created on the
cells under certain conditions. Therefore, mineral particles produced based on
the BRM process are well-defined crystals with narrow particle size distribution.
Nanoparticles that are produced via this process have various functions for mic-
roorganisms. For example, well-known magnetotactic bacteria (Figure 3.1.10)
use magnetic nanoparticles to find direction (Sharma et al., 2015, Schuler and
Frankel 1999).

Figure 3.1.10. Magnetotactic bacteria

~ 141 ~
 (The image is published on https://plus.google.com/+Vadilson)MalaquiasdosSantos/posts/THwdoxrumzR

and retrieved from Google Images.)

Figure 3.1.11. Red coloring of the waters as a result of iron production by bacte-
ria (BIM process).
(The images are published on
http://cfb.unh.edu/phycokey/Choices/Tribophyceae/TRIBONEMA/Tribonema_key.html,https://bacteria.ee/
and retrieved from Google Images.)

Alternatively, as exemplified in the production of Mn and Fe oxide nanocrystals

(typical BIM process), NNPs are produced via reduction reactions in microbial
medium that are indirectly related to metabolic processes. Best examples are
bacterial formation of ferric oxyhydroxide that is detected in sedimentation,
underground waters and soil, and the production of ferrihydrite by iron oxidizing
bacteria (Leptothrix, Gallionella) (Figure 3.1.11).
Nanoparticles can be formed naturally in aerosols, waters, soil, deep sea hydrot-
hermal vents, natural ores and microbial systems (Sharma et al., 2015, Hochella et
al. 2015). NNPs are formed by wind erosion at solid-gas phase threshold, by the
evaporation of sea spray at liquid-gas phase threshold, and by the abrasion of rocks
at the solid-liquid phase threshold. NNPs have a wide range in terms of chemical
composition and element diversity;

- metal oxides/hydroxides (for example; iron oxides/hydroxides, goethite, lepi-

dochrosite, akaganeite, manganese oxides/hydroxides etc.)
- metals and alloys (for example; metal nanoparticles)
- carbon allotropes and other non-metals
- silicates (for examples; aqueous aluminum silicate, fiber clay minerals such as
sepiolit etc.)
~ 142 ~
 - sulfides (for example; pyrites containing Cu and Zn (FeS2) etc.)
- sulfates, halogens and carbonates
Metal and noble metal nanoparticles have a particular importance among this
chemical group due to their impacts on the nature (Sharma et al., 2015, Kolar et al.
2014, Quigg et al. 2013).

It is also known that metal salts react with plant extracts, sugars, vitamins and a
wide range of antioxidants, and that the interaction of metal ions with natural
organic substances (NOS) and reactive oxygen species (ROS) has a crucial impor-
tance on the formation of natural metal nanoparticles present in the nature (Sharma
et al., 2015, Adegboyega et al. 2014, Yücel 2011, Hou et al. 2013, Yin et al. 2012,
Yin et al. 2014). NOS are complex matrices consisted of humic substances (HS),
which form the basic elements of underground waters, surface water and rivers,
precipitations and soils, and compositions such as protein and polysaccharides. HS
phenolic groups include conjugated double bonds and aromatic carbons. Their
definite structure is not completely known due to its high complexity. Its estimated
structure is shown in Figure 1. HS can be sub-groups of humic acids (HA), fulvic
acids (FA) and humin. Normally, HA are consisted of components that have high
molecular weight and not soluble in low pH. Contrary to this, FA are consisted of
components with low molecular weight that are soluble in a wide range of pH.
Humin is insoluble in any pH. ROS generally contains 1O2, O2‒•, H2O2 and •OH
which are produced in natural surface waters via Fenton or Fenton-like reactions
and photochemical ways (Sharma et al., 2015, Adegboyega et al. 2014, Yin et al.
2012, Yin et al. 2014).

Inorganic sulfur (H2S and HS-) is the most important part of global biogeochemi-
cal sulfur cycle under anaerobic conditions, which includes mud purification sys-
tems, continental soils, precipitations, mine water, hydrothermal vents (Figure
3.1.12). Metals and sulfurs in the oceans can spread from the high-temperature
ventilations and they can react with each other to be used as the source of metal-
carrying sulfur nanoparticles. Metals and their sulfide nanoparticles can remain in
colloidal form as suspended. A series of metal sulfide nanoparticles (Ag2S, CuS,
CdS and ZnS) are found in sulfide environment (Sharma et al., 2015, Levard et al.
2012, Mullaugh and Luther III 2011, Schaffie and Hosseini 2014, Ma et al. 2014).
Natural formation of noble metal sulfides affects the speciation, motion and bioa-
vailability of many important metals. For example, sulfur inside the metal sulfides

~ 143 ~
resist against oxidation due to the strong complexation with the metal and this
limits the bioavailability of the metal (Sharma et al., 2015, Thalmann et al. 2014).

Although there are many studies about the natural formation of inorganic nano-
particles, it is still difficult to explain the formation mechanisms. There are very
limited number of detailed mechanical studies on chemical, photochemical, mec-
hanical, thermal and biological processes that form natural nanoparticles. In natu-
re, more than one reaction pathway can contribute to the formation of natural
nanoparticles.

Figure 3.1.12. Sulfur cycle

(The image is published on https://commons.wikimedia.org/wiki/File:Sulfur_Cycle_(Ciclo_do_Enxofre).png
and retrieved from Google Images.)

In recent years, some progress has been observed for the explanation of formation
mechanisms of noble metal nanoparticles in various systems. The interaction of
precursor noble metal ions with natural organic substances under thermal and
irradiance conditions of oxygenated water is mostly responsible for the formation
of noble metal nanoparticles (gold and silver nanoparticles). The formation of
noble metal nanoparticles varies by source species, such as sediments, aquatic and
solid, and from fulvic acid to humic acid. It has been suggested that alcohol, al-
dehyde and phenol parts of humic acid can trigger photoreduction and produce
noble metal nanoparticles. However, due to the opposing views on the formation
of noble metal nanoparticles under sunlight, more advanced mechanical details
required more detailed examination for completely understanding the reduction
process under sunlight in the presence of natural organic substance. We need mo-

~ 144 ~
re information to explain the roles of reactive oxygen species and temporary or-
ganic substances on noble metal formation mechanism from special complexes
under natural conditions. In addition to the properties of dissolved organic subs-
tance, valence status of reduction species present in solution mixture also plays an
important in the formation of noble metal nanoparticles. How iron species
(Fe(II)/Fe(III)) increase the formation of noble metal nanoparticles under thermal
conditions and how do sunlights take place in formation mechanisms require mo-
re advanced examinations. In situ demonstration of particle formation is still a
problem.

According to the published results, noble metal nanoparticles, such as silver and
gold nanoparticles, formed via the reduction of ionic salts are produced by humic
and fulvic acids under thermal and irradiation conditions and are stable for long
periods of time in aquatic environment. Naturally occurring noble metal nanopar-
ticles with this high stability are highly likely to be migrated to the distances far
away from their original locations. However, the pH, ionic strength and chemistry
of solid and aqueous phases affect the conversion, dissolution, agglomeration and
hence mobility of natural nanoparticles.

As a result, the natural organic functional groups that surround naturally occurring
noble metal nanoparticles can significantly affect their toxicity. There is very
limited information about how these nanoparticles interact with organisms in the
water. These nanoparticles may exhibit varying toxicity depending on the forma-
tion of reactive oxygen species and the functional properties of the organic subs-
tances. Future studies to assess the mechanisms underlying the toxicity of natu-
rally occurring nanoparticles are of great importance.

Natural nanoparticles have a great importance on global biogeochemical cycles,

weather conditions, metal binding and transport, bioavailability and ecotoxicity in
the earth's system. In addition, the effect of nanoparticles on the bioavailability of
nutrients and toxic elements has been a factor in the evolution and development of
high organisms, potentially buffering the environmental systems against change
(Tipping 2001). Therefore, it is interesting that produced nanoparticles became a
focus of attention since they are present in much lower amounts than their natural
counterparts. This is because the produced nanoparticles differ from those found
in nature and is made from specific structures and chemicals that organisms can
not have the proper defense mechanisms for.

~ 145 ~
Summary

Nanoparticles are substances having the sizes of one billionth of a meter. The
discovery and use of nanoparticles have a long history. The first used nanoparticles
were the nanoparticles produced by the nature in different ways. The developments
in technology have enabled us to see them and allowed diversity in their produc-
tion. There are many natural processes that enable the natural formation of nano-
particles. Lots of processes have been suggested, especially when it is examined in
terms of atmospheric, aquatic and terrestrial formation sources. Since nanoparticles
can be present in every edge of life that covers the world, they can also be formed
through the solar events. The recent and rapid developments in the science have led
nanoparticles to take an important place in the explanation of the theories about
how the universe and the life in our world had taken shape immediately after the
Big Bang. There is still no clear and detailed explanation for the formation of
naturally occurring nanoparticles, but it is known that noble metals and humics
play an active role in such formation. However, there is very limited information
on the toxicity of NNP, and there are many studies on the toxic effects and diffe-
rent applications of nanoparticles produced for engineering purposes.

~ 146 ~
References

Adegboyega, N. F., Sharma, V. K., Siskova, K. M., Vecerova, R., Kolar, M., Zbo-
ril, R., Gardea-Torresdey, J. L., 2014, Interactions of Aqueous Ag+ with Fulvic
Acids: Mechanisms of Silver Nanoparticle Formation and Investigation of Stability
Environmental Science & Technology, 48, 3228–3235.

Batley, G.E., Kirby J.K. and McLaughlin M.J., 2013, Fate and Risks of Nanomate-
rials in Aquatic and Terrestrial Environments, Accounts of Chemical Research, 46,
854-862.

Buffle, J. and Leppard, G.G., 1995, Characterization of aquatic colloids and mac-
romolecules.1. Sutructure and behavior of colloidal material, Environmental Scien-
ce & Technology, 32, 2887-2899.

Bureau, H., Keppler, H., et al. (2000) Volcanic degassing of bromine and iodine:
experimental fluid/melt partitioning data and applications to stratospheric che-
mistry. Earth and Planetary Science Letters, 183, 51-60.

Cadle, R.D., 1980, A comparison of volcanic with other fluxes of atmospheric

trace gas constituents, Reviews of Geophysics and Space Physics ,18, 746-752.

Chin, M., Davis D.D., 1993, Galobal sources and sinks of OCS and CS2 and their
distributions, Global Biogeochemical Cysles, 7, 321-337.

Chun, Y., Cho, H. et al., 2008, Historical records of Asian dust events (Hwangsa)
in Korea. Bulletin of the American Meteorological Society, 89, 823–827.

Donald D, Clayton W et al., 1999, Condensation of carbon in radioactive superno-

va gas, Science, 283, 1290–1292.

Donald, D., Clayton, W., 2011, A new astronomy with radioactivity: radiogenic
carbon chemistry, Reviews, 55,155–165.

Formenti, P., Elbert, W.J., Maenhaut, W., Haywood, J., Andreae, M. O., 2003,
Chemical composition of mineral dust aerosol during the Saharan Dust Experiment
(SHADE) airborne campaign in the Cape Verde region, September 2000, Journal
of Geophysical Research: Atmospheres, 108, DOI: 10.1029/2002JD002648.

~ 147 ~
Goudie, A.S., Middleton, N.J. , 2001, Saharan dust storms: nature and consequen-
ces, Earth-Science Reviews, 56, 179–204.

Gudipati, M.S., Yang, R., 2012 In-situ probing of radiation-induced processing of

organics in astrophysical ice analogs: novel laser desorption laser ionization time-
of-flight mass spectroscopic studies, Astrophysical Journal Letters, 756, 1.
http://iopscience.iop.org/2041-8205/756.

Hartland, A., Lead, J.R., Slaveykova, V., I., O'Carroll, D., Valsami-Jones, E., 2013,
The environmental significance of natural nanoparticles, Nature Education
Knowledge, 4, 7-13.

Hochella, J.M.F., Spence, M.G. and Jones K.L., 2015, Nanotechnology: nature's
gift or scientists' brainchild?, Environmental Science: Nano, 2, 114-119.

Hou, W.C., Stuart, B., Howes, R., Zepp, R.G., 2013, Sunlight-Driven Reduction of
Silver Ions by Natural Organic Matter: Formation and Transformation of Silver
Nanoparticles, Environmental Science & Technology, 47, 7713–7721.

Humphreys, W., Roberta, M. et al.,1972, Spectroscopic and photometric observa-

tions of M Supergiants in Carina, The Astrophysical Journal, 172, 75.

Juravle D., 2012, Geologia Romaniei, Vol 1 Editura Universitatatii, Iaşi.

Konishi, H., Xu, H. and Guo, H., 2012, Nanostructures of natural iron oxide nano-
particles, Nature's Nanostructures, 75–113.

Levard, C., JHotze, E. M., Lowry, G. V., Brown, J. G. E., 2012, Environmental
Transformations of Silver Nanoparticles: Impact on Stability and Toxicity, Envi-
ronmental Science & Technology, 46, 6900–6914.

Love, S.G., Joswiak, D.J. et al., 1992, Densities of stratospheric micrometeorites.

Icarus, 111, 227–236.

Ma, R., Levard, C., Judy, J. D., Unrine, J. M., Durenkamp, M., Martin, B., Jeffer-
son, B., Lowry, G. V., 2014, Fate of Zinc Oxide and Silver Nanoparticles in a Pilot
Wastewater Treatment Plant and in Processed Biosolids, Environmental Science &
Technology, 48, 104–112.

~ 148 ~
Marconi M, Sferlazzo DM et al (2013) Saharan dust aerosol over the central medi-
terranean sea: optical columnar measurements vs. aerosol load, chemical composi-
tion and marker solubility at ground level. Atmos Chem Phys Discuss 13:21259–
21299.

McElroy, M.B., Salawitch, R.J., et al. 1992, The changing stratosphere, Planetary
and Space Science, 40, 373-401.

Mullaugh, K. M. and Luther III, G. W., 2011, Growth kinetics and long-term
stability of CdS nanoparticles in aqueous solution under ambient conditions, Jour-
nal of Nanoparticle Research, 13, 393–404.

Nelson, K.E. and Ginn, T.R., 2005, Colloid filtration theory and the Happel sphere-
,n-cell model revisited with direct numerical simulation of colloids, Langmuir, 21,
2173-2184.

Quigg, A., Chin, W.-C., Chen, C.-S., Zhang, S., Jiang, Y., Miao, A.-J., Schwehr, K.
A., Xu, C., Santschi, P. H., 2013, Direct and Indirect Toxic Effects of Engineered
Nanoparticles on Algae: Role of Natural Organic Matter, ACS Sustainable Che-
mistry & Engineering, 1, 686–702.

Saha K., Agasti S.S., Kim C., Li X. and Rotello V.M., 2012, Gold Nanoparticles in
Chemical and Biological Sensing, Chemical Reviews, 112, 2739-2779.

Schaffie, M.and Hosseini, M. R., 2014, Journal of Nanoparticle Research, Journal

of Environmental Chemical Engineering, 2, 386–391.

Schüler, D. and Frankel, R. B., 1999, Bacterial magnetosomes: microbiology,

biomineralization and biotechnological applications, Applied Microbiology and
Biotechnology, 52, 464–473.

Sharma V.K., Siskova K., Zboril R., Gerdea-Torresdey J., 2014, Organic-coated
silver nanoparticles in biological and environmental conditions: Fate, stability and
toxicity, Advances in Colloid and Interface Science, 204, 15-34.

Sharma, V.K., Filip J., Zboril R., Varma, R.S., 2015, Natural inorganic nanopartic-
les- formation, fate, and toxicity in the environment, Chemical Society Reviews,
44, 8410-8423.

~ 149 ~
Shi, Z., Shao, L., Jones, T., Lu ,S., 2005, Microscopy and mineralogy of airborne
particles collected during severe dust storm episodes in Beijing, China. Journal of
Geophysical Research, p 30.

Starkey, N., 2013, Insight into the silicate and organic reservoirs of the comet
forming region, Geochimica et Cosmochimica Acta, 105, 73–91.

Strambeanu N., Demetrovici L., Dragos D., 2015, Nanoparticles' Promises and
Risks, Springer International Publishing, Switzerland. doi 10.1007/978-3-319-
11728-7_2.

Symond, R.B., Rose W.I., et al., 1988, Contribution of Cl- and F-bearing gases to
the atmosphere by volcanes, Nature, 334, 415-418.

Symond, R.B., Rose W.I., et al., 1994, Volcanic gas studies: methods, results and
applications, Reviews in Mineralogy and Geochemistry, 30, 1-66.

Taylor DA (2002) Dust in the wind. Environ Health Perspect 110(2):A80–A87,

http://www. ncbi.nlm.nih.gov/pubmed/?term=Taylor%20DA%5Bauth%5D.

Textor, C., Graf, H.F., Timmreck, C., Robock A., 2003, Emmissions from volca-
noes, Kluwer, Dordrecht.

Thalmann, B., Voegelin, A., Sinnet, B., Morgenroth E., Kaegi, R., 2014, Sulfida-
tion Kinetics of Silver Nanoparticles Reacted with Metal Sulfides, Environmental
Science & Technology, 48, 4885–4892.

Tipping, E. and Higgins, D.C., 1982, The effect of adsorbed humic substances on
the colloid stability of hematite particles, Colloids and Surfaces, 5, 85-92.

Tipping, E., 2001, Cation binding by humic substances, Cambridge, University

Press.

Tufenkji, N. and Elimelech, M., 2004, Deviation from classical colloid filtration
theory in the presence of repulsive DLVO interactions, Langmuir, 20, 10818-
10828.

Wang, G.H., Zhou, C.B., et al. 2012, Impact of Gobi desert dust on aerosol che-
mistry of Xi'an, inland China during spring 2009: differences in composition and

~ 150 ~
size distribution between the urban ground surface and the mountain atmosphere,
Atmospheric Chemistry and Physics Discussions, 12, 21355-21397.

Wu, J., Yao, J. and Cai, Y., 2012, Biomineralization of natural nanomaterials,
Nature's Nanostructures, 225–247.

Xiaodan, D., 2007, Northern dust brings dirty skies in Shanghai. Journal of Ge-
ophysical Research.

Yin, Y., Liu, J., Jiang, G., 2012, Sunlight-Induced Reduction of Ionic Ag and Au to
Metallic Nanoparticles by Dissolved Organic Matter, ACS Nano, 6, 7910–7919.

Yin, Y., S. Yu, J. Liu and G. Jiang, 2014, Thermal and Photoinduced Reduction of
Ionic Au(III) to Elemental Au Nanoparticles by Dissolved Organic Matter in
Water: Possible Source of Naturally Occurring Au Nanoparticles, Environmental
Science & Technology, 48, 2671–2679.

Yücel, M., Gartman, A., Chan, C. S., Luther III, G. W., 2011, Hydrothermal vents
as a kinetically stable source of iron-sulphide-bearing nanoparticles to the oc-
ean,Nature Geoscience, 4, 367–371.

Zook, H.A., 2001, Accretion of extraterrestrial matter throughout Earth’s history.

pp 75–92.

~ 151 ~
3.2 METAL and ALLOY NANOPARTICLES

Dr. Gülşin ARSLAN

garslan@selcuk.edu.tr
Dr. İdris SARGIN
idris.sargin@selcuk.edu.tr
SELÇUK UNIVERSITY
INTRODUCTION
Metal and alloy nanoparticles are nano-scale particles with size of 1‐100 nm.
These particles are agglomerates of atoms and they can be synthesized from the
same atom as well as two or more different atoms [Baletto and Ferrando, 2005].
These nanoparticles draw great attention in recent years since their optical, elect-
rical and catalytic properties can be adjusted depending on the quantum sizes.
Optical, electrical and catalytic properties of alloy nanoparticles can be ad-justed
simply by changing the composition of the alloy. In the syn-thesis of metal and
alloy nanoparticles, it is possible to produce alloy nanoparticles below 10 nm in
size and they can exhibit diverse size-dependent variations [Raveendran et al.,
2006]. Surface structures, compositions and decomposition properties of nano-
alloys determine their reactive and catalytic behaviors. Therefore, bimetallic
nano-alloy can manifest synergistic properties and can have significantly diffe-
rent structures and properties than the metal clusters with the same size [Ferran-
do et al., 2008]. Unlike the metals, synergistic ef-fects enables the improvement
of certain properties of the alloy after it is formed, therefore, metal alloys has
found wide applications fields in ecology, electronics, materials and machinery
[Ruban et al., 1999].

3.2.1 Production Methods in Development of Technology

and the Importance of Material
Nanotechnology covers the design, production and functional use of na-
nomaterials and production of metal nanoparticles (NP) is one of the most im-
portant steps for new materials in nanotechnology. Metal NPs can be produced
in a wide chemical range and morphology. The reason for NPs to stand out can
be listed as quantum size effects, size dependency of electrical structure, unique
characteristics of surface atom and high sur-face/volume ratio [Liveri, 2006].
They take part in the preparation of many technological and pharmacological
products, catalysts, special technolog-ical materials for optical applications, su-
~ 152 ~
perconductors, abrasion-resistant additives, surface active agents and drug carri-
ers. Today, NPs having dif-ferent morphologies such as core-shell, additive,
sandwich, hollow, spheri-cal, rod-like and other geometric features with desired
properties can be prepared from metal, metal alloy, ceramic, polymer-based or
combinations of these.
In the preparation of nano-structured materials, physical approach includ-ing
thermal and heat treatment, diffusion, electrolysis, chemical approach including
core formation, reduction and electrochemical processes or bio-logical approach
including microorganisms and plants are accepted in general. In addition, diffe-
rent systems such as chemical vapor condensa-tion, hydrogen reduction, and
noble gas condensation, production from microheterogeneous systems, flame
synthesis, mechanical abrasion and ultrasonic spray pyrolysis methods are used
for the production of metallic and oxide-based NPs [Liveri, 2006].
Synthesized NP initially starts to form a core for which the shape, size and com-
position can be adjusted, then the nano-sized shell of the second metal is agglo-
merated on top it; this process step is critical and the core/shell nanosystem is
heated up to very high temperatures in order for the metals to diffuse into each
other.
Nanomaterials are of great importance due to their unique properties relat-ed to
their high surface-volume ratio, and they have a wide range of appli-cations
including catalysts, drug industry, optical materials, sensors, ener-gy storage-
transmission [Haverkamp and Marshall, 2009]. Functions and areas of use of
these materials vary depending on the size and composi-tion of the NPs. Silver
(Ag) NPs can be used in household tools, platinum (Pt) NPs in industrial and
biomedical applications and gold (Au) NPs can be used in sensor studies.
Depending on the filling of the electronic shells of the alkali metal bulks formed
by the agglomeration of small atomic masses such as Cu and Ag, the sizes will
be enlarged and certain nuclei will become partially stable like the jellium mo-
del. Bulks of some main group metals (Al, Ca and Sr) and transition metals ge-
nerally have large sizes in polyhedral bulks with con-centric geometric shells
and the competition between the bonding and surface energy effects is what
provides the stable shape of a bulk [Fer-rando et al., 2008].

~ 153 ~
Nano alloys can be synthesized in variety of ways including gas phase, solution
and various mediums supported by a lower layer or a matrix (Figure 3.2.1)
[Schmid, 2011].

Figure 3.2.1. Transmission electron microscope (TEM) image of Bi-Pb alloy

NPs formed through in situ agglomeration
(Copyright 2004 American Physical Society) [Jesser et al., 2004].

3.2.2 Biosynthesis of Metal NPs

Reduction of metal ions with sodium reducing agents is the most widely used
method in the synthesis of metal NP. Sodium borohydride and sodi-um citrate as
well as glucose, fructose and sucrose sugars are used as reducing agents in the
synthesis of metal NPs [Panigrahi et al., 2004]. In addition to health, environ-
mental and economic concerns, it is difficult to keep the particle size and morp-
hology within a certain range with produc-tion using conventional chemical
methods. The production of metal NPs by biological methods has attracted inte-
rest in recent years as an alterna-tive to conventional chemical methods. Not
using toxic agents in the syn-thesis of NP, the ability to carry out the synthesis at
ambient temperature and pressure are among the advantages of the biological
method [Raveendran et al., 2003]. Biomineralization of NPs in protein holes is
one of the biological methods for NP production. This method allows control-
ling the particle size and morphology [Sau and Rogach, 2010]. Bacteria, fungi,
lichens and algae are used in biogenic NP synthesis. These biologi-cal creatures
secrete large amounts of extracellular and intracellular pro-teins, and these prote-
ins function as a template for the reduction of metal cations to metallic form
[Mandal et al., 2006]. The fundamental criteria in microorganism selection are

~ 154 ~
whether the microorganisms have the reduc-tase enzyme. In other words, mic-
roorganisms that are capable of releasing reductase enzyme are used in metal NP
synthesis. From bacteria species; Bacillus subtilis, Bacillus Licheniformis, Bacil-
lus mycoides, Bacillus methylotrophicus, Bacillus cereus, Streptococcus ther-
mophilus, Escherichia coli, Lactobacillus acidophilus and Enterococcus sp.,
from fungi; Aspergil-lus sp., Fusarium sp., Penicillium sp., Trichoderma sp.,
Verticillium sp. ve Trichothecium sp. and from yeasts; Saccharomyces cerevi-
siae, Saccharo-myces boulardii, Yarrowia lipolytica, Candida sp., Rhodotorula
sp. and Pich-ia pastoris) are used in metal NP synthesis [Vaseghi et al., 2017].
Recently, various plant extracts are also being frequently used in metal NP synt-
hesis in addition to the microorganisms [Nadagouda and Varma, 2008; Iravani,
2011].

3.2.3 Metals used in NP synthesis

Metals such as gold, silver, copper, zirconium, cadmium, magnesium, alumi-

num, iron, titanium, platinum, paladium and metal oxides such as TiO2, ZnO,
NiO, MnO2, Cr2O3, Cu2O, Fe3O4, ZrO2, In2O are utilized in NP pro-duction
and being used in various applications [Iravani, 2011; Ng et al., 2013].

3.2.4 Uses of Metal NPs

The properties of metal NPs depend on their size and shape. Many metal NPs
produced in different size, shape and morphology are widely used in chemical
and biosensor manufacturing studies, catalyst synthesis, elec-tronic device com-
ponent preparation, imaging systems, medical and envi-ronmental applications.
Some examples of NPs areas of use can be sum-marized as follows:

Gold NPs are biocompatible and have found widespread use in medical practice
for their affinity in -SH groups. Colloidal gold NPs are used as a cancer-targeted
drug delivery device [Paciotti et al., 2004] and in cancer diagnosis [El-Sayed et
al., 2005].

Silver NPs have been used in healthcare industry, food storage ap-plications and
textile products because of its anti-bacterial proper-ties [El-Nour et al., 2010].
Silver NPs immobilized in hydrogel exhib-ited anti-bacterial effect against E.
coli [Mohan et al., 2007]. In an-other study, silver NPs were used as antibacterial

~ 155 ~
agents in the sur-face coating of plastic catheters [Roe et al., 2008]. In addition,
silver NPs are also widely used in electronics [Alshehri et al., 2012].

Similar with the silver, antimicrobial, antifungal and antiviral proper-ties of cop-
per are also known for centuries. In recent studies, cop-per NPs are frequently
being used as alternatives to silver NPs due to their low costs [Ingle et al., 2014].

Zirconium coated graphite electrodes are used to make peroxide bi-osensor [Liu
et al., 2004]. Zinc oxide NPs are attractive semiconduc-tors for their photolumi-
nescence properties. They are used in ultra-violet laser devices and biomedical
marking because of these prop-erties [Xiong et al., 2009].

Metal and alloy NPs also represent one of the most innovative tech-nologies for
ecological use. For example, nano-scale (1-100 nm) Fe and Pd-Fe particles are
used for the treatment of waste water [Wang and Zhang, 1997]. In addition, Pd-
Au NPs are also used for improv-ing the underground waters containing trichlo-
roethene and other chlor-based compounds [Nutt et al., 2005].

3.2.5 Alloy NPs

Researchers who want to specify the exact structure and properties of nanomate-
rials in nanoscale are shifted from single-atom systems to bi-metallic or multi-
metallic systems. The ability to adjust the physical and chemical properties of
nanomaterials by altering the composition of the compounds in metal alloy sys-
tems is one of the main reasons why nano-alloys draw that much interest. The
composi-tion, distinction degree and surface structure of nano-alloys deter-mine
the chemical reactivity and catalytic activity of nanomaterials. The interesting
thing is alloy NPs may exhibit properties different from the pure particles of the
metals that form them. Sometimes synergistic effect is observed in catalytic
systems where nanoalloys are used.

3.2.6 Arrangement of metal atoms in alloy NPs

Different arrangements are observed as the metal atoms form alloys in the nano
scale. These are;
i. Core-shell configuration (AcoreBshell) is the most common con-
figuration and the metal core composing the shell completely sur-
rounds the metal,
~ 156 ~
 ii. Layered-derived NPs (“Janus” double-sided particles); two diffe-
rent atoms forming the particle compose a different side of the
nanomaterial,
iii. Mixed configuration; is the most general alloy configuration and
atoms may be partially ordered or randomly mixed [Ferrando et
al., 2008].

3.2.7 Uses of Alloy NPs

Like metal NPs, the physical and chemical properties of alloy NPs depend on
their size and morphology. In bimetallic or multi-metallic alloy systems, the
properties of the nanomaterials also depend on the chemical composi-tion of the
materials and the arrangement of the atoms. This way, it is pos-sible to synthesi-
ze nanoparticles with very different properties by manipu-lating the elemental
composition of the nano-alloy, conditions of the syn-thesis process and the array
configuration of the atoms. This versatility of nano-alloys has opened up the way
for use in a variety of areas such as biological identification, drug release, bio-
sensors and catalytic systems [Rosi and Mirkin, 2005].

The reciprocal effect of neighboring metal atoms in catalyst systems can lead to
synergistic effects, and in general, nano-alloy systems can exhibit better catalytic
activity than monoatomic systems [Ferrando et al., 2008; Zaheer et al., 2011]. In
a catalyst study conducted with nano-alloys, silver-rich AgPd nanoaluminum
was used in the reduction of oxygen in an alka-line environment [Slanac et al.,
2012]. In another study, NiCoB nano-alloy catalyst was used in the hydrogena-
tion of p-chloronitrobenzene [Shen and Chen, 2007].

There is increasing interest in the use of nano-alloys in biosensor studies in re-

cent years. Ni–Cu/TiO2 electrodes are used as glucose sensors [Li et al., 2013].
Pt:Co nano-alloy is used for the voltammetric detection of B9 vita-min in food
samples [Jamali et al., 2014].

~ 157 ~
Conclusion

Metal NPs and nano-alloys are very important among nanomaterials. As their
properties can be controlled, many metal particles can be prepared in nano scale
and used in different applications. Biological synthesis of met-al NPs, in addition
to conventional chemical and physical methods, might be an indicator that this
field will further expand.

~ 158 ~
References

Alshehri, A. H., Jakubowska, M., Młożniak, A., Horaczek, M., Rudka, D.,
Free, C., & Carey, J. D. (2012). Enhanced electrical conductivity of
silver nanoparticles for high frequency electronic applications. ACS
Applied Materials & Interfaces, 4(12), 7007-7010.

Baletto, F., and Ferrando, R., (2005). Structural properties of nanoclusters:

Energetic, thermodynamic, and kinetic effects. Reviews of Modern
Physics, 77, 371-423.

El-Nour, K. M. A., Eftaiha, A. A., Al-Warthan, A., & Ammar, R. A. (2010).

Synthesis and applications of silver nanoparticles. Arabian Journal of
Chemistry, 3(3), 135-140.

El-Sayed, I. H., Huang, X., & El-Sayed, M. A. (2005). Surface plasmon reso-
nance scattering and absorption of anti-EGFR antibody conjugated
gold nanoparticles in cancer diagnostics: applications in oral cancer.
Nano Letters, 5(5), 829-834.

Ferrando, R., Jellinek, J., and Johnston, R.L., (2008). Nanoalloys: from theory
to applications of alloy clusters and nanoparticles. Chemical Reviews,
108, 845-910.

Haverkamp, R.G., and Marshall, A.T. (2009), The mechanism of metal nano-
particle formation in plants: limits on accumulation, Journal of Nano-
particle Research, 11(6), 1453-1463.

Ingle, A. P., Duran, N., & Rai, M. (2014). Bioactivity, mechanism of action,
and cytotoxicity of copper-based nanoparticles: a review. Applied
Microbiology and Biotechnology, 98(3), 1001-1009.

Iravani, S. (2011). Green synthesis of metal nanoparticles using plants. Green

Chemistry, 13(10), 2638-2650.

Jamali, T., Karimi-Maleh, H., & Khalilzadeh, M. A. (2014). A novel nanosen-

sor based on Pt:Co nanoalloy ionic liquid carbon paste electrode for
voltammetric determination of vitamin B 9 in food samples. LWT-
Food Science and Technology, 57(2), 679-685.
~ 159 ~
Jesser, W., Shneck, R., and Gile, W., (2004). Solid-liquid equilibria in nano-
particles of Pb-Bi alloys. Physical Review B, 69, 144121-144134.

Li, X., Yao, J., Liu, F., He, H., Zhou, M., Mao, N., ... & Zhang, Y. (2013).
Nickel/Copper nanoparticles modified TiO2 nanotubes for non-
enzymatic glucose biosensors. Sensors and Actuators B: Chemical,
181, 501-508.

Liu, S., Dai, Z., Chen, H., & Ju, H. (2004). Immobilization of hemoglobin on
zirconium dioxide nanoparticles for preparation of a novel hydrogen
peroxide biosensor. Biosensors and Bioelectronics, 19(9), 963-969.

Liveri, V. T. (2006). Controlled Synthesis of Nanoparticles in Microheteroge-

neous Systems, Springer Science+Business Media, Inc., New York.

Mandal, D., Bolander, M. E., Mukhopadhyay, D., Sarkar, G., & Mukherjee, P.
(2006). The use of microorganisms for the formation of metal nano-
particles and their application. Applied Microbiology and Biotechno-
logy, 69(5), 485-492.

Mohan, Y. M., Lee, K., Premkumar, T., & Geckeler, K. E. (2007). Hydrogel
networks as nanoreactors: A novel approach to silver nanoparticles for
antibacterial applications. Polymer, 48(1), 158-164.

Nadagouda, M. N., & Varma, R. S. (2008). Green synthesis of silver and pal-
ladium nanoparticles at room temperature using coffee and tea extract.
Green Chemistry, 10(8), 859-862.

Ng, L. Y., Mohammad, A. W., Leo, C. P., & Hilal, N. (2013). Polymeric
membranes incorporated with metal/metal oxide nanoparticles: a
comprehensive review. Desalination, 308, 15-33.

Nutt, M.O., Hughes, J.B., and Wong, M.S. (2005). Designing Pd-on-Au bime-
tallic nanoparticle catalysts for trichloroethene hydrodechlorination.
Environmental Science & Technology, 39, 1346-1353.

Paciotti, G. F., Myer, L., Weinreich, D., Goia, D., Pavel, N., McLaughlin, R.
E., & Tamarkin, L. (2004). Colloidal gold: a novel nanoparticle vector
for tumor directed drug delivery. Drug Delivery, 11(3), 169-183.
~ 160 ~
Panigrahi, S., Kundu, S., Ghosh, S., Nath, S., & Pal, T. (2004). General met-
hod of synthesis for metal nanoparticles. Journal of Nanoparticle Re-
search, 6(4), 411-414.

Raveendran, P., Fu, J., & Wallen, S. L. (2003). Completely “green” synthesis
and stabilization of metal nanoparticles. Journal of the American
Chemical Society, 125(46), 13940-13941.

Raveendran, P., Fu, J., and Wallen, S.L., (2006). A simple and “green” method
for the synthesis of Au, Ag, and Au–Ag alloy nanoparticles. Green
Chemistry, 8, 34-38.

Roe, D., Karandikar, B., Bonn-Savage, N., Gibbins, B., & Roullet, J. B.
(2008). Antimicrobial surface functionalization of plastic catheters by
silver nanoparticles. Journal of Antimicrobial Chemotherapy, 61(4),
869-876.

Rosi, N. L., & Mirkin, C. A. (2005). Nanostructures in biodiagnostics. Chemi-

cal reviews, 105(4), 1547-1562.

Ruban, A., Skriver, H.L., and Nørskov, J.K., (1999). Surface segregation ener-
gies in transition-metal alloys. Physical Review B, 59, 15990-16000.

Sau, T. K., & Rogach, A. L. (2010). Nonspherical noble metal nanoparticles:

colloid‐chemical synthesis and morphology control. Advanced Materi-
als, 22(16), 1781-1804.

Schmid, G., (2011). Nanoparticles: from theory to application. John Wiley &
Sons.

Shen, J. H., & Chen, Y. W. (2007). Catalytic properties of bimetallic NiCoB

nanoalloy catalysts for hydrogenation of p-chloronitrobenzene. Journal
of Molecular Catalysis A: Chemical, 273(1), 265-276.

Slanac, D. A., Hardin, W. G., Johnston, K. P., & Stevenson, K. J. (2012).

Atomic ensemble and electronic effects in Ag-rich AgPd nanoalloy ca-
talysts for oxygen reduction in alkaline media. Journal of the Ameri-
can Chemical Society, 134(23), 9812-9819.

~ 161 ~
Vaseghi, Z., Nematollahzadeh, A., & Tavakoli, O. (2017) Green methods for
the synthesis of metal nanoparticles using biogenic reducing agents: a
review. Reviews in Chemical Engineering (DOI: 10.1515/revce-2017-
0005).

Wang, C.B., and Zhang, W.X. (1997). Synthesizing nanoscale iron particles
for rapid and complete dechlorination of TCE and PCBs. Environmen-
tal Science & Technology, 31, 2154-2156.

Xiong, H. M., Shchukin, D. G., Möhwald, H., Xu, Y., & Xia, Y. Y. (2009).
Sonochemical synthesis of highly luminescent zinc oxide nanopartic-
les doped with magnesium (II). Angewandte Chemie International
Edition, 48(15), 2727-2731.

Zaheer, M., Motz, G., & Kempe, R. (2011). The generation of palladium sili-
cide nanoalloy particles in a SiCN matrix and their catalytic applicati-
ons. Journal of Materials Chemistry, 21(46), 18825-18831.

~ 162 ~
3.3 NATURAL POLIMERIC NANOPARTICLES

Dr. Arzu YAKAR

ayakar@pau.edu.tr
AFYON KOCATEPE UNIVERSITY
INTRODUCTION
Polymers are comprised of chemical structures called monomers and they have
many molecules, therefore they are also called macromolecules and they form a
class of synthetic or natural matters. Living organisms have many polymers
including cellulose, proteins and nucleic acids. Synthetically produced materials
like cement, glass, paper and plastic are known to be polymers consisted of mi-
nerals such as graphite, quartz and feldspar. Some natural polymers are consisted
of a single monomer. As with copolymer, many natural and synthetic polymers
can be formed by combination of two or more monomers. Some natural poly-
mers are presented in Table 3.3.1. DNA, RNA, protein and polysaccharides are
among the most well-known natural polymers. Natural polymers of polysaccha-
rides and proteins are widely used in nanotechnological studies.

Table 3.3.1. Some natural polymers

This image is published on https://www.studyblue.com/notes/hh/examples-monomers/24537649871212579

and retrieved from Google Images.)

~ 163 ~
3.3.1 Natural Polymers

Various natural polymers are used for the preparation of nanoparticles, especi-
ally to minimize the side effects that may occur during tissue engineering and
drug delivery studies. Polysaccharides and proteins are among the most studied
polymer class.

3.3.2 Polysaccharides

Polysaccharides are complex carbohydrates made up of monosaccharide (Figure

3.3.1) monomer units and they are present in the nature in a wide scale from
microbiological creatures to animals and plants. They are mostly used in drug
delivery studies since they are biodegradable. Polysaccharides are biocompatible
for humans and therefore they are not toxic. They attach to the target tissues due
to their reactive functional groups and they bond to the epithelial cells with non-
covalent bonds. In addition, they have the specific receptor recognition ability.
Since they provide neutral coating with low surface energy, they enable non-
specific protein adsorption. They have many hydroxyl groups that enable special
ligands to join the structure. Dextrine, chitosan and alginate are examples of
polysaccharides (Martínez et al. 2012, Reddy et al. 2015, Yang et al. 2015).

3.3.3 Chitosan

Chitosan is a natural polymer obtained by removing an acetyl from chitin, which

is attained from testaceans such as lobster, shrimp and crab (Figure 3.3.2). Chitin
is the second most abundant polymer in the nature after cellulose (Martínez et al.
2012, Reddy et al. 2015). Therefore, chitosan is an abundant and relatively
cheap product. Chitin is a non-toxic and eco-friendly polysaccharide and it is a
good biocatalyst. Although chitin is insoluble in many solvents, chitosan is so-
luble in all solvents with pH lower than 6.5 such as formic acid, acetic acid,
sitric acid and tartaric acid. Chitosan provides the convenience of working under
moderate conditions for manufacturers and users, and the ability to produce with
desired porosity and polymer length and to control its mechanical/biological
properties. In addition, the presence of suitable chemical side groups to bond
with other molecules extends its use in tissue engineering. Chitosan is also being
~ 164 ~
used for many studies about wound dressing and drug delivery systems. The
most important disadvantage of chitosan in tissue engineering applications is the
low tolerance and inconsistent behaviors of its polymeric structure. Chitosan’s
ability to easily be bonded with the other molecules and cells is its most impor-
tant advantage and turns its disadvantage into positive. With this property, chi-
tosan mixture with synthetic polymers like polyvinyl alcohol and polyethylene
glycol or its mixture with natural polymers such as collagen can be produced.
These mixtures are promising studies conducted to improve the poor properties
of chitosan (Martínez et al. 2012, Hudson and Margaritis 2014, Reddy et al.
2015, Yang et al. 2015).

Figure 3.3.1. Monosaccharide examples

(This image is published on https://socratic.org/questions/what-are-some-examples-of-monosaccharides and
retrieved from Google Images.)

~ 165 ~
 Figure 3.3.2. Structure of chitosan
(This image is published on https://glossary.periodni.com/glossary.php?en=chitosan and retrieved from Google
Images.)

3.3.4 Dextran

Dextran (Figure 3.3.3) is a branched and complex polysaccharide consisted of

chains with various lengths and many glucose molecules. These types of poly-
saccharides are comprised of simple sugar glucose monomer and are stored as
energy sources in yeast and bacteria. In addition to being a natural product,
dextran is also being used in many areas for its superior humidification proper-
ties, clinical safety and excellent biocompatibility (Martínez et al. 2012, Reddy
et al. 2015). They are widely used in food industry applications as thickener,
emulsion former and stabilizer. They are easily soluble in water, methyl sulp-
hoxide, ethylene glycol and glycerol. In spite of that, some of the dextran fracti-
ons are only soluble under strong heating effect. The most important characteris-
tic of dextran is that it is a polysaccharide. Therefore, it has a wide application
field (Martínez et al. 2012, Reddy et al. 2015, Yang et al. 2015).

~ 166 ~
 Figure 3.3.3. Structure of calcium alginate
(This image is published on https://en.wikipedia.org/wiki/Calcium_alginate and retrieved from Google Ima-
ges.)Dekstranın yapısı

3.3.5 Alginate
Alginate is a polysaccharide produced from brown algae. It is also a copolymer
that is naturally formed from glucuronic and mannuronic acid. Alginate is
widely used in wound dressing, food products and pharmaceutical applications
with its characteristics that are similar to chitosan, such as low toxicity, low inf-
lammation, biodegradability, controllable porosity and ability to form bonds
with biologically active molecules (Martínez et al. 2012, Reddy et al. 2015,
Yang et al. 2015). Simple aqueous gel formation of sodium alginate under the
presence of cations with 2 valence electrons such as calcium (Ca2+) (Figure
3.3.4) makes it preferable for drug delivery applications. Drug entrapment capa-
city that is as high as 70-90% can be achieved in such applications. Since they
can be attained in sizes smaller than 100 nm, they are aimed to be used in gene
delivery studies as well. Alginate is obtained in bead and solid gel forms under
mild processing conditions for uses that allow cell entrapment. Entrapment of
cells inside alginate particles increases the survival and growth likelihood of the
cells; therefore, alginate is being investigated to be used in tissue engineering

~ 167 ~
studies. In order to improve the low mechanical resistance and poor cell bonding
properties of alginate, it is being used by mixing with natural polymers such as
agarose, chitosan (Martínez et al. 2012, Hudson D. and Margaritis A. 2014,
Reddy et al. 2015, Yang et al. 2015).

Figure 3.3.4. Structure of calcium alginate

(This image is published on https://en.wikipedia.org/wiki/Calcium_alginate and retrieved from Google Ima-
ges.)Kalsiyum aljinat yapısı

3.3.6 Proteins
Proteins are consisted of many amino acid units that are connected with peptide
bonds (Figure 3.3.5). Proteins are vital units in humans, animals and plants. Cer-
tain proteins have drawn attention as biodegradable polymers. Due to low pro-
duction efficiency and high production costs, very few can be produced on an
industrial scale. Soybean, corn and wheat proteins are obtained from plants,
casein, collagen, gelatin and keratin proteins are obtained from animals in terms
of protein sources. Many proteins are made up of straight polymers made from
approximately 20 different amino acid sequences. The side chains of the stan-
dard amino acid have different chemical structures and properties. Proteins can
be classified as fibrous, spherical and film in terms of shape and solubility. The
fibrous proteins have a relatively simple and regular flat structure. Since the
polypeptide chain is tightly folded in spherical proteins, hydrophilic groups are
located on the outside to interact with solvents and hydrophobic groups are on
the inside. Therefore, spherical proteins are highly soluble in aqueous environ-
ments. Film proteins interact with different membrane systems of the cells. Hyd-
rophobic segments of film proteins are arranged in an outward manner to enable
interaction with the membrane systems. Therefore, they are very slightly soluble
in aqueous environments (Lohcharoenkal et al. 2014, Reddy et al. 2015).
~ 168 ~
 Figure 3.3.5. Peptide bonds that form the proteins
(This image is published on https://en.wikipedia.org/wiki/Amino_acid and retrieved from Google Images.)

3.3.7 Collagen
Collagen (Figure 3.3.6) is a protein that is widely found in mammals and it pro-
vides strength to the tissues. A typical collagen molecule is consisted of three
intertwined protein chains that form helical structures. These molecules undergo
polymerization to produce collagen fibers with different length, thickness and
mesh patterns. It is considered that there are at least 15 different collagens in
terms of their different structures, functions, locations and other properties. The
most dominant form used in biomaterial applications is the string shaped Type I
collagen, which can be found almost anywhere in the body and includes bones
and skins. Collagen can be absorbed by the body and it is not toxic; it just has a
slight immune response. In addition, they are excellent in terms of biological
interaction and bonding with the cells. Collagen can be converted into various
shapes such as porous rubber, gels and layers, and they can be cross bonded with
chemicals to change the degradation speed or to enhance the structure. Collagen
has many different biomedical applications from surgery, cosmetics, bioprosthe-
sis implants and to create artificial organs in tissue engineering. In addition,
collagen may manifest alterations such as unsuitable mechanical properties or
structural reduction (contraction) mainly due to from cell behaviors. Since cells
easily interact with collagen, cells push the collagen fibers and re-organize them.

~ 169 ~
If the collagen is not supported with another material or not chemically bonded,
the structure loses its backbone. In such cases, collagen can be easily bonded
with other biological/artificial materials to have them change their path when the
cells grow or to improve their mechanical properties. Therefore, the studies con-
ducted to bond the collagen as a signaling molecule to the various proteins or
growth factors to adapt cell behavior to special applications are very exciting
(Lohcharoenkal et al. 2014, Reddy et al. 2015).

Figure 3.3.6. Structure of collagen

(This image is published on http://proteopedia.org/wiki/index.php/Collagen#Structure_of_a_Segment and
retrieved from Google Images.)Kollajen yapısı

3.3.8 Gelatin
Gelatin (Figure 3.3.7) is one of the protein materials used in the production of
nanoparticles. Gelatin is obtained from the controlled hydrolysis of collagen, which is
found as the fundamental material of the skin, bones and connective tissue. Gelatin is a
transparent, odorless, tasteless, non-toxic, biodegradable and pale yellow biological
material that can be cross linked and chemically modified, and can be commercially
produced in the forms of powder, granule and plate. Gelatin contains cationic and

~ 170 ~
anionic hydrophilic groups within its structure. Mechanical and thermal properties vary
depending on the cross bonding degree of these cationic and anionic groups. Gelatin is
soluble inside hot water, glycerol and acetic acid, however, it is sometimes insoluble in
less polar organic solvents like acetone. This natural polymer is being used in food,
pharmaceutical and health industries for many years due to its excellent
biocompatibility, easy processing and low costs (Lohcharoenkal et al. 2014, Hudson and
Margaritis 2014, Reddy et al. 2015).

Figure 3.3.7. Structure of gelatin

(This image is published on http://www.madehow.com/Volume-5/Gelatin.html and retrieved from Google
Images.)

3.3.9 Albumin

Albumin is another natural polymer that is widely used to prepare nanocapsules

and nanospheres. Albumin (Figure 3.3.8) is widely preferred for nanoparticle
production for its availability in pure form, biodegradability, non-toxicity and its
properties that have no impact on immune system. Albumin is an important
plasma protein (bovine serum albumin, BSA and human serum albumin, HSA).
Albumin nanoparticles are also biodegradable and it is easy to prepare them in
desired sizes. Due to the reagent groups like thiol, amino and carboxylic groups
it carries on its surface, its surface can be more conveniently modified and bon-
ded with ligand (Lohcharoenkal et al. 2014, Hudson and Margaritis 2014, Reddy
et al. 2015).

~ 171 ~
 Figure 3.3.8. Structure of gelatin
(This image is published on http://www.madehow.com/Volume-5/Gelatin.html and retrieved from Google
Images.)

3.3.10 Synthetic Polymers

In comparison with natural polymers, synthetic polymers have similar chemical

properties, and therefore they are very appealing due to the reproducibility of
synthesized nanoparticles. Polyamides, polyesters, polyortoesters, moly(amino
acids) are among the synthetic polymer class.

3.3.11 Lactide and Glycolide Copolymers

These are the most popular biodegradable polymers that are used in drug deli-
very. They are aliphatic polyester copolymers based on lactide and glycolic
acids. Poly(P;L-lactide-co-glycolide) (PLGA) (Figure 3.3.9) is known as a bio-
compatible polymer produced from the natural products of lactic and glycolic
acid. PLGA is used for the production of implants and inseams. PLGA is widely
used in nanomedicine field. The most important reason of this is the fact that
PLGA is transformed into biologically degradable lactic acid and glycolic acid
monomers through hydrolysis in the body. These monomers are metabolized in
the body via the Krebs cycle and they are disposed of as carbon dioxide and
water. Degredation of PLGA nanoparticles depends on chemical composition,
porosity, hydrophilic/hydrophobic characteristics, morphology (crystalli-
~ 172 ~
ne/amorphous), molecular weight and molecular weight distribution. Lactide
polymer (PLA) is more hydrophobic than glycolide polymer (PGA) due to the
methyl group it contains. The duration these linear (straight) polyesters stay in
the body can be increased by mixing them with more hydrophobic comonomers
such as polycaprolactone (Makadia and Siegel 2011, Mirakabad et al. 2014,
Reddy et al. 2015).
Figure 3.3.9. Chemical structure of poly lactic-co-glycolic acid

(This image was published on http://www.drug-dev.com/Main/Back-Issues/PLGAPEG-Block-Copolymers-

for-Drug-Formulations-406.aspx and retrieved from Google Images.)

3.3.12 Poli(ɛ-Caprolactons)

Despite being hydrophobic and having high crystallinity, poly(ɛ-Caprolactone)

(Figure 3.3.10) is a water permeable polyester type polymer. During its biodeg-
radation, poly(ɛ-Caprolactone) undergoes bulk erosion that is initiated with ran-
dom chain scission at the first stage and results in a reduction in the molecular
weight of the polymer. In the subsequent second stage, these segments with low
molecular weight are exposed to phagocytosis or dissolution in the body fluid.
Poly(ɛ-Caprolactone) breaks down at a significantly low rate than PLA, PGA
and PLGA; therefore, poly(ɛ-Caprolactone) is less appealing for general tissue
regeneration applications. However, it is more attractive for long-term applicati-
ons such as implants and drug delivery systems (Azimi et al. 2014, BaoLin and
Ma 2014,
Reddy et al. 2015, Mohan et al. 2016).
~ 173 ~
 Figure 3.3.10. Structure of polycaprolactone
(This image is published on https://www.intechopen.com/books/periodontitis-a-useful-
reference/polycaprolactone-based-biomaterials-for-guided-tissue-regeneration-membrane and retrieved from
Google Images.)

3.3.13 Polyanhydride

Hydrophobic and crystalline polyanhydride (Figure 3.3.11) are being used in

drug delivery applications. When drugs are embedded in such polymers, they
can be better protected because before polymer is worn away, almost no water
gets inside. The degradation in the body starts with surface erosion, i.e. hydroly-
sis. Monomeric anhydrite bonds on the surface are highly reactive against water
and they undergo hydrolysis to form dicarboxylic acid. At low pH values, oli-
gomeric products formed on the matrix surface have low solubility; this prevents
the nucleus (core) from degradation. They are started to be used in tissue studies
for this characteristics (Vroman and Tighzert 2009, BaoLin and Ma 2014, Reddy
et al. 2015).).

Figure 3.3.11. Structure of polyanhydride

(This image is published on https://en.wikipedia.org/wiki/Polyanhydrides and retrieved from Google Images.)

~ 174 ~
3.3.14 Dendrimers

Polymer chemistry and technology is generally focused on linear (straight)

polymers, which traditionally have wide field of application. Linear macromole-
cules only occasionally contain smaller or longer branches. In recent years, mul-
ti-branched macromolecules are found to have different properties than conven-
tional polymers. They were first disovered by Donald Tomalia and his friends in
the early 1980s. These hyperbranched molecules are called dendrimers. The
term is derived from the Greek word ‘dendron’ which means a tree. Although
they were named differently before, ‘dendrimer’ is the most commonly used
term (Klajnert and Bryszewska 2001, Abbasi et al. 2014).

Dendrimers are nano-sized, well-defined, homogeneous and monodisperse struc-

tures that are consisted of tree-like branches. These hyperbranched molecules
contain symmetrically branched units that are formed around a linear polymer
nucleus or a small molecule. Dendrimer is just a designed architectural pattern, it
is not a compound. As a function of the increased generations (Figure 12), they
change in terms of size, shape and flexibility. Their physicochemical or biologi-
cal properties are modified through the outermost functionalized groups. There-
fore dendrimers have properties that make them very special for very special
applications. These well-defined materials are the best class of nano-scaled deli-
very devices of macromolecules with their advantages. These dendritic macro-
molecules tend to increase their diameter in a linear way and they gain more
spherical shapes with increasing dendrimer generation. Therefore, they are re-
markable for use in cancer treatment and diagnostic imaging applications (Klaj-
nert and Bryszewska 2001, Abbasi et al. 2014).
Structure of dendrimer molecules start with a central atom or a group of atoms
labelled as core. From this central structure, branches of other atoms called
dendrons grow outwards from the core molecule via various chemical reactions.
The core molecule reacts with monomer molecules containing one reactive and
two dormant groups giving the first generation dendrimer. Then the new perip-
hery of the molecule is activated for reactions with more monomers. Each new
generation is numbered to define the dendrimer (G1, G2, G3, etc.) (Figure
3.3.12). Every dendrimer with different number manifests different properties.
Dendrimers can be prepared in a controlled way and this enables the formation
of almost monodisperse, spherical macromolecules which cannot be achieved

~ 175 ~
with most linear polymers that have many peripheral groups (Klajnert and Brys-
zewska 2001, Abbasi et al. 2014).

Figure 3.3.12. . Structure of dendrimer and dendron

(This image is published on https://en.wikipedia.org/wiki/Dendrimer and retrieved from Google Images.

Dendrimers are a new class of polymers. Their chemistry is one of the most att-
ractive and rapidly growing areas of modern chemistry. Dendrimer chemistry
has its own terminology and abbreviations, like in other research areas. In addi-
tion, a short structural nomenclature is applied to describe the different chemical
events that occur on the surface of the dendrimer (Klajnert and Bryszewska
2001, Abbasi et al. 2014).

Summary

Natural polymeric nanoparticles can be classified as sugars and proteins based

on the frequency of use. Chitosan, gelatin and albumin are among the most
common natural polymers. In order to overcome the disadvantages of each of
them, new studies are being conducted by preparing two or more compositions.
In addition, synthetically synthesized polymeric nanoparticles provide new pro-
mises in application. Among these, the most common ones are; poly (lactic
acid-co-glycolic acid), poly (ε-caprolactone). With their monodisperse distribu-
tion and controllable dimensions, the dendrimers are the new class of macromo-
lecules, and they stand out in many applications with their superior properties.

~ 176 ~
References

Abbasi E., Aval S.F.,Akbarzadeh A., Milani M., Nasrabadi H.T., Joo S.W., Ha-
nifehpour Y., Koshki K.N., Asl R.P., Dendrimers: synthesis, applications,
and properties, Nanoscale Research Letters 2014, 9, 247.
Azimi B., Nourpanah P., Rabiee M., Arbab S. (2014) Poly (ε-caprolactone) Fi-
ber: An Overview, Journal of Engineered Fibers and Fabrics, 9, 74-90.
BaoLin G. and Ma P.X. (2014) Synthetic biodegradable functional polymers for
tissue engineering: a brief review, Science China Chemistry 2014 April 1;
57(4): 490–500.
Hudson D. and Margaritis A. (2014) Biopolymer nanoparticle production for
controlled release of biopharmaceuticals, Critical Reviews in Biotechno-
logy, 34, 161-179.
Klajnert B. and Bryszewska M. (2001) Dendrimers: properties and applications,
Acta Biochimica Polonica, 48, 199–208.
Lohcharoenkal W., Wang L., Chen Y.C., Rojanasakul Y. (2014) Protein Nano-
particles as Drug Delivery Carriers for Cancer Therapy, BioMed Research
International, Article ID 180549, pages 12.
Makadia H.K. and Siegel S.J. (2011) Poly Lactic-co-Glycolic Acid (PLGA) as
Biodegradable Controlled Drug Delivery Carrier, Polymers (Basel), 3,
1377–1397.
Martínez A., Fernández A., Pérez E., Benito M., Teijón J.M. and Blanco M.D.
(2012). Polysaccharide-Based Nanoparticles for Controlled Release For-
mulations, The Delivery of Nanoparticles, Dr. Abbass A. Hashim (Ed.),
ISBN: 978-953-51-0615-9, InTech, Available from:
http://www.intechopen.com/books/the-delivery-
ofnanoparticles/polysaccharide-based-nanoparticles-for-controlled-
release-formulations.
Mirakabad F.S.T, Koshki K.N., Akbarzadeh A., Yamchi M.R., Milani M.,
Zarghami N., Zeighamian V., Rahimzadeh A., Alimohammadi S., Hani-
fehpour Y., Joo S.W. (2014) PLGA-Based Nanoparticles as Cancer Drug
Delivery Systems, Asian Pacific Journal of Cancer Prevention, 15, 517-
535.
Mohan S., Oluwafemi O.S., Kalarikkal N., Thomas S., Songca S.P., (2016) Re-
cent Advances in Biopolymers :Biopolymers – Application in Nanoscien-
ce and Nanotechnology, 47-72.

~ 177 ~
Reddy Y. D., Dhachinamoorthi D., Chandra sekhar K.B. (2015) A Brief Review
on Polymeric Nanoparticles for Drug Delivery and Targeting, Journal of
Medical and Pharmaceutical Innovation, 2, 19-32
Vroman I. and Tighzert L. (2009) Biodegradable Polymers Materials, 2, 307-
344.
Yang J., Han S., Zheng H., Dong H., Liu J. (2015) Preparation and application
of micro/nanoparticles based on natural polysaccharides, Carbohydrate
Polymers 123, 53–66.

~ 178 ~
3.4 CERAMIC NANOPARTICLES

Dr.Serpil EDEBALİ
serpicetin@gmail.com
Dr.Mustafa ERSÖZ
mersoz@selcuk.edu.tr
SELÇUK UNIVERSITY

INTRODUCTION
Materials with nanocrystal structures posses very important changes in their
physical, chemical and mechanical properties with their reduced sizes. Deve-
lopment of advanced engineering materials became possible through the combi-
nation of these unique and exceptional mechanical, electrical and thermal pro-
perties of these materials with various matrices (polymers, ceramics and metals).
Nanostructured ceramic materials gained great importance in the past twenty
years with their high durability properties at both normal and high temperatures,
chemical resistance, high mechanical strength and rigidity. These materials are
especially suitable for sintering and reactions with different oxides. These nano-
scaled materials attracted the interest of many studies in various fields from ma-
terial sciences to biotechnology and genetics.

In recent years, use of ceramic materials, which are being used in many applica-
tions for their unique properties when mixed with metal and polymers, has signi-
ficantly increased. The most advantageous properties of ceramic materials are
rigidity, stiffness, abrasive toughness and low density. Ceramics belong to a
material class defined as “inorganic, ametalic solids”. They have the wide range
functions of all known materials. In recent years, exceptional potentials of func-
tional ceramics, which are based on unique dielectric, ferroelectric, piezoelectric,
pyroelectric, ferromagnetic, magnetoresistan, ionic, electronic, superconductive,
electrooptical and gas sensor properties, are being developed. Similar scientific
developments took their place in structural ceramics. Thermal, chemical and
mechanical stability of many oxide and non-oxide compounds have established
the foundation for improvement processes of micro-structured design and error
control. Therefore, this resulted in unique developments about the reliability in
mechanical performance and reliability of components and devices. In addition,
exceptional combinations of thermal, insulating and mechanical properties for-
med the basis of incredible applications in the production of microelectronics

~ 179 ~
and power semi-conductors. Therefore, ceramic materials became the building
blocks of advanced technologies such as energy conversion, storage and supply,
information technologies, transportation systems, medical technology and manu-
facturing technologies. In addition to these trends, today’s environmental regula-
tions, recycling of the materials and awareness will affect the use of these mate-
rials and lead to cheaper production processes. Needs for future ceramic researc-
hes can be divided into four main group in line with the technological trends:
(1) to research the materials and material properties in order to extend the scope
of the field and to meet the needs of future applications,
(2) to research information about economical and ecological production proces-
ses for materials, compounds and devices,
(3) to provide miniaturization and integration
(4) to create complementary or superseding models and numeric simulations for
current areas of experimental studies, thus, not just only directing the research
towards identified questions, but also to reduce practical operation and duration
through product development.
Nanocrystal ceramic materials have been the focal point of researches for the
past 20 years for their significantly improved mechanical properties when partic-
le sizes are decreased to nanometer scale. However, although there are various
technologies for manufacturing nano sized ceramic powders, attainment of true
nanocrystal ceramics (average particle size <100 nm) is very hard due to the
difficulties encountered during the sintering of particle growth. Particle growth
takes place compact or at surface contamination due to use of conventional met-
hods of powder consolidation, high temperatures and long sintering duration.
Therefore, particle growth must be minimized by controlling consolidation pa-
rameters, sintering temperature and careful regulation of time. It is also difficult
to evaluate mechanical properties of nanocrystal ceramic materials because there
are very few published data about true nano-sized particles. Nanoceramic
powder constitute a major part of all nanostructured materials. Indeed, it can be
said these materials are the one third of all new nano-structured materials.
Nanoceramics are commercially available as dry powder or liquid dispersion.
The most important commercially available nanoceramic materials are basic
oxides, silica (SiO2), titanium (TiO2), alumina (Al2O3), iron oxide (Fe3O4,
Fe2O3), zinc oxide (ZnO), cerium dioxide (CeO2) and zirconium (ZrO2). Silica
and iron oxide nanoparticles have more than half a century of commercial his-

~ 180 ~
tory. On the other hand, nanocrystal titania, zinc oxide, cerium dioxide, indium
tin oxide (ITO) and other oxides are new in the market.
Nanostructured materials are known as middle-sized objects between microsco-
pic and molecular structures. With various advantages and disadvantages, metal
oxides, metal nanoparticles, metal complexes, polymers, carbon nanotubes and
recently graphene are among the nanomaterials used for the design of gas sen-
sors. Ceramic nanomaterials offer ideal options for manufacturing of high-
performance gas sensor thanks to the exceptional combination of their physical
and chemical properties. Ceramic nanomaterials increase sensitivity, selectivity
and stability, and reduce process temperature and response time for gas sensors.
Therefore, performance of gas sensors can be improved by using ceramic nano-
materials with their morphology, content, size and physicochemical properties.
Ceramics in nano phase draw special attention because they gain a more ductile
characteristic than coarse-grained ceramics at higher temperatures.

3.4.1 Conventional Sintering Method

Ceramic materials with dense nanostructures are general obtained by using pres-
sure supported pressing methods of nano powders such as hot pressing, hot isos-
tatic pressing, sinter forging and traditional sintering methods [(Mayo, 1997;
Groza, 1999; Veljovic et al, 2007]. ). In conventional sintdering methods, high
sintering temperatures and long sintering durations for assembling ceramic
powders generally result in particle growth, ceramic degradation and deteriora-
tion of mechanical properties of ceramic (Gua et al, 2004; Tang et al, 2009). Hot
pressing of some ceramic materials allows condensation at lower temperatures
than traditional sintering (Halouani et al, 1994; Veljovic et al, 2009). Improved
compression kinetics and limitation of particle growth are the advantages of hot
pressing technique. On the other hand, limited geometry of the final product and
high cost of required equipment are among the disadvantages of this method.

3.4.2 Advanced Sintering Method

Assembly of nanocrystal powders is a difficult problem that needs to be solved.
The weird thing about sintering of nanocrystal powders is the competition
between compression and microstructure growth processes, which take place in
parallel. In order to assembly a material at a density close to its theoretical value
~ 181 ~
and with smallest possible particle size, various techniques are developed that
accelerate the first process and decelerate the second one. Fast heating, high
pressure, shrinking accelerator and particle growth inhibitor agents are the most
widely known agents for such purpose. Non traditional sintering and compres-
sion techniques are recommended to overcome the particle growth problem.
Advanced sintering has a great potential in ceramic processing field. These are;
use of agents that prevent particle growth in a solid solution or form separate
second phase, compression at high pressure, arc-plasma sintering and related
techniques, shock compression, high frequency induction heating and magnetic
pulse compression [Allen et al, 1996; Kim and Khalil, 2006; Godlinski et al,
2002; Krell et al, 2003; Jiang et al, 2007].

3.4.3 Usage areas of nano sized ceramic materials

Nano structured ceramic materials have good thermal resistance at both high and
low temperatures, good chemical resistance and good mechanical resistance and
rigidity. They are especially suitable for sintering and reaction with other oxides.
These nano-scaled materials have attracted the interest of many studies in vari-
ous fields from material sciences to biotechnology and genetics.
In recent years, there is an ever-increasing interest towards nano structured ce-
ramics that are synthesized in sized sizes smaller than 100 nm. This interest has
grown larger with various applications in the industry; sensors, batteries, capaci-
tors, corrosion-resistant coating, thermal barrier coatings, solid electrolytes for
fuel cells, catalysts, cosmetic products, health, automotive, bioengineering, op-
toelectronics, computer and electronic devices [Veljovic et al, 2007].
Nanomaterials in luminescence field also gained importance because these mate-
rials exhibit advanced optical, electronic and structural properties. Many new
physical and chemical production methods are developed in the past twenty ye-
ars. Nanoparticles and nanorods of some ceramic materials are produced. Recent
studies revealed that optical, luminescence and other properties can be modified
by shape and size, integration of impurities in different locations and with the
presence or absence of certain flaws [Godlinski et al, 2002].
Right now, ceramic materials are being rapidly developed for biomedical appli-
cations. Hydroxyapatite (HA), zirconia (ZrO2), silica (SiO2), titanium oxide

~ 182 ~
 (TiO2), and alumina (Al2O3), which are among nano sized ceramics, can be pro-
duced with new synthetic methods to improve their physicochemical properties.
Controlled drug release in biomedicine became the most widely area of use for
ceramic nanoparticles. In this application, where dose and size are of crucial
importance, high stability, high loading capacity, easy inclusion in hydrophobic
and hydrophiliphlic systems and different administration routes (oral or respira-
tory) are the other properties.

Conclusion

Although there are various techniques used to obtain nano sized ceramic powders,
attainment of correct nanocrystal ceramic (average particle size <100 nm) is a
major problem due to the difficulties in controlling the particle growth during
sintering. Instead of conventional methods that result in unwanted ceramic sizes
due to high temperature and long sintering durations, new advanced sintering
methods are recommended that can minimize particle growth by controlling as-
sembly parameters, temperature and duration.

~ 183 ~
References

Allen, A.J., Kruegger, S., Skandan, G., Long, G.G., Hahn, H., Kerck, H.M.,
Parker, J.C., Ali, M.N., 1996. Microstructural evolution during the sintering of
nanostructured ceramic oxides. J. Am. Ceram. Soc. 79, 1201–1212.
Godlinski, D., Kuntz, M., Grathwohl, G., 2002. Transparente alumina with
submicrometer grains by float packing and sintering. J. Am. Ceram. Soc.
85, 2449–2456.
Groza J.R., 1999. Nanosintering, Nanostruct. Mater. 12, 987–992.

Halouani R., Bernache-Assollant D., Champion E., Ababou A., 1994.

Microstructure and related mechanical properties of hot pressed
hydroxyapatite ceramics, J. Mater. Sci: Mater. Med. 5, 563–568.
Jiang, D., Hulbert, D.M., Kuntz, J.D., Anselmi-Tamburini, U., Mukherjee, A.K.,
2007. Spark plasma sintering: a high strain rate low temperature forming
tool for ceramics. Mater. Sci. Eng. A 463, 89–93.
Kim, S.W., Khalil, K.A.R., 2006. High-frequency induction heat sintering of
mechanically alloyed alumina–yttria-stabilized zirconia nano-bioceramics. J.
Am. Ceram. Soc. 89, 1280–1285.
Krell, A., Blank, P., Ma, H., Hutzler, T., van Bruggen, M.P.B., Apetz, R., 2003.
Transparent sintered corundum with high hardness and strength. J. Am.
Ceram. Soc. 86, 12–18.
Mayo M.J., 1997. Nanocrystalline ceramics for structural applications:
processing and properties, in: G.M. Chow, N.I. Noskova, Nanostructured
(Eds.), Materials Science Technology, NATO ASI Series, Kluwer
Academic Publishers, Russia, pp. 361– 385.
Tang C.Y., Uskokovic P.S., Tsui C.P., Veljovic Dj., Petrovic R., Janackovic
Dj., 2009 Influence of microstructure and phase composition on the
nanoindentation characterization of bioceramic materials based on
hydroxyapatite, Ceram. Int. 35, 2171–2178.
Veljovic Dj., Jokic B., Jankovic-Castvan I., Smiciklas I., Petrovic R.,
Janackovic Dj., 2007. Sintering behaviour of nanosized HAP powder, Key
Eng. Mater. 330–332, 259–262.
Veljovic Dj., Jokic B., Petrovic R., Palcevskis E., Dindune A., Mihailescu I.N.,
Janac´kovic Dj., 2009. Processing of dense nanostructured HAP
ceramics by sintering and hot pressing, Ceram. Int. 35,1407– 1413.

~ 184 ~
3.5 MAGNETIC NANOPARTICLES

Dr. Cumhur Gökhan ÜNLÜ

cunlu@pau.edu.tr
PAMUKKALE UNIVERSITY

INTRODUCTION

The concept of magnetism, in its basic form, can be understood by looking at a mag-net
that pulls metal needles at a certain distance towards itself. The question is why those
metal needles are pulled with a greater force as they get closer to the magnet? We can
mention a force field that is invisible but felt by the matter. The pulling or push-ing field
created by the magnet is called the magnetic field.

Figure 3.5.1. Magnetism

Here, another question comes to mind: why does the magnet create such a power-
ful pull field around itself and how do the metal needles detect it? The answer is
hidden in the atoms that form the magnet and the needles. As we all know, each
matter is formed by atoms. According to the classical view, atoms are made of a
nucleus con-sisted of protons and neutrons, and electrons that orbit around this
nucleus. Although all matters are formed by atoms, the difference beetween the
number of these sub-atomic particles creates different types of atoms. And matters
with different physical and chemical properties are obtained when different types

~ 185 ~
of atoms come together. In the most basic level, moving charges create magnetic
fields. Electrons moving around the nucleus have an orbital angular momentum,
which is defined as magnetic moment that depends on the movement direction.
The addition of angular momentum called spin, which depends on the intrinsic

properties of the particles, and the orbital anguar momentum forms the net mag-
netic moment of that particle.

Figure 3.5.2. Electron spin momentum

Similarly, protons inside the nucleus have magnetic moment since they are also
charged particles. Unpaired electrons inside a matter that is formed by the bond-
ing of atoms or ions cause the matter to exhibit magnetic properties and they re-
act against an externally applied magnetic field.

Magnetic Properties of Matter

Materials have three different categories based on their magnetic properties. These are:
• Dia magnetic materials
• Paramagnetic materials and
• Ferromagnetic materials.

Diamagnetic Materials
These materials do not have unpaired electrons, all of them are paired. They re-act
in the opposite direction to the applied magnetic field. Their susceptibility val-
ues, a measure of magnetic properties of materials, are small and negative. Ma-

~ 186 ~
terials such as copper, silver, gold and bismuth have diamagnetic properties. Su-
perconductors, materials that exhibit zero resistance under certain tempera-tures,
are also diamagnetic materials.

Paramagnetic Materials

Paramagnetic materials react to the magnetic field in the same direction but their
reaction is weak. Their susceptibility values are small and positive. Materials such
as aluminum and platinum have paramagnetic properties. There is no magnetic
field inside the paramagnetic matters and the directions of magnetic moments are
random. Therefore, the total magnetisation is zero. If a field is ap-plied, they di-
rect towards the field. When the magnetic field is removed, they align randomly
again and the total magnetisation becomes zero. Nuclear Mag-netic Resonance
(NMR) system used in medicine utilizes the paramagnetism inside the body to
perform imaging.

Ferromagnetic Mateials

These materials have high susceptibility and react to the applied magnetic field in
the same direction. Even when they are placed in-side a weak magnetic field, they
align parallel to the field and create a very strong magnetisation, therefore they
are frequently used in applications. These strong magnetisation properties are due
to the magnetic moments aligned in the same direction with each other as groups
inside the regions called domain within their inner structures.

Figure 3.5.3. Magnetic areas

(http://iopscience.iop.org/article/10.1088/0022-3727/42/3/032006)

Susceptibility values of ferromagnetic materials vary between 50 and 10000.

Many transition metals like iron, cobalt, nickel, and some rare earth elements and
their alloys have ferromagnetic properties.

~ 187 ~
Similar to ferromagnetics, there are materials that have magnetic arrangements
inside. These materials are classified as ferromagnetic materials due to the magne-
tic arrangements they have. These materials are Ferromagnetic,

Antifer-romagnetic, Helimagnetic and Superparamagnetic materials. Especially

the su-perparamagnetic materials are interesting types with nanometric-sized ma-
terials.

Superparamagnetic Materials

Superparamagnetic materials act as single-domain materials due to their sizes.

Therefore, each nanoparticle is like a single domain. When an external magnetic
field is applied, they align parallel to the field, and when the field is removed,
they go back to random alignment and the total magnetisation becomes zero. The-
refore, due to these properties, superparamagnetic particles do not exhibit hystere-
sis, which is observed in ferromagnetics. Although they have high saturation
magnetisation values, their permanent magnetisation and coercivity values are
zero. Such materials are used in many application fields from medicine to electro-
nics. These include medical imaging, hyperthermia, drug delivery and registration
systems. Magnetic hyperthermia treatment is the destruction of cancerous tumor
tissues with heat by using magnetic nanoparticles. In this treatment method, the
magnetic nanoparticles delivered into the cancerous tissue are oscillated by appl-
ying an external AC field. Particles are heated as a result of this oscillation.

Tumor cells, which are extremely sensitive against heat, degrade and die when
they reach approximately 42 oC. This way, cancerous tissues can be destroyed
without damaging the normal tissues.

~ 188 ~
 Figure 3.5.4. Hypotermia
(http://trialx.com/curetalk/2012/11/19/cancer-treatment-multifunctional-magnetic-nanoparticles-for-molecular-
imaging-and-hyperthermia/)

In the drug delivery applications, drug attached to a nanoparticles is injected to

the body and carried to the desired location via the magnetic particles by apply-
ing magnetic field to the target region.

~ 189 ~
References

1) http://iopscience.iop.org/article/10.1088/0022-3727/42/3/032006)

2) (http://trialx.com/curetalk/2012/11/19/cancer-treatment-multifunctional-
magnetic-nanoparticles-for-molecular-imaging-and-hyperthermia/)

~ 190 ~
3.6 CONDUCTOR AND SEMICONDUCTOR NANOMA-
TERIALS
Dr. Yasemin ÖZTEKİN
yoztekin@gmail.com
SELÇUK UNIVERSITY
INTRODUCTION
Everything that has mass, volume and inertia property is made of atoms, and
atoms are consisted of a positive nucleus (proton and neutron) and negatively
loaded particles (electron) moving around the nucleus in different orbitals. Mo-
vement of the electrons create what is known as electrical current, measured in
ampere, which is the number of electrons passing on a conductor per unit of
time. Electron movement is not the same for every material; therefore, materials
are classified as conductors, semiconductors and insulators depending on the
movement of the electrons. However, in recent years, a new category known as
superconductors is added to the group. Reason for this classification is the diffe-
rences between band gaps in solid matters.
Solid-state matters have two different bands; conduction and valence bands, and
there is a band gap between them. Conduction band represent the energy levels
where free electrons participate in conduction, valence band represents the
energy levels filled with valence electrons of the atoms of the solid and the band
gap between these two represents the forbidden energy levels for the electrons
(Figure 3.6.1.). In order to understand whether a material is a conductor, semi-
conductor or an insulator, the distance between the valence band and conduction
band must be examined. To define a material as a conductor, band gap between
the two bands must be small.

Figure 3.6.1. Conductors, semiconductors and insulators based on their band gaps
(This image is published on goo.gl/txgT3s and retrieved from Google Images.)

~ 191 ~
3.6.1 Conductors

Objects where electrical or thermal energy can flow are called conductors. Abi-
lity of an object to conduct heat is called thermal conductivity, and the ability to
conduct electricity is called electrical conductivity.
Heat conduction in thermal conductivity is possible in three different forms;
conduction, convection and radiation. During conduction, heat is conducted to
the different parts of an object through molecular interaction and mechanical
energy changes. In convection, heat is transfered via mass transfer, and in radia-
tion, it is transfered via wave transfer. Each object transfers heat to some degree,
however, heat transfered from a unit section of an object per unit of time is refer-
red as heat transfer coefficient and greater this value, better conductor an object.
In electrical conductivity, electrons take part. The most important factor deter-
mining the conductivity of a matter is the number of valence electrons in the last
orbital of the atoms, known as the valence orbital (Figure 3.6.2.). Valence elect-
rons have a weaker bonding to the atom nucleus than the electrons that are on
the inner orbitals. However, since properties like charge, nucleus diameter, total
number of protons and electrons differentiate the matters, they affect how
strongly the nucleus pulls the electrons. To generalize, matters having more than
4 valence electrons are insulators, and matters with less than 4 valence electrons
are conductors.

Figure 3.6.2. A sample for valence electrons from the periodic table
(This image is published on goo.gl/KXJdTC and retrieved from Google Images.)

~ 192 ~
Resistance of some conductor matters like gold, silver and copper decreases with
the decreased temperature of the matter. But resistance never falls to zero even
when the temperature is close to the absolute zero, which is the lowest possible
temperature, due to impurity and structural irregularities of a metal. However, in
1911, physicist Heike Kamerlingh Onnes discovered the phenomenon of super-
conductivity, a quantum mechanical phenomenon where the electrical resistance
of a matter is exactly zero below a certain “critical” temperature. Electrical cur-
rent can continue inside a superconductor material without having power supply
from a source. Generally, liquid nitrogen is used to cool superconductor materials
to this critical temperature where they present the superconducting state. Materi-
als with critical temperature lower than the boiling point of nitrogen (77 Kelvin)
are called low-temperature superconductors; ones with higher critical temperature
are called high-temperature superconductors.

Superconducting materials posses important properties; zero electrical resistance

against direct current (d.c.), very high current carrying capacity and very low
signal dispersion compared to normal conductors, signal carrying capacity at spe-
eds close to the speed of light, very low resistance even at high frequencies and
electrical current conduction without resistance/dissipationless. Therefore, they
have a significant importance in carrying and storing the electrical current, const-
ruction of powerful magnets, generators, manufacturing of sensitive electrical
devices, communication technologies and defense industry.

3.6.2 Semiconductors

Semiconductors are classified between conductors and insulators, and they are the
crystalline or amorphous solids in the 3rd and 5th groups of the periodic table. Sili-
con and germanium are the most well known and most widely used semiconduc-
tors in applications. Their valence electron number is 4, which allows them to
both receive and give electrons at the same time. They are insulators in their nor-
mal states, however, they are exposed to external impacts such as heat, light and
magnetic effect or activated by some special materials to impart semiconductor
properties, but this conductivity is temporary and is lost when the external effect
is re-moved. Semiconductors are studied in two groups, n- and p-type semicon-
ductors, depending on their free electrons or free holes, respectively. Bonding
between arsenic and silicon can be explained as an example of an n-type semi-
conductor. Arsenic atoms have 5, silicon atoms have 4 electrons in their valence

~ 193 ~
orbitals. As a result of the covalent bonding between these two atoms, 1 electron
of arsenic atom becomes free and separates. This is called n-type semiconductor
due to the presence of a free electron that is not bonded to an atom and it can be
said that conductivity is increased. This situation can be explained as the doping
of silicon to increase the number of holes in the conduction band of a pure silicon
atom. For this purpose, phosphorus, bismuth and antimony, which have 5 elect-
rons in valence orbital, can be used instead of arsenic (Figure 3.6.3).

Figure 3.6.3. Formation of an n-type semiconductor material

(This image is published on goo.gl/pfrGbj and retrieved from Google Images.)

Boron element present in certain proportions in pure silicon may be given as an

example for p-type semiconductors. There are 3 electrons in the valence orbital of
the boron atom and 4 electrons in the silicon atom. When 3 valence electrons of
boron atom and 3 valence electrons of silicon atom form a covalent bond, 1 elec-
tron of silicon atom remains without bonding, thus, creates a lack of electron or in
other words, holes. Since the holes have positive charge, they are called p-type
semiconductors. Aluminum and gallium can be used as well instead of boron
(Figure 3.6.4.).

Figure 3.6.4. Formation of a p-type semiconductor material

(This image is published on goo.gl/pfrGbj and retrieved from Google Images.)

~ 194 ~
3.6.3 Insulators
Electrical insulation is the lack of electrical conductivity in the materials for
which the electric charge can not freely flow. A charge, which is a condition for
conductivity, flows only when electrons can move freely. If this is not the case,
the matter is an insulator. However, perfect isolation is not possible. Insulator
materials have the largest band gaps among the ones shown in Figure 3.6.1.
They are used to support electrical conductors in electric materials and to dis-
connect them without allowing current flow, to wrap electrical cables or other
materi-als, to connect distribution and transmission lines in electrical poles and
transmission towers.

3.6.4 Conductor and semiconductor nanostructures

The most known examples of conductor nanostructures are conducting polymers
that have polymeric chain with high π conjugation or the ones transformed from
insulators via electrochemical doping (Shi et al., 2015). With their conjugated π-
electron backbones, they have electrical properties including high electrical con-
ductivity, high affinity and low ionization potential, as well as optical properties
such as low-energy optical transmittance (Vidal et al., 2003). In addition, their
conjugated structures provide these polymers with strong UV-Vis adsorption.

Neutral conjugated systems with low conductivity between 10-10 and 10-5 S/cm
can be turned into semiconducting or conducting polymers with conductivity va-
lues between 1 and 104 S/cm (MacDiarmid, 2001). This is called doping. Backbo-
ne of the conducting polymer contains positive (p-doping) or negative (n-doping)
charge carriers, therefore, opposite ions are either captured or released to provide
charge balance to the polymer (Figure 3.6.5.).

Conventional conducting polymers are polyaniline, polypyrrole and polythiophe-

ne. Conducting polymer nano-composites, which became an active field in studies
and applications of composite materials, are consisted of conductive nanofilled
materials such as metal nanoparticle, carbon nanotube and graphene, and polymer
ma-trix. Because of their ease of process, low densities, adjustable electrical pro-
perties, oxidation resistance and flexibility, conducting polymer nanocomposites
are used in versatile electrical applications such as antistatic protection, electro-
magnetic interference protection, energy storage electrode, sensors, flexible elect-

~ 195 ~
 ronics and thermoelectric devices (Thomson and Frechet, 2008; Li et al., 2009;
Tang et al., 2017).

Figure 3.6.5. Images of polypyrrole nanospheres, which are synthesized as doped

with different materials or electrochemically, obtained by scanning electron mic-
roscope (Bajpai et al., 2004; Gao et al., 2006; Li et al., 2009; Qu et al., 2003; Qu
et al., 2004; Qu and Shi, 2004; Yuan et al., 2004)

Conducting polymers can be chemically or electrochemically synthesized. In che-

mical synthesis, powder nano-materials that can be easily scaled are obtained.
However, in electrochemical synthesis, electropolymerization reactions occur at the
surface of the electrode, and the nanostructures of the conducting polymers accu-
mulate as a film on the electrode surface. And in some cases, the nanostructures
grow with the electric field to form oriented structures. The electrochemical poly-
merization rate can be easily controlled by the current density or potential, and by
the systems for which the product amount is integrated into the system. The morp-
hology and properties of nanomaterials can be changed by the conditions during
the electrochemical polymerization. Therefore; electrochemical polymerization
method is a single step and effective technique for preparing conductive nanomate-
rials with desired properties (Li et al., 2009; Teng et al., 2017).

~ 196 ~
NOTES

Structure of an atom
(This image is published on goo.gl/NsjCu1 and retrieved from Google Images.)

 Conduction can be in the form of thermal or electrical energy.

 Electron is a charge carrier.
 The unit for electrical charge is Coulomb and it is represented as “C”.
 Flow speed of the electrical charge is called electrical current and its unit is
Ampere.
 There are two types of charge; positive and negative, and opposite charges
attract each other, whereas like charger repel each other.
 Voltage and current in a system encounters with forces that can be defined as
difficulties affecting the passage of the electrons on the system. These forces are
called resistance. Resistance can also be defined as the ratio of voltage to the cur-
rent.
 Resistivity is defined as the ratio of electrical field strength to the current den-
sity. Conductance is the inverse of resistivity.
 Metals can be classified as good and bad conductors.
 Metals with valence electrons, such as gold, silver and copper, are classified as
good conductors.
 Although copper is less conductive than gold and silver, and cannot be obtained
in a completely pure form, it is more commonly preferred because of its low cost
and abundance.
 Gold and silver are the best two conductors but they cannot be preferred due to
their costs.

~ 197 ~
 Current-potential and resistance relation
(This image is published on goo.gl/HRsnA7 and retrieved from Google Images.)

Effects of electric shock

(This image is published on goo.gl/PB538a and retrieved from Google Images.=

~ 198 ~
References
Bajpai, V., He, P., Dai, L., (2004). Conductive-Polymer microcontainers: Cont-
rolled Syntheses and applications, Advanced Functional Materials, 14, 145–151.
Gao, Y., Zhao, L., Li, C., Shi, G., (2006). Electrosynthesis of poly(3,4-
ethylenedioxythiophene) microcups in the aqueous solution of LiClO4 and
tri(ethylene glycol), Polymer, 47, 4953–4958.
Li, C., Bai, H., Shi, G., (2009). Conducting polymer nanomateri-
als:electrosynthesis and applications. Chemical Society Reviews, 38, 2397–2409.
MacDiarmid, A.G., (2001). “Synthetic Metals”: A novel role for organic poly-
mers (Nobel lecture). Angewandte Chemie International Edition, 40, 2581–2590.
Qu, L., Shi, G., Chen, F., Zhang, J., (2003). Electrochemical Growth of Polypyr-
role Microcontainers, Macromolecules, 36, 1063–1067.
Qu, L., Shi, G., Yuan, J., Han, G., Chen, F., (2004). Preparation of polypyrrole
micro-structures by direct electrochemical oxidation of pyrrole in an aqueous
solution of amphorsulfonic acid, Journal of Electroanalytical Chemistry, 561,
149–156.
Qu, L. and Shi, G., (2004). Hollow microstructures of polypyrrole doped by
poly(styrene sulfonic acid), Journal of Polymer Science/Part A Polymer Che-
mistry, 42, 3170–3177.
Shi Y., Peng L.L, Yu G.H., (2015). Nanostructured conducting polymer hydro-
gels for energy storage applications, Nanoscale, 7, 12796–12806.
Tang C., Chen N., Hu X., (2017). Conducting Polymer Nanocomposites: Recent
Developments and Future Prospects. In: Kumar V., Kalia S., Swart H. (eds)
Conducting Polymer Hybrids. Springer Series on Polymer and Composite Mate-
rials. Springer, Cham. https://doi.org/10.1007/978-3-319-46458-9_1
Teng, Y., Liu, F., Kan, X., (2017). Voltammetric dopamine sensor based on
three-dimensional electrosynthesized molecularly imprinted polymers and
polypyrrole nanowires, Microchimica Acta, 184, 2515–2522.
Thomson, B.C., Frechet, J.M., (2008). Polymer–Fullerene composite solar cells.
Angewandte Chemie International Edition, 47, 58–77.

~ 199 ~
Vidal J.C., Garcia-Ruiz E., Castillo J.R. (2003). Recent advances in electropoly-
merized conducting polymers in amperometric biosensors, Microchimica Acta,
143, 93–111.
Yuan, J., Qu, L., Zhang, D., Shi, G., (2004). Linear arrangements of polypyrrole
microcontainers, Chemical Communications, 8, 994-995.

~ 200 ~
 3.7 QUANTUM DOTS

Dr. İmren HATAY PATIR

imrenhatay@gmail.com
Dr. Emre ASLAN
emreaslan89@gmail.com
SELÇUK UNIVERSITY
INTRODUCTION
Quantum dots (QDs) are semiconductor particles with the size of a few nanome-
ters. Quantum dots have unique luminescence and electrical properties such as
wide and continuous absorption spectrum, narrow emission spectrum and high
light stability. Crystal diameters of quantum dots are generally 1-10 nm and their
optical and electrical properties change depending on their sizes [Jamieson,
2007]. As the crystal diameter of the quantum dots increase, the florescence
emission shifts to the red region. This shift to red region occurs due to the nar-
rowing of the band gap between valence and conduction bands. However, this
narrowing of the band gap continues until a certain magnitude of the crystal size
and then remains unchanged depending on the particle size. This is a consequen-
ce of quantum confinement effect, which is the behavior of electrons inside a
particle due to spatial limitations [Murray, 2000]. As it can be seen in Figure 1,
quantum dot structures with different sizes have different radiation colors due to

the quantum confinement effect.

Figure 3.7.1. Appearance of CdSe quantum dots having sizes between 2 nm and
8 nm under UV lamp (quantum confinement effect) [Dabbousi, 1997].

Another factor that affects the optical properties of quantum dot structures is the
surface characteristics. Surface regions originating from the vacancies on the

~ 201 ~
surfaces of quantum dot structures cause the formation of new electronic energy
levels at the band gaps of this semiconductor structure. Abundance of trap regi-
ons on the surfaces of quantum dot structures causes decreased efficiency, dec-
reased florescence quantum efficiency, narrow florescence interval and flores-
cence blinking during recombination in the applications containing quantum
dots. Photocatalytic activity can be increased by coating with a surface active
agent and synthesis in core/shell structure or alloy structures in order to improve
the surface properties of quantum dot structures [Kershaw, 2013].

Since the sizes of the quantum dots can be adjusted experimentally, synthesis of
application-specific quantum dots is possible. With their unique optical and
electrical properties, quantum dots can be used in many application fields like
chemical sensors [Chen, 2002; Frasco, 2009], biosensors [Grigsby ,2012] bio-
imaging [Lim, 2015; Huang, 2012], photocatalysis and electrocatalysis [Zhang,
2016; Li, 2010; Yang, 2011; Tang, 2014], photovoltaic devices [Schaller, 2004]
and light emitting diodes [Frecker, 2016].

3.7.1 Synthesis of Quantum Dot Structures

Quantum dots can be synthesized through various methods [Bera, 2010]. Gene-
rally, methods used for the synthesis of quantum dots are classified in two app-
roaches; top-down and bottom-up. These two methods are briefly explained
below.

Top-down synthesis method: Top-down synthesis method of quantum dot

structures involves techniques such as electron beam litography, X-ray litog-
raphy, ion implantation, beam epitaxy [Bera, 2010; Valizadeh, 2012]. The pur-
pose of top-down synthesis approach is to obtain quantum dot structures by
thinning the bulk semiconductor [Bera, 2010].

Bottom-up synthesis method: Bottom-up synthesis of quantum dot structures

contains spontaneous agglomeration techniques and can be classified in two as
wet chemical and gas phase methods [Valizadeh, 2012].

Wet chemical method involves careful control of the parameters for one disper-
sion or a dispersion mixture, and common precipitation methods. Precipitation
process includes both nucleation and the limited growth of nanoparticles. Gene-
rally, wet chemical methods are classified as microemulsion, sol-gel, hot disso-
~ 202 ~
lution [Bang, 2006; Spanhel, 1991; Qu, 2002; Murray, 1993; Qu, 2011] competi-
tive reaction chemistry, sound waves or microwave [Li, 2005] and electroche-
mistry.
Gas phase method is initiated with atom by atom growth in layers in order to
obtain quantum dot structures [Valizadeh, 2012] and finally, spontaneous agg-
lomeration of quantum dots is realized on the substrate without patterning [Xin,
1996; Leonardi, 1998; Kurtz, 2000; Swihart, 2003].Gas phase methods are gene-
rally classified as molecular beam epitaxy, injection, liquid metal ion sources or
agglomeration of gas monomers [Bera, 2010].

3.7.2 Application Fields of Quantum Dot Structures

Chemical sensors

In the field where quantum dots are used as chemical sensors, there are different
applications such as pH determination, ion sensors and detection of organic
substances. Damping of the luminescence properties of quantum dots and their
sensor properties are studied in these fields. In the ion sensors, surface active
agent on the quantum dots forms a complex with metal ions and causes flores-
cence damping [Chen, 2002]. In the organic substance assays, quantum dots
form a complex with the organic substances present in the medium and causes
florescence damping [Fasco, 2009].

Biosensors

Quantum dots that are used as biosensors are generally utilized in the determina-
tion of different biological materials such as nucleic acids, proteins and enzy-
mes.Here, material determination is performed through florescence resonance
energy transfer [Grigsby , 2012].Florescence intensity drops due to the electron
transfer.

Bioimaging

Quantum dot structures are widely used in bioimaging applications for their high
florescence emission properties. In this field, generally non-toxic and eco-
friendly carbon quantum dots are being used [Lim, 2015]. Bioimaging is per-
formed by florescence microscope and confocal microscope, which are optical
microscopes. In addition, quantum dots in the field of nanomedicine are being
used for both imaging and photodynamic therapy applications [Huang, 2012].

~ 203 ~
Photocatalysis

In recent years, photocatalytic studies using quantum dot structures have gained
great importance as an alternative to organic syntheses. In comparison with or-
ganic dyes, quantum dots are widely used as photocatalytic in environmental
treatment, water splitting and synthetic chemistry due to their low cost, low
toxicity, easy functionalization, high biocompatibility, adjustable florescence
emissions, high light resistance and chemically inert structures [Zhang, 2016].In
addition to being used as photocatalysts, quantum dots are also used to sensitize
photocatalysts that cannot be excited in the UV region, such as TiO2 [Li, 2010].

Electrocatalysis

Quantum dot structures can be used as electrocatalysts in applications that pos-

ses technological importance such as fuel cells and clean fuel production in
clean energy generation. For example, quantum dot structures have been used as
photocatalysts in oxygen reduction reaction and oxygen generation reaction, and
showed a catalytic effect that is very similar to the noble metal of Pt [Yang,
2011; Tang, 2014].

Photovoltaic devices

Properties of quantum dots such as their adjustable absorption spectrum and high
absorption coefficients have made them attractive for use in photovoltaic sys-
tems [Schaller, 2004].Quantum dots can increase the efficiency and reduce the
cost of today’s typical silicon photovoltaic cells.

Light emitting diodes

As quantum dots emit natural monochromatic light, they can be more effective
than light sources with color filters. Quantum dots are very suitable for imaging
systems for their specific emission spectrums. As quantum dot imaging systems
make bright emission in visible regions, they have sharper image quality than
florescence imaging systems [Frecker, 2016].

~ 204 ~
Summary
• Quantum dots are semiconductor particles that are several nanometers in
size.
• Optical and electrical properties of the quantum dots change depending
on their sizes.
• Quantum dot structures with different sizes have different radiation co-
lors due to the quantum confinement effect.
• Another factor that affects the optical properties of quantum dot structu-
res is the surface characteristics.
• Synthesis of quantum dots can be achieved by two methods that are cal-
led top-down and bottom-up.
• Quantum dot structures can be used in different applications such as
sensors, imaging, photocatalysis, photovoltaic devices and LEDs.

~ 205 ~
References
Bang J., Yang H., Holloway PH.,2006, Enhanced and stable green emission of
ZnO nanoparticles by surface segregation of Mg, Nanotechno-
logy,17(4),973-8
Bera D, Qian L, Tseng T-K, Holloway PH., 2010, Quantum Dots and Their Mul-
timodal Applications: A Review, Materials 2010, 3(4), 2260-2345
Brus, L. E., 1984, Electron–electron and electron-hole interactions in small se-
miconductor crystallites: the size dependence of the lowest excited
electronic state, J. Chem. Phys., 80, 4403–4409.
Chen, Y., Rosenzweig, Z., 2002, Luminescent CdS quantum dots as selective ion
probes, Anal. Chem., 74, 5132–5138.

Dabbousi B. O.,Rodriguez-Viejo J., Mikulec F. V., Heine J. R., Mattoussi H.,

Ober R., Jensen K. F., Bawendi M. G., 1997, (CdSe)ZnSCore-Shell
Quantum Dots: Synthesis and Characterization of a Size Series of
Highly Luminescent Nanocrystallites, Journal Physical Chemistry B,
101, 9463-9475.
Frasco M. F., Chaniotakis N., 2009, Semiconductor Quantum Dots in Chemical
Sensors and Biosensors, Sensors 9(9), 7266-7286.

Frecker T., Bailey D., Arzeta-Ferrer X., McBride J., Rosenthal S. J., 2016, Re-
view—Quantum Dots and Their Application in Lighting, Displays,
and Biology, ECS J. Solid State Sci. Technol., 5, R3019-R3031.

Grigsby C.L., Ho Y-P., Leong K.W., 2012, Understanding nonviral nucleic acid
delivery with quantum dot-FRET nanosensors, Nanomedicine, 7(4),
565-577
Huang P., Lin J., Wang X. S., Wang Z., Zhang C. L., He M., Wang K., Chen F.,
Li Z. M., Shen G. X., Cuiand D. X., Chen X. Y., 2012, Light-
Triggered Theranostics Based on Photosensitizer-Conjugated Car-
bon Dots for Simultaneous Enhanced-Fluorescence Imaging and
Photodynamic Therapy, Adv. Mater., 24, 5104–5110.

Jamieson, T.,Bakhshi, R., Petrova, D., Pocock, R., Imani, M., Seifalian, A.M.,
2007, Biological applications of quantum dots, Biomaterials, 28,
4717-4732.
Kershaw S. V., Susha A. S., Rogach A. L., 2013 Narrow bandgap colloidal me-
tal chalcogenide quantum dots: synthetic methods, heterostructures,

~ 206 ~
 assemblies, electronic and infrared optical properties, Chem. Soc.
Rev., 42, 3033.

Kouhi M., Akbarzadeh A., Davaran S., 2012, Quantum dots: synthesis, bioapp-
lications and toxicity,Nanoscale Research Letters, 7:480
Kumar, S.,Ade, M., Nann, T., 2005, Synthesis and Structural Metastability of
CdTe nanowires, Chem. Eur. J., 11, 2220– 2224.
Kurtz E., Shen J., Schmidt M., Grun M., Hong S.K., Litvinov D.,2000, For-
mation and properties of self-organized II–VI quantum islands,
Thin Solid Films,367(1–2),68–74.
Leonardi K., Selke H., Heinke H., Ohkawa K., Hommel D., Gindele F.,
Woggon U.,1998, Formation of self-assembling II–VI semiconduc-
tor nanostructures during migration enhanced epitaxy, Journal of
Crystal Growth, 259–263.
Li L., Qian H., Ren J., 2005, Rapid synthesis of highly luminescent CdTe na-
nocrystals in the aqueous phase by microwave irradiation with cont-
rollable temperature, ChemCommun (Camb),
DOI:10.1039/B412686F.
Li, H., He, X., Kang, Z., Huang, H., Liu, Y., Liu, J., et al., 2010. Water and
soluble fluorescent carbon quantumdots and photocatalyst design,
Lindsay, S., 2009. INTRODUCTION to nanoscience: Oxford University
Press.
multimodal applications: a review, Materials, 3(4):2260–2345.
Murray, C., Norris, D.J., and Bawendi, M.G., 1993. Synthesis and characteri-
zation of nearly monodisperse CdE (E = sulfur, selenium, tellu-
rium) semiconductor nanocrystallites, Journal of the American
Chemical Society, vol. 115, pp. 8706-8715.
Murray, C.B., Kagan, C.R. and Bawendi, M.G., 2000, Synthesis and charac-
terization of monodisperse nanocrystals and close packed nanocrys-
tal assemblies, Annual Review of Materials Science, 30, 545–610.
Najeh Al-Salim, Aidan G. Young, Richard D. Tilley, A. James McQuillan,
and James Xia, Synthesis of CdSeS Nanocrystals in Coordinating
and Noncoordinating Solvents: Solvent’s Role in Evolution of the
Optical and Structural Properties, Chem. Mater. 2007, 19, 5185-
5193
nanocrystals in growth. J.Am.Chem.Soc., 124(9), 2049–2055
Pan, D.,Wang, Q., Jiang, S., Ji, X., An, L., 2005, Synthesis of extremely

~ 207 ~
 small CdSe and Highly luminescent CdSe/CdScore/shell nanocrys-
tals via a novel two-phase thermal Approach, Adv. Mat., 17, 2, 176-
179
Qu L., Peng X., 2002, Control of photoluminescence properties of CdSe, J.
Am. Chem. Soc., 124 (9), 2049–2055
Quinlan, F. T.,Koether, J,. Tremel, W.,Knoll, W,. Rishbud, S.,Stroeve, P.,
2000, Reverse micelle synthesis and characterization of ZnSe nano-
particles, Langmuir, 16, 4049–4051.
Rogach, A. L., 2008. Semiconduct or nanocrystal quantumdots, Wien-New
York: Springer.
Schaller, R.; Klimov, V. (2004). "High Efficiency Carrier Multiplication in
PbSe Nanocrystals: Implications for Solar Energy Conversion".
Physical Review Letters. 92 (18): 186601.
Spanhel L, Anderson M.A., 1991, Semiconductor clusters in the sol–gel
process: quantized aggregation, gelation and crystal growth in con-
centrated zinc oxide colloids. J. Am. Chem. Soc, 113(8):2826–2833.
Swihart M.T., 2003, Vapor-phase synthesis of nanoparticles, Current Opi-
nion in Colloid&Interface Science, 8(1),127–133.
Tang, D., Liu, J., Wu, X., Liu, R., Han, X., Han, Y., Huang, H., Liu, Y.,
Kang Z., 2014, Carbon Quantum Dot/NiFe Layered Double-
Hydroxide Composite as a Highly Efficient Electrocatalyst for
Water Oxidation, ACS Appl. Mater. Interfaces, 6(10), 7918–7925.
Valizadeh A., Mikaeili H., Samiei M., Farkhani S.M., Zarghami N., Xin
S.H., Yin A., Kim C., Dobrowolska M., Merz J.L.,1996, Formation
of self Assembling CdSe quantumdots on ZnSe by molecular beam
epitaxy, Appl.Phys.Lett., 69(25), 3884–3886.
Yang, S., Feng, X., Wang, X., Müllen K., 2011, Graphene-Based
Carbon Nitride Nanosheets as Efficient Metal-Free Electrocatalysts
for Oxygen Reduction Reactions, Angew. Chem. Int. Ed., 50: 5339–
5343.
Zhang, Z.,Zhang, J., Chen, N., and Qu, L., 2012. Graphene quantum dots: an
emerging material for energy-related applications and beyond,
Energy&Environmental Science, vol. 5, pp. 8869-8890.

~ 208 ~
 3.8 CORE SHELL

Dr. Gülşin ARSLAN

garslan@selcuk.edu.tr
Dr. Canan BAŞLAK
cbaslak@selcuk.edu.tr
SELÇUK UNIVERSITY
INTRODUCTION
Analysis and quantification of toxic pollutants in the ecological and biological
samples have gained significant importance due to the ever-increasing pollution
as a result of meeting the needs of increas-ing population of the world. In addi-
tion, energy need of the world is increasing every day and this led the science
communities to look for alternative energy sources. In this context, studies to
perform analysis with cheap techniques and methods, and produce renewa-ble
energy sources using cheap electronic materials are becoming more and more
prevalent in the science world. This energy need is expected to be met at least
partially through obtaining nanocrystals with florescence properties and using
these crystals to make optical (light emitting diodes) and electrical (solar cells)
devices by taking advantage of their improvable optical properties, in addition to
their applications in quantification of biological and chemical materials. These
materials, which stand out with their very small particle sizes and florescence
properties, can be prepared in types called core, core-shell and alloy.

3.8.1 Preparation and Importance of Core Shell Structure

In recent years, nanomaterials are drawing great attention with their interest-ing
properties and their benefits in many fields such as nanocatalysis, nanoelectro-
nics and medicine. Nanoparticles containing noble metals func-tion as active
catalytic compounds and these materials can be synthesized in different compo-
sitions and structures having different patterns, shapes and sizes. This type of
controlled attainability, potentially leads to the de-velopment of new technolo-
gies for application fields that involve environ-mentally-conscious and economi-
cally practicable processes [Gawande et al., 2015].
Conventionally, composite nanomaterials are consisted of an inner core and an
outer layer called shell, therefore they are called core-shell struc-tures. Materials
that generally have dual structures and are formed by the combination of metals
and anionic types (chalcogen elements) are called core structures. Core structu-

~ 209 ~
res can be obtained in forms such as CdTe, CdSe, CdS, PbS, PbTe, PbSe; Ni/Pd,
Pd/Co and Ag nanoparticles can be obtained in shapes like Ag/Ni, Ag/Co. Inte-
rior of such materials features the same properties everywhere [Li et al., 2009;
Xing et al., 2008; Yu et al., 2009, Son et al., 2004, Wang et al., 2012, Wang et
al., 2010, Guo et al., 2011]. Nanomaterials with core structure are coated with
shell structures to make them more durable against external factors (Figure
3.8.1) [Baslak, 2014].

Figure 3.8.1: A nanomaterial with core/shell structure [Baslak, 2014].

Since crystal surface can break down easily, outside of the core nanocrys-tal is
coated with another crystal shell structure, which has a higher band gap, during
synthesis in order to protect the core structure. Thereby, nano-crystal surface
defect is removed and various optical and electrical proper-ties of the crystal is
improved [Baslak, 2014]. In addition, it is possible to attain structures known as
core-shell-shell, which are multi-layered struc-tures defined as onionlike, by
using different synthesis methods. Core-shell nanostructures can be classified as
to involve different types such as inorganic/inorganic, inorganic/organic, orga-
nic/inorganic and organ-ic/organic, depending on the compositions and arran-
gements of the two compounds in the materials [Amouri et al., 2012; Park et al.,
2013]. Both core and shell structures can also be consisted of triple structures in
addi-tion to double ones [Pons et al., 2009].
Nanomaterials with core-shell structure can be classified as organic and inorga-
nic. Organic ones are carbon-based materials (mostly polymers), whereas inor-
ganic ones are the materials containing metal, metalloid and metal salt. Synthe-
ses of organic materials are mostly based on polymeri-zation techniques for the
preparation of organic core, shell or both. Fun-damental strategy of polymeriza-
tion technique is to add several units of suitable monomeric substrates with im-
portant functionalities and to form 3-dimensional structures. Inorganic can be
classified under two main groups as silica- and metal-based. Silica-based ones
are synthesized using the sol-gel method. Metallic nanomaterials are synthesized
through the reduc-tion of corresponding metal salt via trans-metalizing that uses

~ 210 ~
external reducing agents (NaBH4, hydrazine etc.) or intrinsic redox properties of
metallic initiators. Reaction medium, temperature and the type of reducing agent
affect the reaction and changing of these parameters also changes the particle
growth, size, shape, and therefore the chemical, physical, opti-cal and biological
properties.
The properties of the obtained materials must be firstly determined in order to
use them in various applications. Performance and properties of the nanomateri-
als depend on their sizes, morphologies and structural compo-sitions. Combina-
tion of inner material and outer shell in the core-shell struc-tures and the distri-
bution of various functional groups on the material have a significant impact on
the variety of the applications. Therefore, character-ization studies are not just
important in terms of learning the structural and physical properties of the core-
shell nanomaterials, but also important to provide a deep insight to the mecha-
nisms involved in many applications utilizing these nanosystems. To do this,
chemical and physical properties of these materials, such as size and shape of the
particles, surface proper-ties, nature of the surface coating and the presence of
foreign additives, must be clarified. There are many methods to clarify and cha-
racterize the structures of the materials. To give brief information on these tech-
niques;
Images obtained from SEM - scanning electron microscope, TEM - trans-
mission electron microscope and HRTEM - high resolution transmission elect-
ron microscope devices are used to determine the morphology, size and homo-
geneity of nanomaterials. However, since the signal collection on SEM is achie-
ved through the collection of secondary electrons reflected from the surface, this
instrument provides only the surface images of a material. Therefore, it is diffi-
cult to differentiate the core from the shell using the SEM analysis. However,
different fingerprint regions of core and shell can be clearly observed from an
image of a single nanomaterial seg-ment using the HRTEM technique (Figure
3.8.2).

~ 211 ~
Figure 3.8.2: a) UCN core structure, b) amorphous silica coated UCNs, TEM
images of mesoporous silica coated UCNs c) in 50 nm and d) in 25 nm [Gnana-
sam-mandhan et al. 2016].
X-Ray Diffraction (XRD) device is widely preferred to examine the phases and
microstructures within the crystal structure of various materials, includ-ing the
core-shell nanomaterials. XRD device is especially important in-strument that
can shed light to the presence of core-shell structures and it even enables the
simultaneous detection of separate phases of the core and shell. In addition, it is
possible to determine the distribution of materi-als inside a specified region by
using the energy distribution spectrometer (EDS) integrated into the TEM devi-
ce. Another important technique, espe-cially for elemental mapping and someti-
mes depth profiling of the com-pound, is the Electron Energy Loss Spectroscopy
(EELS), which is con-sidered as a complementary technique to EDS. Various
spectroscopic techniques are also developed for direct or indirect characteriza-
tion of optical properties of core-shell nanomaterials due to their absorption,
emission and plasmonic properties. UV-Vis spectroscopy is one of the spectros-
copic techniques that can absorb especially the UV-Vis region of electromagne-
tic radiation. Infrared spectroscopy can be used to identify the organic core/shell
nanostructures and the organic molecules inside them. Raman spectroscopy is
also very important in terms of surface properties of core-shell structures. Bru-
nauer-Emmett-Teller (BET) method is used for the determination of specific
surface area of porous core-shell nanomaterials [Gawande et al., 2015].

~ 212 ~
These nanomaterials are developed as a very important class of materials with
such unique, useful and practicable properties and they have a wide variety of
application fields. For examples these materials are widely used in areas such as
bio-nanotechnology [Rosenthal et al., 2011], advanced optical devices [Nann et
al., 2011], special magnetic devices [Muckel et al,. 2017], electronic optical
devices (Anikeeva et al., 2008), biological imaging systems [Jin et al., 2011],
energy storage materials, genetic engineering and stem cells [Jamieson et al.,
2007], fuel cells [Robel et al., 2006], dye-sensitized solar cells [Tian et al., 2013]
and very important catalytic pro-cesses [Iyer et al., 2014]. The ones with flores-
cence properties are used to make light emitting diodes (LED), semiconductor
ones with absorption ability are used for solar cells, catalyzing reactions due to
their catalytic activities, and for making sensor probes by using their optical and
electri-cal properties.

Conclusion

These nanomaterials are developed as a very important class of materials with

such useful and practicable properties arising from their core-shell structures and
they have a wide variety of application fields.

~ 213 ~
References

Amouri, H., Desmarets, C., and Moussa, J. (2012). Confined Nanospaces in

Metallocages: Guest Molecules, Weakly Encapsulated Anions, and
Catalyst Sequestration, Chemical Reviews, 112, 2015–2041.

Anikeeva , P.O., Madigan, C.F., Halpert, J. E., Bawendi, M. G., and Bulović,
V. (2008). lectronic and excitonic processes in light-emitting devices
based on organic materials and colloidal quantum dots, Phys. Rev. B
78, 085434.

Baslak, C. (2014). Ağır Metal Temelli Alaşım Kuantum Nokta Yapıların Elde
Edilmesi Optik Ve Membran Özelliklerinin İncelenmesi, Konya.

Du, J., Li, X., Wang, S., Wu, Y., Hao, X., Xu, C. and Zhao, X. (2012). Mic-
rowave-assisted synthesis of highly luminescent glutathione-capped
Zn1−xCdxTe alloyedquantum dots with excellent biocompatibility,
Journal of Materials Chemistry,22, 11390–11395.

Gawande, M.B., Goswami, A., Asefa, T., Guo, H., Biradar, A.V., Peng, D.L.,
Zboril, R. and Varma, R.S. (2015). Core–shell nanoparticles: synthesis
and applications in catalysis and electrocatalysis, Chemical Society
Reviews, 44, 7540-7920.

Gnanasammandhan, M.K., Idris, N. M., Bansal, A., Huang, K., Zhang, Y.

(2016). Near-IR photoactivation using mesoporous silica–coated
NaYF4:Yb,Er/Tm upconversion nanoparticles, Nature Protocols, 11,
688–713.

Guo, H.Z., Chen, Y.Z., Chen, X.Z., Wen, R.T., Yue, G.H. and Peng, D.L.
(2011). Facile synthesis of near-monodisperse Ag@Ni core-shell na-
noparticles and their application for catalytic generation of hydrogen,
Nanotechnology, 22, 195604- 195608.

Iyer, A., Chandra, A., Swaminathan, R., (2014). Hydrolytic enzymes conjuga-
ted to quantum dots mostly retain whole catalytic activity, Biochim
Biophys Acta., 1840(9):2935-43.

~ 214 ~
Jin, S., Hu, Y., Gu, Z., Liu, L. and Wu, H.-C. (2011). Application of Quantum
Dots in Biological Imaging, Journal of Nanomaterials, Article ID
834139, 13 pages.

Jamieson, T., Bakhshia, R., Petrovaa, D., Pococka, R., Imanib, M., Seifalian,
A.M., (2007). Biological applications of quantum dots, Biomaterials,
28, 4717–4732.

Li, J., Zhang, J.Z. (2009). Optical properties and applications of hybrid semi-
conductor nanomaterials, Coordination Chemistry Reviews, 253,
3015–3041.

Muckel, F., Barrows, C.J., Graf, A., Schmitz, A., Erickson, C.S., Gamelin,
D.R., Bacher, G. (2017). Current-Induced Magnetic Polarons in a Col-
loidal Quantum-Dot Device, Nano Lett., 17(8):4768-4773.

Nann, T., and Skinner, W.M. (2011). Quantum Dots for Electro-Optic Devi-
ces, CS Nano, 5 (7), 5291–5295.

Park, H.H., Woo, K., and Ahn, J.-P. (2013). Core-shell bimetallic nanopartic-
les robustly fixed on the outermost surface of magnetic silica microsp-
heres, Scientific Reports,3, 1497.

Pons, T., Lequeux, N., Mahler, B., Sasnouski, S., Fragola, A. and Dubertret, B.
(2009). Synthesis of Near-Infrared-Emitting, Water-Soluble
CdTeSe/CdZnS Core/Shell Quantum Dots, Chemistry of Materials,
21, 1418–1424.

Robel, I. , Subramanian, V., Kuno, M., and Kamat, P.V. (2006). Quantum
Dot Solar Cells. Harvesting Light Energy with CdSe Nanocrystals
Molecularly Linked to Mesoscopic TiO2 Films, J. Am. Chem. Soc.,
128 (7), 2385–2393.

Rosenthal, S.J.,Chang, J.C., Kovtun, O., McBride, J.R., and Tomlinson, I.D
(2011). Biocompatible Quantum Dots for Biological Applications,
Chem Biol. 18(1), 10–24.

Son, S.U., Jang, Y., Park, J., Na, H.B., Park H.M., Yun, H.J., Lee, J. and
Hyeon, T. (2004). Designed synthesis of atom-economical Pd/Ni bi-
~ 215 ~
 metallic nanoparticle-based catalysts for sonogashira coupling reac-
tion, Journal of the American Chemical Society, 126, 5026–5027.

Tian, J., and Cao, G. (2013). Semiconductor quantum dot-sensitized solar

cells, Nano Reviews, 4: 22578.

Wang, D., Xin, H.L., Wang, H., Yu, Y., Rus, E., Muller, D.A., DiSalvo, F.J.
and Abrun˜a, H.D. (2012). Facile Synthesis of Carbon-Supported Pd-
Co Core-Shell Nanoparticles as Oxygen Reduction Electrocatalysts
and their Enhanced Activity and Stability with Monolayer Pt Decora-
tion, Chemistry of Materials,24, 2274–2281.

Wang, D. and Li, Y. (2010). One-Pot Protocol for Au-Based Hybrid Magnetic
Nanostructures via a Noble-Metal-Induced Reduction Process, Journal
of the American Chemical Society, 132, 6280–6281.

Xing, B., Li, W.-w., Sun, K. (2008). A novel synthesis of high quality CdTe
quantum dots with good thermal stability, Materials Letters, 62, 3178–
3180.

Yu, K., Ouyang, J., Zaman, Md. B., Johnston, D., Yan, F. J., Li, G., Ratcliffe
C. I., Leek, D. M. Wu, X., Stupak, J., Jakubek, Z., and Whitfield, D.
(2009). Single-Sized CdSe Nanocrystals with Bandgap Photoemission
via a Noninjection One-Pot Approach, The Journal of Physical Che-
mistry C, 113, 3390–3401.

~ 216 ~
3.9 CARBON-BASED NANOMATERIALS

Dr. Cumhur Gökhan ÜNLÜ

cunlu@pau.edu.tr
Dr. Yasemin ÖZTEKİN
yoztekin@gmail.com
PAMUKKALE UNIVERSITY
SELÇUK UNIVERSITY
INTRODUCTION

Carbon atom has 6 electrons and belongs to the group IV of the periodic table
together with silicon, germanium, tin, lead and flerovium elements. However, in
contrast with other groups in the periodic table, these 6 elements are signifi-
cantly different than each other chemically and the most distinct element of this
group, the carbon atom, is the lightest (12.011 g/mol) and the least metallic ele-
ment of the group.
The first two electrons in the 1s2 2s2 2p2 electron distribution of neutral carbon
atom has no impact on binding and the energy difference between other elect-
rons is large, therefore, carbon atom has 4 valence electrons ready for bonding
and this enables carbon to form different structures. Carbon atom generally
forms covalent bonds instead of ionic bonds since it has a small atomic number,
thus, valence electrons that are closest to the nucleus are very strongly held.
Materials formed with carbon atoms manifest different physical and chemical
properties due to the sp, sp2 ve sp3 bonding geometry, which is caused by the
combination of electrons that are involved in the bonding of carbon atoms
between themselves. In the bonding formed with sp hybridization, for which the
acetylene can be given as an example, carbon atoms form a linear geometry with
each other and each atom has two bonds. In the bonding formed with sp2 hybri-
dization, for which the graphite plates can be given as an example, carbon atoms
form a triangular geometry with each other and each atom has three bonds. And
in the bonding formed with sp3 hybridization, for example diamond crystal, car-
bon atom has four bonds. Each different geometric shape of bondings means
different materials. Carbon atom is a special element in the periodic table since it
is the only element that can form bondings with sp, sp2 and sp3 hybridization.

~ 217 ~
The most abundant carbon compounds found in the nature are carbonate mine-
rals, such as carbon dioxide, calcite, coal and marble, and hydrocarbons, which
are the building blocks of coal, petroleum and natural gas. In addition, diamond
and graphite are other natural forms with their different crystal forms. In the
transparent diamond, among natural materials, which is rigid and robust, has
scratching and abrasive properties, has no electrical conductivity but a good
thermal conductor, each carbon bonds with four different carbon atoms to form a
three-dimensional solid structure.
On the other hand, graphite, which is known with its softness due to the weak
bonding between its layers, a good electrical conductor with a poor thermal con-
ductivity, has carbon atoms bonded on a two-dimensional plane where they form
wide, flat plates that are piled up on each other. These flat plates can slide on top
of each other, which makes graphite a suitable dry lubricant to reduce or prevent
the moving parts in the machines from abrasion due to friction. The reason why
graphite leaves a trace on paper is that these thin plates are separated from the
graphite by friction and remain on paper, for which the pencil tips hardened by
adding clay into the graphite can be given as an example. In addition to diamond
and graphite, carbon also has natural allotropes such as hexagonal diamond, and
unnatural artificial allotropes like glassy carbon, fullerene, carbon nanotube,
linear acetylenic carbon (Figure 3.9.1.). Alltropes of carbon, which do not have
any distinct, unique structure or form, are called amorphous carbon. Coal is an
amorphous carbon type.
With its unique properties, the carbon element has an undeniable importance
within the context of nanotechnology, which was pioneered by renowned physi-
cist Richard Feynman in 1974 and has made great contributions since then with
its theory and applications. There are interesting structures consisted of only
carbon atoms in nanometer scale that can be classified as balls, tubes, rods and
rings. How a cluster structure that can be represented with Cn in this classifica-
tion is formed depends on the “n” value. If the atomic number is an odd number,
cluster structure is formed as a one-dimensional like a chain, if atomic number is
an even number, than the cluster becomes two-dimensional like a ring. However,
n=2 is exempt from this generalization.
Carbon nanostructures have many theoretical study and applications in funda-
mental sciences like physics, chemistry and biology, as well as in engineering
fields and health applications with their robustness, different electrical and mec-

~ 218 ~
hanical properties (Ahmadi et al., 2017; Chen et al., 2017; Dasgupta et al., 2017;
Kumar et al., 2017).

Figure 3.9.1. Some carbon allotropes: a) diamond; b) graphite; c) hexagonal

diamond; d-f) fullerenes (C60, C540, C70); g) amorphous carbon; h) carbon
nanotube
(This image was published in page goo.gl/CEzPJv and retrieved from Google Images.)

3.9.1 Carbon nanoballs

Harold W. Kroto, Robert F. Curl ve Richard E. Smalley won the 1996 Nobel
Prize in Chemistry with their discovery of a new carbon allotrope where atoms
are arranged in closed shells back in 1985. They determined that this new form
had an icosahedral structure and named it as Buckminster-fulleren after the arc-
hitect Buckminster Fuller, who designed geodetic domes in 1960s.
Carbon nanoballs can have many different sizes from twenty atoms to thousands
of atoms. The smallest one has 20 atoms consisted of 12 regular pentagons (Fi-
gure 3.9.2.). The most widely known carbon nanoball is C60, which is called
fullerene and formed with 60 carbon atoms that are bonded together with sp2
hybridization. C60 is a spherical structure and consisted of 12 pentagonal and 20
hexagonal sides with its dodecahedral symmetry (icosahedral symmetry). Anot-
her structure that can be classified as carbon nanoballs is C8 (cubane) which
consisted of 8 carbon atoms with less than 20 atoms. Although this structure
does not have a ball shape, it is classified in this group due to its cage structure.
~ 219 ~
Generally, nanoballs with icosahedral symmetry are single-walled with different
sizes, but they can also be in dimer groups or structures similar to interwoven
onion layers.

Figure 3.9.2. Some fullerene examples (Guo et al, 2013)

Carbon nanoballs can be found in pure form, but they can also be doped by pla-
cing different atoms into the balls without disrupting their geometric structure.
Doping of carbon nanoballs causes changes in their electrical, mechanical and
optical properties (Tayfun et al., 2015; Kausar, 2017; Noh et al., 2017; Youn et
al., 2017).

3.9.2 Carbon nanotubes

Carbon nanotubes were first discovered experimentally by Iijima in 1991 and

they are an allotrope of carbon element with the largest length: diameter ratio of
28x106:1 that no other material can possess. The tubes, obtained from graphite
by evaporation method, are structures formed by curving the graphite plate into
the cylinder (Figure 3.9.3.).

Figure 3.9.3 a) graphene, b) single layered carbon nanotube

(This image is published on goo.gl/m79Rvx and retrieved from Google Images.)
~ 220 ~
In orderly carbon nanotube structures, atoms are bonded together with sp2 hyb-
ridization as in graphite plates. Atoms form only hexagonal geometry and each
atom has just three neighbors. Carbon tubes can be very fragile in macroscopic
sizes or very flexible and robust in nanometer dimensions. An undamaged car-
bon nanotube is robust enough to withstand a load of 300 million times its own
weight and has a larger mass:area ratio than normal materials, therefore, it is the
most robust material known. Today, there is no other material with this level of
robustness.
These structures, which can have different diameter and sizes, can be found as
single layered (single walled-SWCNT) or multi layered (multi walled-MWCNT).
Depending on the curling direction of the graphite plate, tubes can have zigzag
and armchair structures, and bent nanotubes can be formed by bending one of
these structures. Tubes manifest different mechanical and electrical properties
depending on their directions (Figure 3.9.4.). For example, armchair structure has
metallic properties, whereas zigzag structure has semiconductor properties. For
zigzag structure to have metallic properties, number of rings around the tube must

a b c

be multiples of 3.

Figure 3.9.4. a) Armchair, b) Zigzag and c) Bent carbon nanotubes

(This image is published on goo.gl/8aX4RR and retrieved from Google Images.)

Depending on whether the carbon is in a solid or gas state, carbon nanotubes can
be obtained through methods like arc discharge, laser abrasion, chemical vapor
precipitation and electrolysis, and can be purified by processes like oxidization,

~ 221 ~
acid application, thermal treatment and filtering. Carbon nanotubes are mostly
used in electronics and energy fields.

3.9.3 Carbon nanorods

Carbon nanorods are less flexible than carbon nanotubes and they are consisted
of interwoven and walled carbon nanotubes. The distance between the walls of
these interwoven tubes is longer than the distance between two carbon atoms. In
case the distance between the walls become shorter than that of between two
carbon atoms, carbon atoms in the different interwoven walls bond with each
other through sp3 hybridization. Carbon nanorods are formed as a result of the
bonding between the walls of carbon nanotube. Mechanical and electrical pro-
perties of nanorods change depending on the nanotubes that take part in the bon-
ding.

3.9.4 Carbon nanorings

Nanotubes can be turned into rings with 0.7 micron diameter that are consisted
of single walled nanotubes or helical structures. Nanotubes used to form rings
have very small diameters of 1.4 nm. Very different ring models can be obtained
by using structures having different inner and outer diameters, and rings have
different properties depending on the properties of the structures used. However,
this is just a corporate taught for now.

NOTES:

 Carbon has different stable structures from three-dimensional (3D) semi-

conductor diamond structure and two-dimensional (2D) semi-metallic
graphite in macro scale to one-dimensional conductor and semiconduc-
tor nanotubes and zero-dimensional (0D) nano-balls in nano scale.
 Since 1D and 0D structures are in nano scale, these systems called nano-
tubes and nanoballs, which form the basis of carbon nanostructures.

~ 222 ~
 Years of 1996 and 2010 Nano Carbon Nobel Prize

Only reason for the difference between these structures is the different arrays of
carbon atoms!!!

~ 223 ~
References

Ahmadi, M., Elmongy, H., Madrakian, T., Abdel-Rehim, M., (2017).

Nanomaterials as sorbents for sample preparation in bioanalysis: A review,
Analytica Chimica Acta, 958, 1-21.

Chen, M., Qin, X., Zeng, G., (2017). Biodegradation of carbon nanotubes,
graphene and their derivatives, Trends in Biotechnology, 35, 836-846.

Dasgupta, A., Rajukumar, L.P., Rotella, C., Lei, Y., Terrones, M., (2017).
Covalent three dimensional networks of graphene and carbon nanotubes: synthesis
and environmental applications, Nanotoday,12, 116-135.

Guo, J.H., Zhang, H., Miyamoto, Y., (2013). New Li-doped fullerene-intercalated
phthalocyanine covalent organic frameworks designed for hydrogen storage, Phy-
sical Chemistry Chemical Physics, 15, 8199-8207.

Kausar, A., (2017). Advances in polymer/fullerene nanocomposite: A review on

essential features and applicaitons, Polymer-Plastics Technology and Engineering,
56, 594-605.

Kumar, S., Rani, R., Dilbaghi, N., Tankeshwar, K., Kim, K.H., (2017). Carbon
nanotubes:a novel material for multifaceted applications in human healthcare,
Chemical Society Reviews, 46, 158-196.

Noh, S.H., Kwon, C., Hwang, J., Ohsaka, T., Kim, B.J., Kim, T.Y., Yoon, Y.G.,
Chen, Z., Seo, M.H., Han, B., (2017). Self-assembled nitrogen-doped fullerenes
and their catalysis for fuel cell and rechargeable metal-air battery applications,
Nanoscale, 9, 7373-7379.

Tayfun, U., Kanbur, Y., Abaci, U., Guney, H.Y., Bayramli, E., (2015). Mechanical,
flow and electrical properties of thermoplastic polyurethane/fullerene composites:
Effect of surface modification of fullerene, Composites Part B: Engineering, 80,
101-107.

Youn, Y.S., Kwag, D.S., Lee, E.S., (2017) . Mutifunctional nano-sized fullerenes
for advanced tumor therapy, Journal of Pharmaceutical Investigation, 47, 1-10.

~ 224 ~
3.10 GRAPHENE

Dr. Cumhur Gökhan ÜNLÜ

cunlu@pau.edu.tr
PAMUKKALE UNIVERSITY

INTRODUCTION
Graphene is carbon allotrope with superior properties and is consisted of a single
layer of carbon atoms arranged in an hexagonal lattice and it is the first two-
dimensional material to be obtained in the world. Graphene was discovered by
Russian scientists Andre Geim and Kostas Novoselov from Manchester Univer-
sity in 2004 and they won the Nobel Prize in 2010 as graphene is the first two-
dimensional material ever to be produced. It became the focus of science world
since 2010 and it is being studied as the main material in many research. Grap-
hene earned its ever-increasing reputation with its superior electrical and thermal
conductivity and mechanical properties.

Figure 3.10..1. Graphene

(http://tr.wikipedia.org/index.php?q=aHR0cHM6Ly90ci53aWtpcGVkaWEub3JnL3dpa2kvR3JhZmVu)
(http://www.techandfacts.com/what-is-graphene/)

In fact, graphene is the fundamental structure of graphite, the raw material of lead
pencil which we use every day. Graphite is the name of the structure that is formed
when multiple graphene layers are combined together on top of each other. There-
fore, when we examine our lead pencil under microscope, we can easily its layered
structure. The reason why our lead pencil breaks when we write is this layered
structure. Now, we may think about another question. Why is our lead pencil,
which is made of graphene that is even stronger than strongest material diamond,
can be broken under very small pressures. We should remember that in fact, dia-

~ 225 ~
mond is another carbon allotrope that is formed by the three-dimensional crystalli-
zation of carbon atoms, which also form the graphene. The answer is the way that
carbon atoms come together. We call this the crystal structure of carbon atoms. The
forms, in which the carbon atoms come together with different shapes, are called
the allotropes of carbon. Different allotropes of carbon are shown in Figure 3.10.2.

Figure 3.10.2. 2D graphene, which is the building block of all other graphitic
materials (Geim and Novoselov 2007)

The study that helped Andre Geim and Kostas Novoselov to discover graphene
in 2004 is actually based on an experiment that everyone can try at their homes.
Despite the long-standing prediction of theoretical physicists that a 2-
dimensional material cannot remain stable, these scientists made their discovery
by using a piece of sellotape and some graphite. They put some graphite powder
on the tape, sticked the tape together and then pulled it back again; this way,
layers inside the graphite were separated and they transferred these separated
layers onto a silicon substrate. They showed the presence of graphene through
the examinations that had conducted under microscope. This method is called
mechanical exfoliation method (Fig. 3.10.3).

~ 226 ~
 Figure 3.10..3. Mechanical exfoliation method
http://pubs.rsc.org/en/content/articlehtml/2015/ta/c5ta00252d)

Figure 3.10.4. Andre Geim

(http://www.nature.com/news/andre-geim-graphene-s-buzz-has-spread-1.17861)

Folding mobile phones, tablets and screens are produced, flexible and elastic
energy related and electrical applications become possible with the discovery of
graphene. Today, studies are rapidly ongoing for the wide use of graphene in
many areas such as energy, electronics, biosensor, implant, medicine, food and
environment.

~ 227 ~
 Figure 3.10.5. Different graphene applications

Properties of Graphene:
Mechanical Properties:
Graphene is an extremely rigid, durable and highly elastic material. The young
modulus of graphene, which is a concept used to understand mechanical proper-
ties of materials, is approximatel y1 TPa and its fracture resistance is 130 GPa.
These superior mechanical properties is a result of the ways that carbon atoms of
the graphene come together. Due to the hexagonal shape of carbon atoms, C-C
bonds have 120o degrees of angle and this enables them to bend under pressure
and constraint. Graphene is the thinnest material ever to be produced to date and
it is 200 times more durable than steel used in structures thanks to this bonding
structure.
Thermal Properties:
Graphene has the highest thermal conductivity of all materials. Thermal conduc-
tivity of graphene is 6000 W/m K. Therefore, it rapidly conducts temperature.

~ 228 ~
Optical Properties:
Graphene absorbs 2.3% of the light, and it has 97.7% transparency. Therefore, it
is a potential material that can be used for conductive screen applications neces-
sary for mobile phones and tablets. The reason for this high transparency is the
single-layered structure of graphene. Experiments conducted on the number of
layers of graphene, structures with more than 10 layers were shown to lose

transparency.

Figure 3.10.6. Graphenin optic mikroskop görüntüsü (Fine Structure Constant

Defines Visual Transparency of Graphene R. R. Nair,1 P. Blake,1 A. N. Grigo-
renko,1 K. S. Novoselov,1 T. J. Booth,1 T. Stauber,2 N. M. R. Peres,2 A. K.
Geim1* Science 320 (5881), 1308)

Electrical Properties:
Graphene is a semimetal that exhibits semi-conductors properties with zero for-
bidden energy interval. Valance and conductivity bands of graphene meet at
Dirac point, so, graphene is a semi-conductor material with zero forbidden
energy interval. Therefore, graphene has very good electrical conductivity. Car-
rier mobility of graphene is approximately 200000 cm2.V-1.s-1. This value is
even higher than that of gold and copper, which are known to be very good con-
ductors.

~ 229 ~
Figure3.10.1.7. Optic microscop image of graphene (Fine Structure Constant
Defines Visual Transparency of Graphene R. R. Nair,1 P. Blake,1 A. N. Gri-
gorenko,1 K. S. Novoselov,1 T. J. Booth,1 T. Stauber,2 N. M. R. Peres,2 A.
K. Geim1* Science 320 (5881), 1308)

Production Methods:
After its discovery, many production methods are developed to obtain high qua-
lity single-layered graphene that has large surface area. Today, researches are
ongoing to obtain better quality and cheaper graphene via different methods.
Production methods have many advantages and disadvantages compared to each
other. For graphene production, there are two methods parallel to the nanomate-
rial production techniques; bottom-up methods and top-down methods. Bottom-
up method is the attainment of structures by constructing atoms, the building
blocks of the matter, one by one. Obtaining nano structures with this method
contains extremely complex and difficult processes. Top-down methods involve
the reduction of bulk materials into nano sizes by mechanical, physical and che-
mical dissolution. These methods include simpler and cheaper processes than the
bottom-up method. The mechanical exfoliation, the method that enabled the
discovery of graphene, is an example for top-down production methods.

~ 230 ~
Figure 3.10.8. Production schematics of graphene based on bottom-up and top-
down processes (Edwards, R. S. and Coleman, K. S., “Graphene synthesis: rela-
tionship to applications”, Nanoscale, 5 (1), 38-51, (2013)).
To give examples, top-down methods: Mechanical exfoliation, reduction of
graphite oxide, arc discharge method, divergence of carbon nanotubes, chemical
exfoliation methods. Bottom-methods are: Epitaxial growth on SiC, chemical
vapor deposition (CVD) etc. Among these, CVD methods is the successful one
in attaintment of quality graphene with large surface area.
Post-production graphene presence and structure can easily be determined via
Raman spectroscopy, optical microscopy, electron microscopy, atomic force
microscopy methods.

Figure 3.10.9. Raman spectroscopy of graphene

(https://www.azom.com/article.aspx?ArticleID=10130)

~ 231 ~
 Figure 3.10.10. Image of graphene under electron microscope
(http://www.megantech.pl/en/top/graphene/graphene-oxide/powders-
flakes/single-layer-graphene-oxide/)

~ 232 ~
3.11 THIN FILMS

Dr. Volkan ONAR

vonar@pau.edu.tr
PAMUKKALE UNIVERSITY

INTRODUCTION

Coating glass and ceramic materials with pure metals in the past centuries has
increased the interest towards thin films in 1940s and 1950s, and this trend con-
tinues to grow in recent years. Thin films are materials that are thinner than 1
m . These materials form an atomic or molecular thin layer, on a surface that
supports the formation of the film by using different production methods. This
thin film significantly improves the mechanical, electrical and optical properties
of the new materials and tools. Large number of particles forming the thin films
shows a gradual transition from solid structure to molecular structure [2]. These
are present in all kinds of devices that we use in our daily lives. Different pro-
perties of the thin films are used for desired purposes.

Thin films are used in many applications: on surfaces with reflection ability by
using their optical properties, on memory disks of electronic circuits by using
their magnetic properties, on circuit components of superconduc-
tor/semiconductor devices by using their electrical properties, coating of insula-
tion surfaces, for anti-corrosion purposes by using their superior chemical pro-
perties. In recent years, use of thin films in nanomaterial industry is rapidly inc-
reasing for their cost-effective application [5].
Keywords:Thin Films

3.11.1 Thİn Fİlms

Thin films were first used for decorative purposes on leaded glasses and
ceramics. After these processes, they were used to obtain silver films on glass
surfaces by using silver salts. Their first scientific attainment was achieved in
1838 by using electrolysis method. Later on, thin films were produced through
chemical reaction by Bunsen in 1852, through vaporization in noble gas by
Faraday, and via Joule heating method by Kundt and Nahrwold [6].

~ 233 ~
Types of thin films can be classified as follows depending on the type of
material used:
 Superconductor films
 Semiconductor films
 Transparent conductor films
 Organic films
 Semiconductor alloy films with amorphous structures
 Ferroelectric films
 Inorganic polymeric films
 Pyroelectric films

3.11.2 Thin Films Production Teqniques

Thin film production methods include all nanomaterial production methods.

However, properties of thin films can be very different from each other depen-
ding on their production method. The method to be used for thin film production
must be determined based on the type and size of the surface to be coated with
thin film, coating temperature, coating material of of the surface to be coated,
cost and the intended purpose of the thin film. Thin film production methods are
listed in Figure 3.11.1.

~ 234 ~
Figure 3.11.1. Thin film production techniques

~ 235 ~
References

1. David A., Shah S.I., “Handbook of Thin Film Process Technoloy”, Insti-
tute of Physics Publishing, Bristol and Philadelphia, 25, 1995.
2. Kiyotaka W., Shigeru H., “Handbook of Sputter Deposition Techno-
logy”, Hardcover, 1992.
3. Ekinci, H., “Metal-organik Kimyasal Buharlaştırma Yöntemi ile Kristal
Büyütme (MOCVD) Sisteminin İncelenmesi”, Yüksek Lisans Tezi,
Cumhuriyet UNIVERSITY Fen Bilimleri Enstitüsü, Sivas, 2008
4. Pejova B., et al., “Structural and Optical Properties of Chemically Depo-
sited Thin Films of Quantum-Sized Bismuth (III) Sulfide”, Materials
Chemistry and Physics, 99, 39–49, 2006.
5. Eckertova, L., “Pysics of Thin Films”, s. 340, Plenum Press, 340,
Newyork and London , 1986.
6. Hass, G., Thun, R.E., “Physics of Thin Films Advances in Research and
Development”, 341, Acedemic Press, USA, 1969.
7. Bilgin, V., “ZnO Filmlerinin Elektrik, Optik, Yapısal ve Yüzeysel Özel-
likleri Üzerine Kalay Katkısının Etkisi”, Doktora Tezi, Osmangazi
UNIVERSITY, Eskişehir, 2003.
8. Canci, U., “CBD Yöntemiyle Hazırlanmış Katkılı ve Katkısız CdS İnce
Filmlerin Elektriksel ve Optik Özelliklerinin Belirlenmesi”, Yüksek Li-
sans Tezi, Gebze İleri Teknoloji Enstitüsü Mühendislik ve Fen Bilimleri
Enstitüsü, Gebze, 2009.
9. Özkan, İ., “Nanoteknolojik Yöntemler ile Malzemenin Yüzey Özellikle-
rinin İyileştirilmesi”, Yüksek Lisans Tezi, Dokuz Eylül UNIVERSITY
Fen Bilimleri Enstitüsü, İzmir, 2006.
10. Sönmezoğlu S., Koç M., Akın S., “ İnce Film Üretim Teknikleri”, Erci-
yes Üniversity Journal of The Institute of Science and Technology, 28
/5, 389 – 401, Kayseri, 2012.

~ 236 ~
3.12 NANOPARTICLE SHAPES

Dr. İmren HATAY PATIR

imrenhatay@gmail.com
Dr. Emre ASLAN
emreaslan89@gmail.com
SELÇUK UNIVERSITY

INTRODUCTION
Nanomaterials have different shapes than bulk materials and this makes them
unique for use in common applications such as biomedicine, catalysis, fuel cells,
solar cells and magnetic data storage. There are two fundamental approaches to
the synthesis of nanomaterials; “bottom-up” and “top-down”. Nanomaterials
with different size and structure can be obtained through the application of diffe-
rent methods of synthesis. Shapes can be classified as 0D (isotropic structure),
1D, 2D and 3D (anisotropic structure) in terms of nanomaterial sizes. Solid and
mesoporous/hollow morphologies of size-based nanoparticles are shown in Fi-
gure 3.12.1.

Figure 3.12.1. Typical morphologies of solid and mesoporous/hollow nanopar-

ticles with 0D, 1D and 2D shapes and other 3D complex structures [Wu, 2016

Primary shapes of 0D nanoparticles include spherical, pseudo-spherical, dodeca-

hedral, tetrahedral, octahedral, cubic and their corresponding hollow morpholo-

~ 237 ~
gies.1D shapes can be classified as nanotubes, nanoneedles, nanorods or na-
nowires, nanoshuttles, nanocapsules and their hollow structures [Zhang, 2014;
Lu, 2015]. Circular disks, hexagonal / triangular / tetragonal plates or layers,
belts, mesoporous hollow nanospheres, hollow rings etc. are known as 2D shape
class [Li, 2012].3D morphologies of nanoparticles are complex and include na-
nothorns, nanoflowers, nanostar, polyhedral nanoframes, poly hollow shell, hol-
low bundle and similar nanoparticles [Lv, 2015; Lin, 2012; Wu, 2016].

In addition, examples of 0D, 1D, 2D and 3D shape classifications of nanopartic-

les are given in Figure 3.12.2 [Tan, 2011]. In each row, from left to right, partic-
les become geometrically higher-level structures in terms of aspect ratio, edge
and face number or dendrite number. Last particle of each row represents a hol-
low structure. Sixth row includes various complex nanoparticles, seventh row
includes various hollow polygonal and polyhedral nanoparticles.

A great deal of effort has been put to control the shape of nanoparticles [Ho,
2011; Radi, 2010]. Generally, shape formation of nanoparticles is thermodyna-
mically or kinetically controlled as dispersion. Production of thermodynamically
controlled shapes of nanoparticles is achieved through chemical potential driving
based on the temperature and supersaturation of the reaction dispersion.

On the other hand, kinetically controlled morphologies with different sizes can
be obtained by changing the reaction conditions depending on the nucleation
theory. Growth of nucleus in kinetically controlled processes contributes to the
formation of nanoparticles with anisotropic shapes [Nyugen, 2013]. Therefore,
synergistic effect of thermodynamic and kinetic factors plays critic roles in the
determination of final shape of nanoparticles [Zhang, 2013]. Factors affecting
the shape of the nanoparticles are briefly explained below.

~ 238 ~
Figure 3.12.2. Classification of nanoparticles based on geometric parameters (1-
nanosphere, 2- hollow nanosphere, 3- nanobar, 4- nanorod, 5- nanobone, 6- na-
nobeam, 7- nanobelt, 8- nanowire, 9- hollow nanorod, 10- triangle, 11- square,
12- pentagon, 13- hexagon, 14- truncated triangle, 15- disk, 16- nanoring, 17-
tetrahedron, 18- cube, 19- decahedron, 20- octahedron, 21- icosahedron, 22-
rhombicuboctahedron, 23- hollow nanocage, 24- monopod, 25- bipod, 26- tri-
pod, 27- tetrapod, 28- star-shaped, 29- octapod, 30- nanopyramid, 31- nanoclo-
ver, 32- nanosnowflake, 33- nanothorn, 34- nanotree, 35- dendtrite, 36- na-
nocrescent, 37- nanoshell (ring), 38- porous triangle, 39- nanoshell (cubic), 40-
truncated octahedron, 41- nanocage, 42- nanoskeleton, 43- nanobox) [Tan,
2011].

3.12.1 Factors affecting the shape control of nanoparticles

Supersaturation
Nanoparticle synthesis processes include reaction dispersion, precursor mono-
mers, reducing agents, solvents, stabilizers and other additives. Supersaturation

~ 239 ~
means the initial monomer concentration or the monomer ratios in the presence
of multiple monomers. According to classical nucleation and growth theory,
supersaturation plays a direct and significant role in the determination of nuclea-
tion and growth ration [Chang, 2014; Do, 2011]. Therefore, supersaturation is
one of the important factors that affect the shape of nanoparticles.

Concentration of Precursor Monomer and Additives

Supersaturation is directly and significantly dependent factors such as on precur-
sor concentration, reducing agent concentration [Ho, 2011] or ratio [Wang,
2014]. As it can be seen on Figure 3, shape of the nanoparticles, formed by inc-
reased ascorbic acid concentration, which is used as a reducing agent.

Figure 3.12. 3 SEM images showing the change in the shape of Au nanoparticles
induced by reducing agent concentration [Eguchi, 2012].

pH effect

Changing the pH by adding acid or base (H+, OH- or NH3) may change the states
of chemical types in the dispersion and cause coordination bonds with ions insi-
de the precursor monomer dispersion to form a complex. Therefore, pH is an
important factor in the control of the nanoparticle shapes (Figure 3.12.4).

~ 240 ~
Figure 3.12.4. TEM images of α-Fe203 with different shapes due to the changes
in pH [Jia, 2006]

Solvent
Solvents with different functional groups like ionic liquids provide coordination
with precursor monomer. This is significantly advantageous for thermodynami-
cally- or kinetically-controlled nanoparticle synthesis due to increased supersatu-
ration [Wagle, 2004; Niederberger, 2006; Kobayashi, 2012]. In addition, diffe-
rent solvent mixtures and solvent compounds enable the control of nanoparticle
shape [Han, 2009; Liu, 2012].

Temperature
Temperature is the thermodynamic parameter of the reaction dispersion. Increased reac-
tion temperature in the synthesis of nanoparticles also increases the supersaturation and
the reduction rate of the precursor agent in the dispersion. Temperature increase leads to
faster thermodynamically-controlled nucleation and growth, therefore reducing the dura-
tion of the reaction [Guy-Lopez, 2008].

Surfactants and additives

Most nanoparticles tend to agglomerate as large particles with irregular and
unwanted shapes due to their high free energy at nanoscale. Surfactants and ad-
ditives reduce the surface energies of the nanoparticles and are considered as
most suitable tools to achieve the desired shapes. Beside this, the stable layers
formed on the surface of nanoparticles by surfactants and additives, protects the
dispersed particles against agglomeration [Xing, 2014; Wang, 2010].

~ 241 ~
Summary
• There are two fundamental approaches to the synthesis of nanomaterials;
“bottom-up” and “top-down”.
• Shapes can be classified as 0D (isotropic structure), 1D, 2D and 3D
(anisotropic structure) in terms of nanomaterial sizes.
• Shape formation of nanoparticles is thermodynamically or kinetically
controlled as dispersion.
• Factors affecting the shape control of nanoparticles can be listed as su-
persaturation, concentration of precursor monomer and additives, pH ef-
fect, solvent, temperature, surfactants and additives.

~ 242 ~
 References

Chang J., Waclawik E. R., 2014, Colloidal semiconductor nanocrystals: control-

led synthesis and surface chemistry in organic media, RSC Adv., 4(45),
23505–23527.
Do T. O., Nguyen T. D., Dinh C. T., 2011, A general procedure to synthesize
highly crystalline metal oxide and mixed oxide nanocrystals in aqueous
medium and photocatalytic activity of metal/oxide nanohybrids, Nanos-
cale, 3(4), 1861–1873.
Eguchi M., Mitsui D., Wu H. L., Sato R., Teranishi T., 2012, Simple reductant
concentration-dependent shape control of polyhedral gold nanoparticles
and their plasmonic properties, Langmuir, 28(24), 9021–9026.
Goy-Lopez S., Castro E., Taboada P., Mosquera V., 2008, Block copolymer-
mediated synthesis of size-tunable gold nanospheres and nanoplates,
Langmuir, 24(22), 13186–13196.
Han Y. C., Liu S. H., Han M., Bao J. C., Dai Z. H., 2009, Fabrication of hierarc-
hical nanostructure of silver via a surfactant-free mixed solvents route,
Cryst. Growth Des., 9(9), 3941–3947.
Ho C. H., Tsai C. P., Chung C. C., Tsai C. Y., Chen F. R., Lin H. J., Lai C. H.,
2011, Shape-controlled growth and shape-dependent cation site occu-
pancy of monodisperse Fe3O4 nanoparticles, Chem. Mater., 23(7),
1753–1760.
Ho C. H., Tsai C. P., Chung C. C., Tsai C. Y., Chen F. R., Lin H. J., Lai C. H., 2011,
Shape-controlled growth and shape-dependent cation site occupancy of
monodisperse Fe3O4 nanoparticles, Chem. Mater., 23(7), 1753–1760.
Jia C., Cheng Y., Bao F., Chen D. Q., Wang Y. S., 2006, pH value-dependant growth
of α-Fe2O3 hierarchical nanostructures, J. Cryst. Growth, 294(2), 353–
357.
Kobayashi M., Kato H., Kakihana M., 2012, Synthesis of spindle and square
bipyramid-shaped anatase-type titanium dioxide crystals by a solvot-
hermal method using ethylenediamine, J. Ceram. Soc. Jpn., 120(1407),
494–499.
Li X. L., Zhang F. Q., Ma C., Deng Y., Wang Z. F., Elingarami S., He N. Y., 2012,
Controllable synthesis of ZnO with various morphologies by hydrother-
mal method, J. Nanosci. Nanotechnol., 12(3), 2028–2036.

~ 243 ~
Lin X. H., Ji G. B., Liu Y. S., Huang Q. H., Yang Z. H., Du Y. W., 2012, Formation
mechanism and magnetic properties of hollow Fe3O4 nanospheres synt-
hesized without any surfactant, CrystEngComm, 14(24), 8658–8663.
Liu J., Xu B., Song C., Luo H. D., Zou X., Han L. X., Yu X. B., 2012, Shape-
controlled synthesis of monodispersed nano-/micro-NaY(MoO4)2 (do-
ped with Eu3+) without capping agents via a hydrothermal process,
CrystEngComm, 14(8), 2936–2943.
Lu Z. X., Huang Y. F., Zhang L. M., Xia K., Deng Y., He N. Y., 2015, Preparation of
gold nanorods using 1,2,4-Trihydroxybenzene as a reducing agent, J.
Nanosci. Nanotechnol., 15(8), 6230–6235.
Lv H. L., Ji G. B., Liu W., Zhang H. Q., Du Y. W., 2015, Achieving hierarchical
hollow carbon@Fe@Fe3O4 nanospheres with superior microwave ab-
sorption properties and lightweight features, J. Mater. Chem. C, 3(39),
10232–10241.
Niederberger M., Garnweitner G., Buha J., Polleux J., Ba J., Pinna N., 2006,
Nonaqueous synthesis of metal oxide nanoparticles: Review and indium
oxide as case study for the dependence of particle morphology on pre-
cursors and solvents, J. Sol-Gel Sci. Technnol., 40, 259–266.
Radi A., Pradhan D., Sohn Y., Leung K. T., 2010, Nanoscale shape and size control
of cubic, cuboctahedral, and octahedral Cu-Cu2O core-shell nanopartic-
les on Si(100) by one-step, templateless, capping-agent-free electrode-
position, ACS Nano, 4(3), 1553–1560.
Tan S. J., Campolongo M. J., Luo D., Cheng W., 2011, Building plasmonic nanost-
ructures with DNA, Nature Nanotechnology, 6, 268-276.
Wagle, D. V. Zhao H., Baker, G. A., 2014, Deep eutectic solvents: Sustainable
media for nanoscale and functional materials, Acc. Chem. Res., 47(8),
2299–2308.
Wang J., Hou S. C., Zhang L. Z., Chen J. C., Xiang L., 2014, Ultra-rapid forma-
tion of ZnO hierarchical structures from dilution-induced supersaturated
solutions, CrystEngComm, 16(30), 7115–7123.
Wang W., Howe J. Y., Li Y. A., Qiu X. F., Joy D. C., Paranthaman M. P.,
Doktycz M. J., Gu B. H., 2010, A surfactant and template-free route for
synthesizing ceria nanocrystals with tunable morphologies, J. Mater.
Chem., 20(36), 7776–7781.
Wu Z., Yang S., Wu W., 2016, Shape control of inorganic nanoparticles from
solution, Nanoscale, 8, 1237.

~ 244 ~
Xing R. M., Xu F. L., Liu S. H., Niu J. Y., 2014, Surfactant free fabrication of
Fe3O4 nanospheres with selective shape, Mater. Lett., 134, 71–74.
Zhang L. M., Xia K., Lu Z. X., Li G. P., Chen J., Deng Y., Li S., Zhou F. M., He
N. Y., 2014, Efficient and facile synthesis of gold nanorods with finely
tunable plasmonic peaks from visible to Near-IR range, Chem. Mater.,
26(5), 1794–1798.

~ 245 ~
3.13 SURFACE MODIFICATION of NANOMATERIALS
Dr. Arzu YAKAR
ayakar@aku.edu.tr
AFYON KOCATEPE UNIVERSITY

INTRODUCTION
Nanoparticles aggregate very easily due to their high surface energy and large
surface area. On the other hand, NP has poor affinity for materials with relati-
vely poor surface energy. When these two types of materials are mixed, a phase
separation occurs since these materials are not compatible inside each other. If a
solution to prevent agglomeration of nanoparticles in the material is found, na-
noparticles can be used for different and good applications in special material,
and therefore material performance in mechanical, optical, thermal and other
aspects can be significantly improved. Therefore, the effort to maintain the nano
size of the NP in the material is one of the purposes of surface modification pro-
cess in nanotechnology field. NP surface modification is the most important part
of surface engineering.

3.13.1 Surface Modification of Nanoparticles

Surface engineering is a design consisted of a system surface, and substrate
materials integrated onto this surface. Surface engineering is a system
engineering that involves the use of various surface technologies that allows the
required modification to the surface of material, which is absent from the
material itself but needed to have the necessary performance (Figure 3.13.1).

Nano-surface engineering is an advanced technology derived from the combina-

tion of conventional surface technologies and modern physical and chemical
methods. This technology covers a wide material range from metallic and non-
metallic to ceramic and composite etc. and deals with all areas of these materi-
als, including their intermediate surfaces. Surface coating, surface thin film and
surface modification come to mind in nano-surface engineering. Manufacturing
technology moved from submicron level to nanometer and even to atomic or
molecular level when the development of nanotechnology was combined with
the design and manufacturing of microelectromechanical systems. Since nano-
particles are presented with different characteristics than macro materials in
terms of power, electrical, sound, light, thermal and magnetic properties, it is

~ 246 ~
understood that modification of surface characteristics and use of conventional
surface processing and design methods are no longer applicable. Nanotechnolo-
gical surfaces are particularly important for conventional materials and caused
nano-surface engineering to be formed. Nano-surface engineering is an enginee-
ring field that equips the material with nanotechnological surface through the use
of special processes. Nanostructure process is the series of processes applied to
modify the surface, to add a new property or to enhance it. Depending on the
surface characteristics needed to be achieved, nano-surface engineering has a
comprehensive application field including high technology fields such as avia-
tion, MARITIME, computer technologies, electronics, and in other important
aspects of human life from transportation to oil, chemistry, construction, irriga-
tion and machinery industries.

Figure 3.13.1. Nanoparticle sample with surface modification

(This image is published on https://www.slideshare.net/Reset_co/surface-modification-of-
nanoparticles-for-biomedical-applications and retrieved from Google Images.)

Inorganic materials (e.g. Al2O3, SiO2, ZnO etc.), organic materials (alkaly ami-
nes, fatty acids like oleic acid and stearic acid, sodium laurat, sodium dodesil
benzene sulphonate etc. ) and polymers (polyethylene glycole, polyvinyl alco-
hol, polyoxypropylene etc.) can be used as surface regulators in nanomaterials.

3.13.2 Surface Modification Mechanism of Nanoparticles

This is the reaction performed between the surface and surface regulator to inc-
rease the intermediate surface compatibility of nanoparticles and to improve
their solubility through the concept of surface modification of nanoparticles.
Thus, nanoparticles can easily disperse in organic compounds or water. Molecu-
lar structure of a surface regulator must have the properties of the substrate
~ 247 ~
group which can easily react with the surface of nanoparticles. This special
group can be obtained from the design of the molecular structure of the surface
regulator. Modification can be divided into coating modification and synthesis
modification based on the reaction between the surface regulator and nanopartic-
les.

Coating application is the improvement process performed for preventing or

reducing the agglomeration of nanoparticles by coating the surface of nanopar-
ticles with organic or inorganic compounds (Figure 3.13.2). Coated materials
provide a steric hindrance effect, which makes it significantly more difficult for
particles to aggregate, in order to enable the modification to be successful. Coa-
ting mechanism may occur as adsorption, fixation, simple chemical reaction or
aggregation of the coating on the surface.

Figure 3.13.2. Schematic representation of surface modification reactions of

magnetic nanoparticles using imidazol
(This image is published on http://nmstr.org/2015/08/05/preparing-modified-silica-coated-magnetite-
nanoparticles-by-co-precipitation-method-and-the-application-in-removal-of-iodine-from-water-samples/ and
retrieved from Google Images.)

Synthesis mechanism corresponds to the chemical coupling reaction that occurs

on the surface of the nanoparticles. In addition to coordination bonds, hydrogen
bonds or Van der Waals forces, ionic or covalent bonding between two compo-
unds may also occur. Surface of nanoparticles are highly compatible with the
organic materials in the process that is conducted with the help of synthesis
agents. Synthesis agent molecules must have two groups: Groups that can che-
mically react with the surface of inorganic nanoparticles, or organic functional
groups that can compatible with organic substrates, e.g. dioxin acetate titanate,

~ 248 ~
vinyl trietoxysilane etc. Synthesis modification process has many options in
terms of synthesis agents and easier that the other method. Therefore, this met-
hod is more widely used in nanocomposite materials.

Three methods, mechanical dispersion, ultrasonic dispersion and high-energy

processing, are used in the modification of nanoparticles.

In the application where mechanical force is used, generally the mechanical ef-
fects formed through external shear force or impact force are utilized (Figure
3.13.3). The surface of the nanoparticle under this effect undergoes chemical
changes to react with its chemical environment. Either branching occurs from
organic chain compounds on the surface or a protective layer forms on the surfa-
ce in order to catalyze the dispersion of the nanoparticles.

Figure 3.13.3. Mechanical surface modification of carbonyl iron powder

(This image is published on http://iopscience.iop.org/article/10.1088/0964-1726/25/11/115005 and retrieved
from Google Images.)

It is widely used in chemistry due to its important effects such as ultrasound,

dispersion of particulate structures, polymer degradation, and synthesis of com-
pounds (Figure 3.13.4).

~ 249 ~
 Figure 3.13.4. Ultrasonic surface modification of iron oxide nanoparticles
(This image is published on http://iopscience.iop.org/article/10.1088/1468-6996/16/2/023501 and retrieved
from Google Images.)

High-energy approach includes the use of plasma radiation, electrical discharge,

infrared and ultraviolet for the modification of nanoparticle surface (Figure
3.13.5).

Figure 3.13.5. Nanoparticle synthesis using high energy

(This image is published on http://pubs.rsc.org/-
/content/articlelanding/2015/ra/c4ra14212h/unauth#!divAbstract and retrieved from Google Images.)

~ 250 ~
Summary
Nanoparticles aggregate very easily due to their high surface energy and large
surface area. Since agglomeration of nanoparticles disrupts their nano-sizes, it
prevents NPs from being used in many important fields. If agglomeration of NPs
can be hindered, these important applications can be possible. NPs can be pre-
vented from agglomeration via surface modification methods. Therefore, surface
engineering emerged. Through various studies, this engineering field investiga-
tes methods that will allow NPs to maintain their nano-scale sizes in applicati-
ons. Three different methods have been put forward for this purpose. Nanopar-
ticles can be maintained at nano sizes by applying surface modification via mec-
hanical force, ultrasonic impact or high-energy sources.

~ 251 ~
References
Kango S., Kalia S., Celli A., Njuguna J., Habibi Y., Kumar R., 2013, Surface
modification of inorganic nanoparticles for development of organic–
inorganic nanocomposites—A review, Progress in Polymer Science, 38,
1232-1261.
Neouze, MA. and Schubert, U., 2008, Surface Modification and Functionaliza-
tion of Metal and Metal Oxide Nanoparticles by Organic Ligands, Mo-
natshefte für Chemie-Chemical Monthly, 139, 183–195.
Shi D., Guo Z., Bedford, N., 2015, Nanomaterials and Devices, Tsinghua Uni-
versity Press, Elsevier.
Sperling R.A. and Parak W.J., 2010, Surface modification, functionalization and
bioconjugation of colloidal inorganic nanoparticles, Philosophical Transacti-
ons of the Royal Society A: Mathematical, Physical and Engineering Scien-
ces, 368, 1333–1383.
Zhang, Y., Kohler, N. and Zhang, M., 2002, Surface Modification of Superpa-
ramagnetic Magnetite Nanoparticles and Their Intracellular Uptake, Biomate-
rials, 23, 7, 1553–1561.

~ 252 ~
QUESTIONS

~ 253 ~
~ 254 ~
QUESTION 1) If the material has ……………………….., these materials are
called nanoparticles, quantum dots, nanoshell, nanoring and micro capsule.
a) Three dimensions smaller than 100 nm
b) Two dimensions smaller than 100 nm
c) One dimension smaller than 100 nm
d) Three dimensions smaller than 100 µm

QUESTION 2) If the material has ……………………….., these materials are

called nanotube, nanowire and fiber.
a) Three dimensions smaller than 100 nm
b) Two dimensions smaller than 100 nm
c) One dimension smaller than 100 nm
d) Three dimensions smaller than 100 µm

QUESTION 3) If the material has ……………………….., these are called thin

film, layer and coating.
a)Three dimensions smaller than 100 nm
b) Two dimensions smaller than 100 nm
c) One dimension smaller than 100 nm
d)Three dimensions smaller than 100 µm

QUESTION 4) As the ………………. Increases, materials with low molecular

weight can be created.
a) Volume/surface area ratio
b) Temperature
c) Temperature and time
d) Surface area/volüme

QUESTION 5) Microelectromechanical systems (MEMS) are the integration of

microsensors, microactuators and microelectronic components
……………………………….
a) in an emulsion
b) with ultrasound waves
c) on a silicon chip
d) none of the above

~ 255 ~
QUESTION 6) Which of the following is a Nanotechnology product?
a) Lycurgus Cup
b) Stained-glass Windows in Churches
c) Damascus Swords
d) all of the above

QUESTION 7) Who used the term nanotechnology first and when this term
was used?
a) Richard Feynman, 1959
b) Norio Taniguchi, 1974
c) Eric Drexler, 1986
d) Sumio Lijima, 1991

QUESTION 8) "What is Buckyball?

a) a Carbon molecule (C60)
b) Mercedes-Benz's modern car design (C111)
c) Plastic explosive nanoparticles
d) Gold nanoparticles

QUESTION 9) What is the title of the famous talk of Richard Feynman, who
was accept-ed as the mastermind of modern nanotechnology on 29 December
1959?
a) Nanoscopic Things happen at the bottom
b) There is plenty of room at the bottom
c) There is plenty of discover at the bottom
d) There is a small room at the bottom

QUESTION 10) In which country was the scanning tunnel microscope (SEM)
capable of displaying the nanoscale?
a) Germany
b) United States
c) Switzerland
d) Japan

~ 256 ~
QUESTION 11) Which of the following is an example for nanotechnology use
today?
a) Stain-proof fabrics
b) Scratch-proof surfaces
c) Color changing dyes
d) All of the above

QUESTION 12) How does nanotechnology work?

a) Production by controlling nano-scaled structures.
b) Production by processing the metal containing mineral ores.
c) Production by controlling polymers.
d) Production by changing the chemical structures, energy contents or phy-
sical states of the materials.

QUESTION 13) Which of the following is not an expected benefit of nano-

technology for environment?
a) Efficient use, storage and generation of energy
b) Detection of environmental pollutants
c) Developing molecular-level chemicals to protect plants against insects
d) Creating a sustainable environment

QUESTION 14) Which of the following is a nanotechnology application

developed for foods?
a) Batteries with nanowires
b) Drugs embedded into nanoparticles
c) Clay nanotubes preventing rotting and bacteria growth
d) Nano-scale fertilizer

QUESTION 15) Which of the following is not an application of nanotechno-

logy in medicine?
a) Drugs loaded onto nanoparticles
b) Tumor detection with iron oxide nanoparticles
c) Destroying the cancer cells with nanoshells
d) All of the above

~ 257 ~
QUESTION 16) Which of the below cannot be said for nanometrology?
a) It is necessary to conduct studies at atomic and molecular level.
b) It is used for measuring structures which are sized as billionth of a meter
or less.
c) It is used for measuring structures which are sized as 10-12 and less.
d) It is the science of measurement.

QUESTION 17) What is the scale of measurement that nanotechnology deals

with?
a) 1-100 nm
b) 1-10 nm
c) 1-100 µm
d) 1-10 µm

QUESTION 18) At nanoscale:

a) Metals become harder.
b) Chemical resistance increases.
c) Ceramics become softer.
d) All of the above are correct.

QUESTION 19) Which formula is used for calculating the number of atoms in
1 ng of an element whose molar mass is 40,08?
,
a) 10
,

,
b) 10
,

c) 6,022 10

,
d)
,

QUESTION 20) Which of the below is not a nanoscale measurement require-

ment?
a) Thickness and density of thin film
b) Height at structured surface
c) Diameter of engineered nanoparticles
d) Microelectronic measurements

~ 258 ~
 QUESTION 21) The technologies that exist, it could have a negative impact on
society in what concerns aspects of:
a) confidentiality;
b) division of society;
c) communication;
d) risks.

QUESTION 22) Nano Impact aims to play an important role in disseminating

knowledge about nanomaterials in human and environmental systems. It focu-
ses on four main areas:
a) Human nanotoxicology
b) Nano-eco toxicology
c) Exposure
d) Risk and life cycle assessment

QUESTION 23) Choose the correct answer

True False

Nano Impact aims to play an important role in disseminating knowledge about

nanomaterials in human and environmental systems.

QUESTION 24) Identify somenew concepts for future nanotechnology im-

pact products
a) Nano spaces
b) Nano robot
c) Nano elevator
d) Nano morph

QUESTION 25) Mention some application of nanotechnology.

QUESTION 26) What systems can you prepare by using microemulsion met-
hod? Choose one of these systems, explain your reason and which parameters
you should pay attention as you prepare the system.

QUESTION 27) Is there a chance for us to encounter precipitation method in

daily incidents? Discuss.

~ 259 ~
QUESTION 28) Which nanoparticles can be produced by using precipitation
method? Research.

QUESTION 29) What are the nanoparticles systems where you can use ultra-
sonic energy? For what purpose would you use, explain.

QUESTION 30) Green chemistry aims to......

a) design chemical products and processes that will increase the profitability.
b) design safer chemical products and processes that will reduce or cease the
use and production of hazardous substances.
c) design more efficiently working chemical products and processes.
d) use non-renewable energy.
e) None of the above

QUESTION 31) Dr. Paul Anastas and Dr. John Warner authored the 12 prin-
ciples of “Green Chemistry” to reduce or cease the use and production of ha-
zardous substances.

a) True
b) False

QUESTION 32) Which of the following is one of 12 principles of Green Che-

mistry?
a) Designing commercially applicable products
b) Using only new solvents
c) Using catalysts instead of stoichiometric reagents
d) Re-using the wastes
e) None of the above

QUESTION 33) Green chemistry is more expensive than conventional che-

mistry.
a) True
b) False

~ 260 ~
QUESTION 34) Which of the following can be an example of green chemistry?
a) Recycled carpet
b) A product prepared on world day
c) A sublimation reaction
d) Bioplastics
e) None of the above

QUESTION 35) Which of the following is not one of the primary benefits of
SOL-GEL method?
a) High-purity product attainment
b) Product attainment at low temperature
c) Product attainment at high temperature
d) High homogeneity

QUESTION 36) Which of the following is not related to condensation process?

a ) Removal of the water inside the structure
b ) Obtaining large molecules from smaller molecules inside the structure
c ) Removal of the alcohol inside the structure
d ) Removal of the oxide inside the structure

QUESTION 37) Which of the following is the correct order of SOL-GEL pro-
cess?
a) Drying + gelling + hydrolysis of pre-initiators + high temperature proces-
sing + aging + condensation
b) Hydrolysis of pre-initiators + condensation + gelling + aging + drying +
high temperature processing
c) Condensation + hydrolysis of pre-initiators + gelling + aging + drying +
high-temperature processing
d) Gelling + aging + hydrolysis of pre-initiators + drying + high-temperature
processing + condensation

QUESTION 38) Which of the following is not a coating process conducted with
SOL-GEL method?
a) Angle-based dip coating
b) Dip coating process
c) Spin coating process
d) Coating with electrolysis method
~ 261 ~
QUESTION 39) Which of the following is not an advantage of SOL-GEL
method?
a) Process is easy.
b) Process can be conducted under laboratory conditions
c) Process does not take place at high temperatures
d) Process does not allow the production of different types of nanomateri-
als

QUESTION 40) Which of the following is not a lithography technique?

a) Electron beam
b) Spin
c) Nano-stamp
d) Micro-contact printing
e) Photolithography

QUESTION 41) ................................. is an image and it is formed by creating

a pattern on the stone, inking it and printing the inked stone onto a paper.
a) Quantum dot
b) Nanophotonic crystal
c) Lithography
d) Microfabrication
e) Etching

QUESTION 42) Which of the following is (are) correct?

(I) Positive resists - These become more soluble when they are exposed to UV
rays.
(II) Negative resists - These become less soluble when they are exposed to UV
rays.
(III) Photoresists general initiate the reaction with ultraviolet (UV) or visible
light, therefore they are called optical resists.

a) Only I
b) Only II
c) I and II
d) Only III
e) II and III

~ 262 ~
QUESTION 43) Which of the following is not a component of photoresist?
a) Catalyst
b) Polymer
c) Sensitizer
d) Solvent
e) Additives like paint

QUESTION 44) Which of the following is not an area of use of lithography?

a) integrated circuits
b) internal computer components
c) production of microcircuits (NEMs, MEMs)
d) organic memory devices
e) scanning electron microscope (SEM)

QUESTION 45) Which of the following is not a reason that causes the formation
of nanoparticles?
a) Volcanic eruption
b) Biomineralization
c) Comets
d) Desert dusts
e) Agglomeration of humic substance

QUESTION 46) Which of the following is not an example of organic natural

nanoparticles?
a) Humic acid
b) Fulvic acid
c) CdS
d) Peptides
e) Proteins

QUESTION 47) Which is the most striking difference of produced nanoparticles

from NNPs?
a) Ability to produce at desired ratios
b) Production using chemicals
c) Ability to release to the nature
d) Unknown toxic effects
e) Being used in many applications
~ 263 ~
QUESTION 48) Which of the following does not have the morphological
structure of nanoparticles synthesized today?
a) Core-shell
b) Sandwich
c) Doped
d) Hollow
e) 4D structure

QUESTION 49) Which of the following exhibits different morphological na-

noparticle shapes?
a) Metal alloy
b) Ceramic
c) Polymer-based
d) Metal composite
e) Plant-based

QUESTION 50) With which of the following mediums can nano alloys be pre-
pared?
I. Gas phase
II. Precipitate phase
III. By supporting with a matrix
a) Only I
b) Only II
c) I and II
d) I, II and III
e) None of the above

QUESTION 51) Which of the following is not a method used for the synthesis
of metal nanoparticle?
a) Bacteria species
b) Fungi
c) Yeasts
d) Plant extracts
e) Waste water

~ 264 ~
QUESTION 52) Which of the following is an area of use for nanoparticles?
a) Milk industry
b) Fruit juice
c) Drug delivery
d) Bread making
e) Salt production

QUESTION 53) In which applications would you prefer to use natural and
synthetic polymeric nanoparticles and dendrimers. Explain with reasons.

QUESTION 54) If you want to produce a nanomaterial related to your profes-

sional field, which material do you choose? Explain why. What are the disad-
vantages of using the material you choose? To get rid of these disadvantages,
what materials and what method do you consider to improve the surface of
your material? Please explain.

QUESTION 55) What is electrical puncture?

QUESTION 56) What is the Meissner effect?

QUESTION 57) What is the working principle of solar cells?

QUESTION 58) What can you say about the resistances of two conductors
with the same length but different diameters, assuming all other conditions are
the same except their diameters?

QUESTION 59) What can you say about the resistances of two conductors, as-
suming that only the lengths of two conductors are different and they are the
same in all other conditions?

QUESTION 60) Which of the following is not a quantum dot property?

a) They have wide and continuous absorption spectrum
b) They have narrow emission spectrum
c) They have high light stability
d) They have quite good luminescence and electrical properties
e) Quantum dots have sizes in micrometer scale

~ 265 ~
QUESTION 61) Which of the following explains why quantum dot structures
with different sizes radiate in different colors?
a) Quantum confinement effect
b) Surface properties
c) Use of different surface active agents in the synthesis of quantum dot
structures
d) Quantum dots having different crystal
e) Quantum dots being synthesized in core/shell structure

QUESTION 62) Which of the following quantum dot structure synthesis met-
hods cannot be used as top-down synthesis method?
a) Electron beam litography
b) X-ray litography
c) Sol-Gel method
d) Molecular beam epitaxy
e) Ion implantation

QUESTION 63) Which of the following is not a reason why quantum dot
structures are being used in photocatalysis applications?
a) Low cost
b) Low toxicity
c) Adjustable florescence emissions
d) Having sizes in nanometer scale
e) Chemically inert structure

QUESTION 64) Which of the following is referred to as “florescence quantum

efficiency”?
a) The ratio of the number of absorbed photons to the number of emissions
b) The ratio of the number of emissions to the number of absorbed photons
c) Difference between the number of emissions and the number of absorbed
photons
d) The number of absorbed photons
e) The number of emissions

~ 266 ~
QUESTION 65) Which of the following does not have the morphological structu-
re of nanoparticles synthesized today?
a) Core-shell
b) Sandwich
c) Doped
d) Hollow
e) 4D structure

QUESTION 66) Which of the following exhibits different morphological nano-

particle shapes?
a) Metal alloy
b) Ceramic
c) Polymer-based
d) Metal composite
e) Plant-based

QUESTION 67) With which of the following mediums can nano alloys be prepa-
red?
I. Gas phase
II. Precipitate phase
III. By supporting with a matrix
a) Only I
b) Only II
c) I and II
d) I, II and III
e) None of the above

QUESTION 68) Which of the following is not a method used for the synthesis of
metal nanoparticle?
a) Bacteria species
b) Fungi
c) Yeasts
d) Plant extracts
e) Waste water

~ 267 ~
QUESTION 69) Which of the following is an area of use for nanoparticles?
a) Milk industry
b) Fruit juice
c) Drug delivery
d) Bread making
e) Salt production

QUESTION 70) Discuss the importance of different hybridization of carbon

atom.

QUESTION 71) Which company owns the most patents in the world on studies
at nano-scale studies? Explain the nan-otechnology-based design in the logo of
the related company.

QUESTION 72) Which country makes the most nanotube production in the
world? Mention the related country’s nano-technology-based productions for
daily life.

QUESTION 73) What is Bucky ball?

QUESTION 74) Which of the following does not belong to the shape classifica-
tion of nanomaterials in terms of their sizes?
a) Isotropic structure
b) 1D structure
c) 2D structure
d) Anisotropic structure
e) 4D structure

QUESTION 75) Which of the following is not a 1D shape of nanoparticles?

a) Spherical structure
b) Nanorods
c) Circular disks
d) Nanostar
e) Nanoflower

QUESTION 76) Which of the following parameters contribute to the kinetically-

controlled shape formation of nanoparticles?
a) Temperature
b) Concentration
c) Chemical Potential
d) Nucleation theory
e) pH effect

~ 268 ~
 QUESTION 77) Which of the following is not a factor that affects the shapes of
nanoparticles?
a) Supersaturation
b) Concentration
c) Light
d) Solvent effect
e) pH effect

QUESTION 78) Which factor that affects the shape control of nanoparticles is
used for reducing the surface energies of nanoparticles?
a) Surfactants and additives
b) Temperature
c) Precursor monomer concentration
d) Supersaturation
e) pH effect

QUESTION 79) Which of the following is not a nanoceramic material?

a) SiO2
b)TiO2)
c)Ca(OH)2
d) Al2O3
e) ZrO2

QUESTION 80) Which of the following can be applied to nanoceramics to obtain

the smallest possible particle size?
a) fast heating
b) high pressure,
c) addition of shrinking accelerator agents
d) addition of particle growth inhibitor agents
e) instant cooling

QUESTION 81) Which of the following can be given as an advanced sintering

technique for synthesis of desired nanoceramics?
a) electron beam litography
b) high pressure compression
c) arc-plasma sintering
d) shock compression,
e) high frequency induction heating

QUESTION 82) List at least 3 application fields where nanoceramics are used.

~ 269 ~
QUESTION 83) Which of the following(s) is a disadvantage of traditional sinte-
ring method?
(I) frequent particle growth
(II) deterioration of ceramic,
(III) worsening of mechanical properties of ceramic
a) I and II
b) I, II, III
c) Only I
d) Only III
e) II and III

QUESTION 84) Which of the following is not a superior property of thin film?
a) Optical properties
b) Chemical properties
c) Electrical properties
d) Physical properties

QUESTION 85) Which of the following is not within the size range of thin films?
a) Materials smaller than 1 m
b) Materials larger than 5 m
c) Materials larger than 1 m
d) Materials smaller than 10 m

QUESTION 86) Which of the following is a thin film production method?

a) Physical abrasion method
b) Chemical abrasion method
c) Sol – Gel method
d) Chemical liquid deposition method

QUESTION 87) Which of the following is a type of thin film?

a) Double conductor films
b) Mega conductor films
c) Superinsulator films
d) Superconductor films

QUESTION 88) Which of the following is one of the advantages of thin film
production method?
a) Process is easy.
b) Allows for the use of any kind of production method.
c) Coating thickness depends on the production method.
d) Poor optical properties.

~ 270 ~
~ 271 ~
~ 272 ~