Materials Today Chemistry 16 (2020) 100248

Contents lists available at ScienceDirect

Materials Today Chemistry

journal homepage: www.journals.elsevier.com/materials-today-chemistry/

Fused deposition modeling-based additive manufacturing (3D

printing): techniques for polymer material systems
S.C. Daminabo a, S. Goel a, b, c, S.A. Grammatikos d, H.Y. Nezhad a, **, V.K. Thakur a, b, *
a
Enhanced Composites and Structures Center, School of Aerospace, Transport and Manufacturing, Cranfield University, Bedfordshire, MK43 0AL, UK
b
Department of Mechanical Engineering, School of Engineering, Shiv Nadar University, Uttar Pradesh, 201314, India
c
School of Engineering, London South Bank University, 103 Borough Road, London, SE1 0AA, UK
d
Group of Sustainable Composites, Department of Manufacturing and Civil Engineering, Norwegian University of Science and Technology, Gjøvik, 2815,
Norway

a r t i c l e i n f o a b s t r a c t

Article history: While the developments of additive manufacturing (AM) techniques have been remarkable thus far, they
Received 3 November 2019 are still significantly limited by the range of printable, functional material systems that meet the re-
Received in revised form quirements of a broad range of industries; including the health care, manufacturing, packaging, aero-
20 January 2020
space, and automotive industries. Furthermore, with the rising demand for sustainable developments,
Accepted 21 January 2020
Available online xxx
this review broadly gives the reader a good overview of existing AM techniques; with more focus on the
extrusion-based technologies (fused deposition modeling and direct ink writing) due to their scalability,
cost efficiency and wider range of material processability. It then goes on to identify the innovative
Keywords:
3D printing
materials and recent research activities that may support the sustainable development of extrusion-
Additive manufacturing (AM) based techniques for functional and multifunctional (4D printing) part and product fabrication.
Multifunctional materials systems © 2020 Elsevier Ltd. All rights reserved.
Fused deposition modeling
Sustainable
Polymer-based composites

1. Introduction identified to be vastly beneficial in the biomedical industry

amongst others; including the healthcare, aerospace, construction,
The concept of additive manufacturing (AM) e that is most automotive, food and dental industries [1e12,14]. 3DP requires no
commonly referred to as rapid prototyping (RP) and free-form mold tool and offers near-net-shape manufacturing in a relatively
fabrication is governed by 3D printing (3DP), which covers a set short period of time: a feature that is most beneficial in customized
of techniques that use a layer-by-layer approach to build parts or part and product production while being capable of harnessing
products; usually with a small size, in low quantities, and with a digital information for the realization of a robust, decentralized 3D
complex, tailored design [1e13]. Such characteristics have been manufacturing system. Critically, there is a rising interest in the
development of software for data protection and security in 3DP
systems, which indicates the growing level of risks associated with
their implementation; that must be tackled appropriately for the
Abbreviations: 3DP, Three-Dimensional Printing; 4DP, Four-Dimensional Print-
protection of intellectual property within organizations [15e17].
ing; AM, Additive Manufacturing; ASTM, American Society for Testing and Mate-
rials; BJ, Binder Jetting; CAD, Computer-Aided Design; CAM, Computer-Aided With the high demand for lightweight, more functional and cost-
Manufacturing; CNT, Carbon Nanotube; DED, Direct Energy Deposition; FDM, Fused efficient product systems, polymer-based composites have
Deposition modeling; FFF, Fused Filament Fabrication; ISO, International Standards become ‘state of the art’ in material system design and develop-
Organization; ME, Material Extrusion; ME3DP, Material Extrusion Three-
ment for 3DP applications [18e20]. The recent levels of research
Dimensional Printing; MFMS, Multifunctional Material Systems; MJ, Material
Jetting; PBS, Poly Butylene Succinate; PHA, Poly Hydroxy Alkanoate; PLA, Poly
and developments in nanomaterials, biomaterials, and composites,
Lactic Acid; SL, Stereo Lithography; SMP, Shape Memory Polymer; VFR, Volumetric supported by improving metrological methods [21] have certainly
Flow Rate; VP, Vapor Deposition. created more opportunities for exploring potential applications for
* Corresponding author. polymer-based material systems [4,18]. This is especially in the
** Corresponding author.
development of advanced, multifunctional material systems
E-mail addresses: h.yazdani-nezhad@cranfield.ac.uk (H.Y. Nezhad), Vijay.
kumar@cranfield.ac.uk (V.K. Thakur). (MFMSs), i.e. polymer composites in the form of polymer blends,

https://doi.org/10.1016/j.mtchem.2020.100248
2468-5194/© 2020 Elsevier Ltd. All rights reserved.
2 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

nano-based polymer composites, hydrogels, etc. which continue to modeling (FDM), and fused filament fabrication (FFF) fall into
be a very promising area for driving product system developments this category [6,29,33].
that meets the sustainability, high performance requirements of  Material jetting (MJ), which is an AM technique (similar to
global supply chains, especially in light of toughening government stereolithography) which involves the selective deposition of a
regulations, and increasing demand from developing economies photopolymer and initiator as build material (in the form of
[22,23]. droplets) to form thin layers that are further cured to form the
Multifunctional Material Systems in the basic sense, are material 3D part. These systems use machines with an inkjet head and
systems that have multiple functionalities that define more include the popular polyjet machine [29,33].
autonomous systems [24]. As the name implies, Multifunctional  Binder jetting (BJ), which is an AM technique based on bonding
Material Systems (MFMS) usually create the possibility of using one powder materials with the aid of a liquid bonding agent; to form
part/product for different functions as required during application. the 3D part. The liquid bonding agent is selectively deposited to
This is achieved with the help of constituent materials that can aid enable the a selective fusion process [6,29,33].
the adoption of multiple mechanical, physical, or chemical, prop-  Sheet lamination (SL), which is an AM technique, which in-
erties when desired by the user [24,25]. Material resources remain volves bonding sheets or foils of material together to form an
a key aspect of manufacturing systems that contributes signifi- object. Laminated Object Manufacturing (LOM), and Ultrasound
cantly to the output of a 3DP process; just as they would in other Additive Manufacturing (UAM) make up the prominent tech-
conventional and non-conventional manufacturing processes. They nologies in this AM category [6,29,33].
are critical for manufacturing process efficiency and effectiveness,  Vat photo Polymerization (VP), which is an AM technique in
and part/product functionality, eco-friendliness, and performance which a liquid photopolymer is placed inside a moveable vat,
[26]. Considering these, there has been an increasing demand by and selectively cured using an ultraviolet light-activated poly-
industry to harness more functional and sustainable materials as merization process. Numerous lithography-based AM ap-
candidates for future AM processes [27,28]. In general, 3DP tech- proaches like digital light stereolithography (SLA) as well as
niques have primarily been used for applications that do not processing (DLP) can be classified and included in this AM
require a high level of part functionality and/or performance [29]; category [6,29,33].
like in prototypes, toys, fixtures, etc., which directly implies that  Powder Bed Fusion (PBF), which is the AM technique that uses
there are still opportunities for innovation. As a result, broadening thermal energy to fuse regions of the powder bed of the build
the applicability of 3DP technologies; i.e. by developing machine- material. Selective laser sintering (SLS), electron beam melting
compatible, reliable and eco-friendly materials, and printing stra- (EBM), and selective laser melting (SLM) fall into this category of
tegies that can deliver improved part functionality and perfor- AM processes [6,29,33].
mance; is understandably a goal for industrial fabrication [8,30].  Directed Energy Deposition (DED), which is an AM technique
Aspects related to 3DP systems and MFMSs have gained significant that uses a focused beam of thermal energy (e.g. in laser or
interest in the last two decades. The use of MFMS is a development plasma arc technologies) to fuse metal and metal-hybrid ma-
that allows savings in the number of parts required for producing a terials by controlled melting while being deposited. Laser
useful product. This consequently reduces the need for joining deposition (LD), laser-engineered net shaping (LENS), and
operations that will usually have a higher time and cost-resource plasma arc melting are some of the main technologies within
requirement. An effective integration/adoption of multifunctional this category [6,29,33].
capabilities to a material, composite and/or structure should enable
one to eliminate inefficient/ineffective product components like These techniques offer freedom in design (for mass product
connectors, bulky units, etc.; thereby leading to major weight and customization), waste minimization (for lower costs), rapid proto-
size savings; and thus increasing system-level efficiency as desired typing and manufacturing (for faster delivery to market), and ul-
by multiple industries. Fig. 1 highlights the route to multifunctional timately a more efficient manufacturing and supply chain - as the
3D printed polymer composites, and the set of functionalities that main advantage of AM. Consequently, the development of AM and
an innovative composite, or structure can incorporate towards 3DP has created greater opportunities for advanced design, pro-
improving the quality and performance of products and services duction, and end-user applications. In 2016, the consumption of
across multiple industries. These developments are therefore also 3DP systems, printing materials systems, software, and services
critical for the effective realization of the next industrial revolution amounted to approximately $13 billion and suggested an annual
(industry 4.0) [31]; characterized by increased collaboration be- growth rate of 22.3% over 4 years, amounting to ~$29 billion by
tween information and manufacturing/product systems. 2020 [3].
Fig. 2 shows a great representation of the basic concept of 3DP as
the defining process in the AM paradigm. 3DP (the production
1.1. Additive manufacturing process in AM) uses a layer-by-layer approach to build-up physical
parts and products from a 3D CAD model with the help of a
Additive manufacturing (AM) is a layer-by-layer manufacturing computer-aided manufacturing (CAM) system. Initially, (step a-b), a
paradigm, which involves using a computer-based 3D model, a 3D 3D computer model is obtained by three-dimensional computer-
printer, and a step after the printing activity to fabricate a physical aided design (3D CAD) design or 3D scanning, or any other available
model based on the initial model design. The International Stan- method. Next, is the slicing stage (step b-c), where a CAM software
dards Organization/American Society for Testing and Materials is used to obtain a model, process the model into slices, and plan
standards (ISO/ASTM 52900:2015) identifies that there are seven the printing path (including adding support structures that aids to
main categories of Additive Manufacturing/Three-Dimensional maintain the stability and integrity of the during 3DP). Note that
Printing (AM/3DP) techniques available [29,33,34]. As a brief the print path defined by computer numerical control (CNC) codes
explanation of each AM technique, they include: is used by the 3DP machine to print the model. Last in this AM/3DP
paradigm is the stage following the processing (step c-a), which
 Material extrusion (ME), which is an AM technique in which a occurs after the print process is finished; it usually involves
material heated and selectively dispensed through a nozzle to removing the support structures or carrying out any other
form a 3D part. Direct Ink Writing (DIW), Fused deposition required operations/techniques in the nature of those performed
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 3

Fig. 1. Route to achieving multifunctionality in composite materials systems (reprinted with permission from Ref. [32]). Copyright with license number: 4700460162923.

after processing, required to meet best net-shape results, in relation range of materials that are compatible with ME technologies, there
to the initial 3D model. is clearly a significant promise for developing advanced materials
systems via AM/3DP. Other AM techniques capable of processing a
1.2. Comparing AM techniques similar range of materials include the BJ, PBF, and MJ techniques.
However, for PBF and BJ, biological systems cannot be employed
Table 1 helps to compare the 7 AM/3DP techniques with key due to the harsh effects and biocompatibility issues associated with
information on compatible materials options, typical product using binders. This leaves MJ and ME as the only techniques capable
feature resolution, and maximum cartesian dimensions of build of processing biological systems. Between these two techniques
volumes (found in literatures). Furthermore, it also gives a brief also, MJ has a greater capability of producing parts with higher
idea of the advantages and disadvantages surrounding their use. resolution and accuracy, however, it requires a low viscosity
These points are important for understanding the capabilities of printing media, which further limits its materials to mainly
each AM/3DP technique for successful commercial applications, photopolymer and thermoset resins. ME, on the other hand, offers
while also identifying their limitations. Understanding these is more industrially desirable properties like cost-effectiveness, scal-
expected to strengthen and drive the focus on the research and ability, and a higher viscous range of processing, despite the lower
development of AM technologies as is required for achieving better resolution and higher processing temperature features of its a
quality processes and product fabrication. process. In another key aspect, BJ, PBF and ME, in that order, were
Very importantly, material extrusion was found to be a process highlighted to have the largest build volumes amongst those cat-
category capable of using thermoplastics, hydrogels, ceramics, egories capable of processing a broad range of materials; thereby
composites or bio-based materials to print parts. This is very unique allowing for the fabrication of small to large-sized components.
and highlights a strong advantage over some other 3DP techniques Fig. 3 shows each of the 7 discussed AM process categories; iden-
like the DED and VP, which have more limited material options. tifying the state, form and suitability of material feedstock for each
Such a capability has been widely considered to hold significant AM principle/category.
opportunities for tissue engineering and other biomedical product From Fig. 3, we can identify polymers to be highly suitable with
developments [36,37], which identifies a possible reason for the all AM process techniques, except for PBF and direct DED. More
increasing literature on bioprinting. Furthermore, considering the importantly, in the consideration of polymer composites; only
4 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

Fig. 2. Depicting the route in 3DP to obtain a physical model from the digital model (Reprinted with permission from Ref. [6] under the copyright creative commons attribution
license).

ceramics are identified to be suitable in a polymer matrix. They manufacturing processes, a hybrid 3D manufacturing system;
were also found to be only compatible with printing with the ME which is enabled by the growing capability of executing multi-
and SL process techniques. Clay, glass, and cement are good ex- machines and multimaterial processes [33,34]; can have significant
amples of ceramics, which can offer semiconducting, super- advantages for the production of advanced electronics and devices
conducting, insulating and ferroelectric properties depending on [33,34].
composition. Therefore, their compatibility with the material As a concept, 3DP and AM techniques have been present since
extrusion process highlights unique advantages and incentives for the 1980s and have been the building block for developments like
material and process developments that can potentially yield better rapid tooling/prototyping. However, more recently there have been
functional products in. These findings also highlight the material developments in the area of ‘bioprinting’. Fig. 5 highlights the
limitations associated with manufacturing polymer composite recent trends in AM-based publications ending in 2016. It also
systems; as it offers sheet lamination as the only alternative to the highlights the publication trend by 3DP technique for the top four
versatile ME process. This is likely due to the different temperature- publishing countries, amongst others.
factors associated with processing the different material classes (i.e. The recent development of bioprinting has been backed by a
metals, polymers, and ceramics). In an attempt to further assess the rapid increase in research publications for at least a decade ending
features of all AM/3DP techniques, Fig. 4 below presents critically in 2016, since its interest surfaced [6]. This is likely supported by
reviewed factors during the printing operation. Three parameters, other recent developments in advanced material systems (com-
including energy, speed, and resolution, which are very important posites and nanocomposites), biomaterials and biomimetics. These
for affecting part quality, time and cost efficiency, and process eco- advanced material systems give hope to greater possibilities in
friendliness, were compared. As observed, ME techniques were product design; specifically within the healthcare, dental, pack-
identified to yield next to the lowest resolution (i.e. between 10 and aging, automotive, and aerospace industries [30,40]. In the
100 elements/mm3); only outperforming the DED technique. In healthcare industry, current and prospective developments in
another case, the ME3DP technique was found to use significantly materials systems and bioprinting is suggesting that considerably
less energy than all other techniques, except for the BJ technique, high revenue is to be expected (~$1 billion) to come from the
however, MJ also appeared to have similar energy than. Lastly, in medical, dental, prototyping, and prosthetics printing sectors alone
the case of speed, which is greatly significant in high throughput by 2020 [3].
manufacturing applications, ME critically comes up as the slowest
3DP technology; slower than both the BJ and MJ processes 1.3. Achieving sustainable developments in AM/3DP
especially.
The development of AM/3DP technologies has taken several Achieving environmentally sustainable solutions has become a
routes; involving printer technology and material system variations very important topic for the global community; so important that
[8,38], which helps to deliver a wider range of possibilities for investors, chief executive officers (CEOs), managers, and other
product system manufacturing. However, ME3DP has been, business leading professionals have AM as a key subject of focus
amongst all other AM technologies, found to be the most popular, within their businesses. Consequently, there is also a growing
cost-efficient, and easily accessible technique for the realization of a awareness of the public community towards issues of sustainabil-
decentralized, agile 3D manufacturing future. Furthermore, with ity; a factor, which is also expected to affect the choice of products
the incorporation of robotic systems as a resource for and services that attract the market. AM techniques and
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 5

Table 1
Comparing the typical materials, build volume, and resolution used for each AM technique (including advantages and disadvantages) [4,6,20,35].

AM category Typical materials Advantages Disadvantages Max. individual cartesian Typical

dimensions of existing resolution
3DP
machines (mm)

Vat Photo Photopolymer Large parts Only uses photopolymers x  2100 0.1e100 mm
polymerization (acrylates Very good process accuracy Has a low shelf life y  700
(VP) and epoxides) Very good surface finish poor mechanical properties z  800
Ceramics (e.g. Zirconia, and details. of photopolymers
alumina) Generally high build speed Expensive precursors
Powder Bed Metals Relatively inexpensive Relatively slow x  1400 50e100 mm
Fusion (PBF) Ceramics High specific strength and Lack of structural integrity y  1400
Polymers stiffness of parts (very good mechanical Limited scalability z  500
Composites properties) High power required
Hybrid Powder bed acts as an Finish depends on precursor
integrated support structure powder particle size.
Relatively high resolution Poor reusability of
Large range of processing unsintered powder
material options.
Material Polymers High accuracy in Usually requires some x  1000 10e25 mm
Jetting (MJ) Ceramics droplet deposition. support material. y  800
Composites Low waste Limited to photopolymers z  500
Hybrids Multimaterial and and thermoset
Biologicals multicolor parts can resins can be used.
be fabricated Requires highly controllable
The good surface finish ink viscosity.
of parts Limited to low-strength
applications
Binder Polymers Wide options of materials. Produces parts with x  4000 ~100 mm
Jetting (BJ) Ceramics Relatively high print speed. limited mechanical y  2000
Composites Relatively low cost properties (inherent porosity z  1000
Metals due to limited
Hybrids solvent welding or chemical
reaction bonding)
Requires low viscosity ink
Require significant
activities performed
after processing (e.g.
infiltration
process)
Sheet Polymers High speed process. May require -post-processing x  250 200e300 mm
Lamination Metals Low cost. Quality of part is dependent y  220
(SL) Ceramics Ease of material handling. on z  145
Hybrids adhesive used
Material Polymers Multimaterial and Parts usually exhibit x  1005 100 mme1 cm
Extrusion Ceramics multicolor parts can vertical anisotropy. y  1005
(ME) Composites be fabricated. Step-structured surface z  1005
Hybrids Inexpensive (poor surface finish)
Biological Easily scalable. Relatively medium-high
Can build fully temperature process
functional parts. Low resolution.
Direct Energy Metals/metal hybrids The high degree of Limited to metals and x  3000 100 mme1 cm
Deposition grain structure control. metal hybrids. y  3500
(DED) Yields high-quality parts. Good balance between z  5000
Very good for repairing surface quality and print
applications. speed is required.

technologies have seen rapid growth in interest as a technology these industries (left). The medical/dental, consumer products/
with disruptive potential. The adoption of AM has been widely electronics, industrial machines, aerospace, and automotive sectors
accepted to introduce flexibility, reduce material waste, and deliver were found to be prominent industries involved with AM. Hence, as
rapid manufacturing at a lower cost than traditional manufacturing AM can be considered to deliver various forms of business solu-
methods (e.g. machining and injection molding) when tions, partaking organizations within these industries, therefore,
manufacturing complex/bespoke parts/products. In essence, AM is have a vitally responsible role to play in the development of AM
capable of cost-effectively improving innovation, production, and technologies; using material systems and processes that are eco-
service lead times, whilst delivering a high level of flexibility to friendly and sustainable.
manufacturing. This enables a decentralized manufacturing system
that enables more efficient, effective and agile manufacturing sys-
tems to be deployed; especially when in collaboration with other 1.4. Limitations to AM/3DP
existing manufacturing paradigms. Fig. 6 below gives a good
reflection of the industries applying AM and 3DP (right); with the The rapid development of AM technologies has been a key
most common applications for which AM is being used within limitation to its development as this is leading to the lack of specific
design principles, manufacturing guidelines, and standard that
6 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

Fig. 3. 7 AM techniques (in red), processing principles and compatible materials; with level of suitability (Reprinted with permission from Ref. [4], Copyright with license number:
4692830626888).

Fig. 4. Comparing operational and feature factors of the 7 AM/3DP techniques (Reprinted with permission from Ref. [4], Copyright with license number: 4692830626888).

guides AM. These challenges are more relevant when considering considerably new for AM. Following a survey by Pricewaterhou-
the fact that advancements, for example in materials processing seCoopers (PwC), almost half of the manufacturers that were sur-
and optimization, generates a positive feedback effect, which in- veyed highlighted that ‘uncertainty in the quality of the final
troduces new changes within a system; thereby making these product’ has been a barrier to their adoption of the available AM
guidelines, principles, and standards more difficult to define. This is technologies [4]. This was a key finding that further suggests that
a challenge that needs to be tackled strategically, maybe by meeting the measurements (metrology) that underpin key aspects of in-
the requirements of AM system users within specific industries and spection, monitoring and part/product quality assurance are not
niches. well developed. This may be linked to the effects of a rapidly
Following a production process in AM or any other developing sector, as it is with the case of limited ‘standardization
manufacturing paradigm, inspection and quality assurances are of design principles’, ‘manufacturing guidelines’, and best practices.
critical next steps used for ensuring high part and product quality The limited range of commercially available materials for com-
for its users and the environment. These are the cornerstones of mercial to home-friendly AM technologies [41e43] is also a sig-
ancient as well as modern manufacturing; a narrative that is nificant setback to AM advancement. The FDM technology is the
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 7

Fig. 5. Recent trends in publications covering key AM areas (Reprinted with permission from Refs. [6,39] under the copyright creative commons attribution license).

Fig. 6. Industries applying 3DP technologies (left) and some of their popular product and/or service applications in AM (right). Reprinted with permission from Ref. [6], under the
copyright creative commons attribution license.

most suitable for home-friendly printing and with only specific developing sustainable and robust decentralized manufacturing
filaments available, commercial and casual users can find it difficult systems. The potential synergy that can be obtained from de-
to print parts that deliver the desired property or set of properties velopments in machine and material systems are identified to be
required for a function. capable of leading to significant improvements in environmental
Another significant problem in the development of 3DP, espe- sustainability; in the key areas of reusability, recyclability, recovery,
cially for mechanically functional requirements, is the fact that and disposal of products at their end-of-life, while being potentially
printed parts are largely anisotropic [4,6,44]. Because of this, capable of supporting a variety of standard or customized product
achieving isotropic AM parts, or understanding anisotropic be- and service quality improvements.
haviors better will enhance the potential for the adoption of 3DP for
structural product fabrications. 2. FDM: the underlying technique for ME3DP

1.5. Review focus Extrusion-based AM methods generally run a process where a

feedstock (usually a filament formed beforehand) is fed to the head
Considering the points made so far, it is very important to raise of the printing system by an electrical or hydraulic motor-
the awareness of polymer-based materials as being considered the controlled pinch roller mechanism [47]. In the head, the filament
most attractive and commonly used material. In high-waste is of heated and extruded in a molten filament material form onto a
generating processes, it is however an environmentally concern- platform to create a 2D layer. Repeatedly, this 2D layer, one on top
ing class of materials used globally; as it has low-cost and light- of another creates a three-dimensional part that is representative of
weight characteristics [45,46]. Furthermore, the prospect of high or a design specification [3,47,48]. In other words, material extrusion
increasing population demand and the reality of increasing gov- techniques, which is based on fused filament fabrication (FFF) along
ernment regulations creates concerns that would require sustain- with fused deposition modeling (FDM) processes [49], can be
able ‘material and process developments’ for the benefit of the described as a 3DP manufacturing technique involving a thermo-
ecosystem, while also meeting the sustainable and functional de- plastic material (in filament or pellet form) being extruded through
mands of several industries. Hence therefore, this article aims to one or more heated nozzles [49]. The viscous material or melt
critically review the ME3DP technique, and their use in printing emerging from the nozzle(s) is deposited on either a moveable or
functional and multifunctional polymer-based material systems; as immoveable build plate, before solidifying to form a part, with
machines and materials systems play the crucial roles in dimensional accuracy in the order of 100 mm [43]. Direct Ink
8 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

Writing (DIW), which are considered more advanced extrusion-

based processes, have been considered as relevant for delivering
smarter, eco-friendlier, and more biocompatible parts. According to
Ref. [50], intimately blended colors and materials cannot be ach-
ieved in the process design of FFF or FDM processes, hence making
other ME3DP (i.e. FDM technology developments, e.g. DIW)
invaluable options for meeting greater product quality demands.

2.1. FDM machines & developments

The co-founder of Stratasys, Scott Crump, patented the name:

fused deposition modeling (FDM) in 1989, and in recent times,
FDM-based 3D printers have emerged as the most popular 3D
printers used in printing thermoplastic polymers and composites
Fig. 8. Important aspects in material flow during an FDM process (Reprinted with
[3,51,52]. Industrially, FDM machines (see Fig. 7) are also consid- permission from Ref. [43] under Copyright creative commons attribution license).
ered to have significant advantages for cost-efficiency and
simplicity [53].
An FDM machine can be directly related to conventional,
extrusion-based polymer processing machines [55]. In its basic introduced by another external system like a human or robotic/
form, the FDM technology uses only a thermoplastic filament as it is automated system.
a material option [56]. The printer head, which holds the heating Dual head FDM printers make the production of polymer com-
element, extruder, and nozzle, operates at a relatively high tem- posites a simpler problem to solve as they can alternate the printing
perature (150e250  C) before extruding and depositing the molten of two material systems. These printers offer the capability of
thermoplastic material to form 2D layers and consequently, 3D printing with support structures. It can also be applied in the
printed parts. As seen in Fig. 8 below: each unit of polymer printing of layered and skeletal based composites. Additionally, in
extruded is considered a road/bead and shows swelling effects that special cases, multiple parts can be printed faster by using both
must be controlled partly by adequate heat distribution for the printer heads simultaneously, and will therefore, lead to at least a
printing of dimensionally accurate parts. Also, prior to deposition, 50% improvement in time-efficiency, thereby making it a great
buckling or the structural failure of the filament may occur too and option for small-sized, multiple component fabrication activities
highlights other aspects of the FDM process that must be controlled using FDM.
correctly. The ability of the extruded material to maintain a pre- The in-nozzle impregnation technique is a recently developing
determined diameter, shape or structure throughout the printing type of ME3DP method similar to FDM that introduces the heated
stage is an important point to consider. reinforcing material (usually fibers) into the nozzle head to facili-
The simplicity of the actual process has led to rapid adaptations tate better mixing and incorporation of the fibres into the poly-
being made to suit developing material systems other than ther- meric filament matrix [8]. These are strongly developing as a
moplastics alone. Fig. 9 shows the different forms in which FDM unique option for printing short and continuous fiber-reinforced
machines have been adapted for the production of multi or com- polymer composites (FRPs) [57], but currently, lack significant ev-
posite material systems and parts. idence for industrial adoption [21,58].
The single head design of FDM machines is the basic form of the These have also further led to greater interest in the develop-
technology, allowing only one material system to be printed at ment of processes that allow advanced composites, and bio-based
relatively high processing temperatures. When a compatible materials to be processed correctly. 3D bio plotting and direct ink
polymer-based composite material system (usually polymer writing are examples of other forms of ME3DP techniques that have
blends) is obtained as a filament; composite blends can be printed been more recently developed via the process and material opti-
in this way, hence obtaining a composite product. Alternatively, mization of the FDM technology; to deliver parts and products with
printing can be done on a reinforcement material, which can be more advanced material systems, and for bioprinting applications
[59]. In DIW (also referred to as Robocasting), which is heavily
utilized in mesoscale and microscale structures; a liquid-phase
“ink” is dispensed out of small nozzles under controlled flow
rates and deposited along digitally defined print paths to fabricate
the desired 3D structures [21,60]. In the case of bioprinting,
extrusion or FDM-based printing technologies are modified to be
capable of printing biological systems like organs and tissue scaf-
folds and is a developing area of extrusion-based 3DP with major
interest according to literature findings [36,37,59,61]. Uniquely,
these methods follow the same extrusion principle as in FDM but
can process materials with higher and lower temperature and
physical property processing requirements.
As earlier discussed, achieving a 3D printed part involves
creating a part or product from a 3D computer model; either
designed in 3D software or scanned using any available scanning
methods (e.g. CT and MRI scans). This is the same for all the AM
Fig. 7. Typical FDM machine design with a printed part on an immovable print bed/hot methodologies. However, in the use of a specific 3DP technique
plate (Reprinted with permission from Ref. [54] under the copyright creative commons (considering their processes required to be performed after
attribution license).
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 9

Fig. 9. Development of FDM for advanced fabrication capabilities [5].

printing), there is a need for the 3D manufacturing system to be 2.1.1. Factors affecting the FDM process: CAM, FDM printer and
tailored to that specific 3DP category. This will enable the appro- material resources
priate ‘design of configuration’ and ‘control’ that affects the specific Below are factors that are responsible for the quality of parts
3D printing process. In light of this, the following sections discuss, produced in the ME3DP (FDM) with respect to the design and
from the viewpoint of an AM process design, the configuration and control system, printing process; as they affect process quality,
control factors of CAM systems, 3D (FDM) printer and material surface finish, mechanical properties, and dimensional accuracy of
resources in a ME3DP process. These sections cover the actual 3D printed parts and/or products. Highlighting these gives a good
printing process (including insight into the material feedstock and breakdown of key factors and aspects to consider during experi-
filament production process). These should extensively help the mental review and future experimental design processes (see
reader to gain an improved understanding of the process aspects Table 2). They cover all the main aspects of computer design, ma-
and technicalities that affect the final part quality of ME3DP chine, and material design; used in most manufacturing processes
processes. to define the part or product output.

Table 2
Important resources factors and key aspects of the ME3DP process [3,7,47,62].

Factors Aspects Affecting

CAM: Design & information system (i.e. Control system)  path planning, ✓ Part surface finish
 part orientation, ✓ Part mechanical properties
Machine (FDM or FFF machine)  speed of 3D dispensing or filament feed, ✓ Part dimensional accuracy
 pressure and temperature gradient, ✓ Process efficiency and effectiveness
 nozzle design,
Materials  die swelling,
 long-chain branching,
 melt viscosity,
 crystallization rate of melt material,
 shear-thinning induced by tailored molar mass distributions,
 addition of stabilizers and other additives,
10 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

2.1.1.1. Computer aided manufacturing: for part and process design & 2.1.1.1.1. Part orientation & path planning. The part orientation
control. A CAM system is an embodiment of part and process of a part; in relation to the infill orientation and to the printing
design system software and/or functionalities, which typically en- system's main axes of movement for Cartesian 3D printers plays an
ables a streamlined part production process - from part design to important role in the mechanical behavior, dimensional accuracy
production. CAM systems allow the user to importantly control the and surface finish of printed parts [47]. Also importantly, part
part/model design, and process parameters, which ultimately de- orientation can further define the need or extent to which support
termines the quality of the ME process, and especially the printed structures are needed, which is important for managing the cost
part quality. Prior to printing, the CAM system uses a CAD or 3D efficiency of the process.
model (in tessellated file format, e.g. .stl) to define a tool-path (in G- An important aspect of path planning is the choice of infill
code) [47,48]; which is to be followed by the nozzles' tip during the patterns. When using a rectilinear pattern, each individual layer is
extrusion and deposition stage of the 3DP process. The G-code is a filled with a raster (see Fig. 10) of parallel roads with the next
computer language that can be understood by computer numerical adjacent raster layers at a fixed alternating angle of 90 (see Fig. 10)
control (CNC)-based machines; such as those used for extrusion- between them. Adjusting the infill density, affects the level of
based processes [47,48]. Other processing information regarding occupied space in the hollow sections of the part, and can therefore
the individual fibres’ width and height can be set before or after create a scantier or denser part with bigger or smaller distances
printing starts, assuming in the latter case, that a preferred value is between the extruded fibres/roads [47]. A slightly negative raster to
realized to be more beneficial for the printing process. Various raster distance; corresponding to fibre overlapping, has been found
deposition strategies can be exploited and developed during the to limit void density and increase the contact area among fibres,
slicing stage with several parameters available to the user. Once a hence leading to stronger fiber-to-fiber bonds. However, on the
strategy has been developed and set in the slicing software (e.g. other hand, the excessive build-up of polymer material at the lay-
Cura, Quickslice, etc.), slices (i.e. cross-sections of the part model) is er's perimeters can significantly affect the dimensional accuracy of
developed in the CAM system, and a tool path is defined as a G- the part in the XY plane. This, therefore, highlights the sort of
code; before being communicated to the extrusion-based 3D considerations to make when deciding on the many factors in FDM
printer [47,48]. If support structures are desired, they can also be or ME3DP processes.
included prior to slicing the model. Essentially, as the varying
process factors are updated, the tool path and G-code are updated 2.2. The FDM production process
accordingly; to reflect on orientation, size, or any other process
factor change that causes a change in point location. The tool path The FDM printing process was considered to generally involve
and G-code should, therefore, be well considered, as they have a three main stages; highlighted below: i.e. stage prior to deposition,
significant effect on the thermal stress accumulation in the deposition stage, and stage after deposition, as a means of gaining a
deposited fibers. This signifies that when various CAM programs better understanding of the processing factors involved throughout
using the same inputs may produce parts with different responses the FDM part production process (see Fig. 11).
to the environmental stresses experienced by the extruded fibers. ME3DP techniques are similar to conventional extrusion pro-
In a study by Ref. [62], an open-sourced G-code program, Slic3r 1.2 cesses, using the same mechanism as in other extrusion-based
was used to fabricate specimens. Another G-code program, Voxel- manufacturing processes like injection molding. However, in the
izer 1.4, with a differing G-code generating algorithm, was used case of ME3DP, molds are unnecessary, and the extrusion nozzle is
with the same input values for tool path and process parameters as vertically mounted. They are however both significantly
the Slic3r 1.2; to check the effect that different CAM programs have temperature-dependent processes; requiring relatively higher en-
on the properties of the final printed part [47]. It was found that ergy input at the prior to deposition stages of the process - to
specimens created with the different CAM programs exhibited achieve better control of the feed material's rheology.
different fracture morphologies [47]. Therefore, in choosing a suc- The prior to deposition and deposition stages, respectively
cessful printing and deposition strategy, the tool path and G-code involving ‘filament in-feed’ and ‘molten material flow through the
must be optimized for a specific set of CAM and 3DP machines so melting reservoir and nozzle’ of the print head is a pressure-driven
that more reliable sets of results can be obtained for improved part flow of material mass (non-Newtonian polymer melt). This
quality. Usually, a good deposition strategy is to deposit continuous controlled flow is mainly related to:
contours of the 2D-layers boundary for a given cross-section of the
3D model, before filling the spaces in between them with a choice  nozzle geometry [34,43,47],
of infill patterns [48]. This could enable the design of deposition  pressure gradient [34,43,47], and the
strategies that suites a desired mechanical property.  melt's apparent viscosity, and can, at the point of extrusion, be
described to be a fully developed laminar flow of polymer
through a capillary die with a generally circular cross-section
[34,43,47].

The desired pressure for polymer fiber extrusion is applied by

the parts of the 3D printing filament that had been heated be-
forehand, acting as a piston as it is being pushed by a pinch-roller
feeding mechanism into the melting reservoir of the printer head
[47]. This helps in a successfully controlled extrusion and deposi-
tion process of semimolten thermoplastic fibers on a fixed or
spatially translatable platform. Some important process parame-
ters, using example values for PLA include: filament feed velocity
(e.g. 15e30 mm/s), extrusion temperature (e.g. 160e210  C), cool-
Fig. 10. Shows a raster of parallel roads deposited to form a layer. Also shows the raster
ing rate (e.g. 20% cooling fan speed), print bed temperature (e.g.
angle of relative roads in a rectilinear road pattern Reprinted with permission from 0e60  C), print area/chamber temperature (e.g. 0e60  C), and
Ref. [43] under the Copyright creative commons attribution license). volumetric flow rate (VFR in m3/s or mm3/s). As printing initiates,
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 11

Fig. 11. Deposition, and after deposition stages of the ME3DP process.

the rate at which the filament is fed to the liquefier/melting strength (for the same polymers); [64]. However, the tensile
reservoir (i.e. feed velocity) is dynamically controlled and related to strength test results obtained for these parts fluctuated when a
velocity changes of the print head, thereby allowing the printing large sample set was observed, thereby suggesting the ease with
system to maintain a constant material volumetric flow rate (VFR). which slight changes in fabrication method and resources specifi-
The amount of melt material that is present in the reservoir cations can affect the reliability of printed part quality. Although
chamber, the melt temperature, and consequently, the viscosity composites like polymer blends use similar polymeric materials,
and surface energy of the melt are inherent material factors that the nature of polymer composites and nanocomposites are
control with feed rate/feed velocity of the extruded molten poly- different.
mer. On extrusion, the print head generally exhibits a constant In summary, an AM part is created by superimposing a number
linear movement; where the extruder motor within the print head of 2D layers, such number of layers defined beforehand, in a pattern
is set at a speed that is proportionate to the printing speed, defined by a G-code. The printer head uses the G-code for each 2D
therefore enabling an indirect control of feed and extrusion velocity layer to generate a specific pattern of fibers (with widths defined
of the thermoplastic polymer material. beforehand and heights). Achieving a functional, robust part in-
Consequently, the extrusion temperature and feed/deposition volves optimum control of filament production, 3DP extrusion
rate represent the most important process parameters influencing temperature, deposition rate, and print-bed area conditions
the inter-layer and intra-layer bonding of deposited roads as each (pressure, temperature, etc.), amongst several other factors that
fiber layer is deposited on a previously deposited layer/road of favor the best inter and intralayer bonding of a given material
material [43,47]. Once an extruded fiber makes contact with other system. These factors will also have implications on the total print
previously deposited roads, heat exchange by conduction occurs; time, which is an important factor when considering the cost of
and by convection and radiation with their surroundings to facili- production, and other resources available for the job.
tate or hinder the bonding process. This consequently creates new
physical-chemical interactions that lead to the formation of bonds 2.2.1. Potential part limitations with FDM
among individual fibers via a complicated heat and mass transfer The most common challenges or drawbacks associated with
phenomena, which also causes phase changes, and thermal and printing parts with the FDM technology include:
mechanical stress within the printed structure and material fibers.
During the heat transfer and bond formation process, air traps can  Stepped layers [5,52]: these are visible trails of the material
also be developed between contiguous filaments depending on the deposited because of a certain distance among subsequent
level of bonding achieved. The degree of bonding depends on the layer's edges. Through reduction of the diameter of the extruder,
neck growth between adjacent fibers, and the random molecular this effect can be minimized by and/or printing lower layers and.
diffusion at each interface [34,43]. When heat transfer and bonding However, it will also lead to longer print times and more ma-
processes are limited, partial bonds are created, which conse- terial usage, which increases the cost of the process.
quently leads to a printed part with inherent pores - hence pro-  Overhang and bridging [5]: this is an overhang effect, which
ducing a part with lower integrity. This phenomenon, which occurs occurs when elements of a part set at an angle comparative to
after the deposition (i.e. stage requiring performance after depo- the vertical axis; the filament may not have support, thereby
sition) is a critical stage of the process where the printed fibers or leading to a collapse. In these cases, support should be gener-
roads can be further controlled by thermal, chemical and/or at- ated at the model preparation stage to prevent the part from
mospheric conditions surrounding the print bed are and highlights breakdown and damage during and after printing. A bridge is
the extent of control that can be achieved during the FDM process. highly similar to an overhang but has support at both ends.
This control feature, exhibited after the deposition stage, can be Therefore, a bridge characterized by a long overhanging part is a
used during the ME3DP process to address issues like air traps, non- big problem, which usually requires auxiliary supports added
uniform cooling and poor inter or intra-layer bonding. during the design stage and subsequently removed through the
According to Ref. [54], the extrusion process particularly affects final machining of the print.
the maximum strain, because during material extrusion through  Stringing [5]: this is an issue that occurs when the extruder is
the nozzle; the polymer chains are subjected to stress-induced moving between two discontinues points and leaks some of the
orientation, that reduces the elongation characteristics of the plasticized filament from the nozzle due to gravitational forces
extruded material, hence leading to the development of anisotropic or loading from the filament. Improving this effect usually in-
properties. In a typical case of FDM-printed parts showing aniso- volves an appropriate retraction of the filament back into the
tropic properties, fully dense PLA blocks were fabricated [63]. In nozzle; to limit any acting forces.
another case where printed parts were obtained using a RepRap  Warping [5]: this takes place when the edges/corners of the
printer that used the same FDM-based technology, can match and model deflect because of shrinkage of material and uneven
even outperform commercial 3D printers in terms of the tensile temperature distribution across the model. This is a popular
12 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

issue with polymer-based fabrication processes like injection biomedical and pharmaceutical areas, it also has some disadvan-
and compression molding, We can partly counteract the warp- tageous properties. These include its lack of cell motif sites, hy-
ing effect by controlling the cooling rate, and other temperature drophobic nature, small particle size, low ultimate elongation
settings, An alternative method has involved putting a Kapton strain, and the generation of acidic by-product during degradation;
tape on the print bed surface, as this was thought to likely limit some of which could induce foreign bodies or cause clinical com-
the transfer of heat. plications [68]. As these may lead to the limited use of PLA in
 Hygroscopicity [5,52]: this is a term, commonly used to refer to biomedicine, there are increasing efforts to enhance the hydro-
occluded or precipitated porosity is a property of polymer ma- philic properties; increase the cell motif properties and introduce
terials that makes them more prone to absorbing moisture from less acidic bioactivities; aspects that should be strongly considered
the air, thereby leading to parts with more inherent pores. in future research and development activities.
 Structural inhomogeneity [5]: this is referring to the heteroge-
neity of structure particle size and/or insufficient density of a
printed part. It relates to the filament's selective deposition on 2.2.3. Filament production
the bed surface, with differing temperature and road-bonding A filament production process uses a single or twin-screw
effects (i.e. inter-layer and intra-layer bonding). Reduction of extruder to extrude a filament with specified diameter tolerance;
the length among the spits of the filament could minimize this based on the screw extruder's nozzle design, and the FDM 3D
[5]. However, faulty or inaccurate nozzle performance may also printing machine used. Considering this, the adjustable screw
hinder improvement. speed, pressure, and temperature were found to be the key pa-
rameters during filament production; that must be well controlled
to achieve the target diameter of the required polymer-based fila-
ment that has been formed beforehand [47,70]. These offer the
2.2.2. Material feedstock for FDM route to achieving optimum extrusion values for the filament
The most frequently used materials for FDM or FFF machine production process. More specifically, the 3D printing filament
processing are acrylonitrile butadiene styrene (ABS) and polylactic should have the capability to provide as well as sustain the pressure
acid (PLA) [65,66], having typical bulk strengths between 30 and needed to achieve a successful extrusion process. However, failure
100 MPa, and elastic moduli in the range of 1.3e3.6 GPa [43,67]. to do this results in filament buckling that occurs at the stage when
Other polymeric material option used includes polycarbonate, the extrusion pressure is higher or lower in comparison to the
polyamide, high-impact polystyrene, poly(oxymethylene) and critical buckling load that the filament supports. In such cases also,
others. In achieving the material extrusion process, a form of ma- load carrying ability of the filament determines elastic modulus,
terial feedstock; either in the form of pellets or filaments is while the resistance to extrusion (or extrusion pressure) is deter-
required. However, filaments are very common for the FFF and FDM mined by the melt viscosity.
processes. Table 3 shows the majority of commercially available Choosing the right filament material for achieving process effi-
filament stocks, which also further highlights, the material limita- ciency and effectiveness would involve using material systems with
tions to ME3DP. It is important to note that these values can differ favorable and controllable physical-chemical, rheological, struc-
depending on the supplier, and their specific filament fabrication tural and mechanical properties [7]; considering their effects on
methods. This is important because mechanical properties can printability, applicability, and performed at a stage subsequent to
diverge meaningfully from the bulk material properties because of processing [7]. These key material factors are highlighted below
the specifics of the process and part design (Blok et al. [43]), hence (see Fig. 12):
also highlighting the need for more standardized research and In highlighting some of the critical physical-chemical and
experimentation in the development of ME3DP operating proced- rheological properties identified above, wettability is the ability of a
ures that yield reliable parts. polymer to wet another solid surface that it comes in contact with.
ABS, ABS blends, and other petroleum-based thermoplastic This is defined by the wetting angle, of which angles greater than
blends have generally been the most frequently encountered ma- 150 indicate superhydrophobicity, while angles less than 5 indi-
terials in FDM before PLA emerged and joined the group as a more cate super hydrophilicity [71]. Essentially, the ability of a polymer
recent and promising material for filament fabrication. PLA is very to wet another surface improves its bonding capability, which is
promising because of its biodegradable characteristics [47,68]. PLA important in the interlayer bonding of polymer roads during
was identified as the most-used renewable polymer in tissue en- ME3DP. Viscosity, which is another critical factor in ME3DP, is
gineering because of a variety of benefits such as biocompatibility, defined as the ‘resistance to flow’ of a given material, or polymeric
low cost, non-toxicity, excellent mechanics, biodegradability, ease material in this case [72,73]. It is the governing characteristics of
of processing, and the green feature of its synthesis routes (from polymers in ME-based manufacturing, which defines the ability of
renewable resources) [36,69]. PLA is gradually making up more of the polymer to maintain a desired flow property while in transit
the FDM 3D printing feedstock, and although the just-mentioned from the heating chamber, through the nozzle, and onto the print
benefits of PLA render them suitable for broad applications in bed; The strength of the intermolecular bonds between individual

Table 3
Commercially available filaments [51,67].

No. Material Tensile Strength (MPa) Tensile Modulus (MPa) Elongation (%)

1 ASA 33 2010 9
2 ABS-ESD7 36 2400 3
3 ABSi 37 1920 4.4
4 PC-ABS 34 1720 5
5 ABSplus-P430 33 2200 6
6 FDM Nylon 12 48 1310 6.5
7 PC 68 2300 5
8 PPSF 55 2100 3
9 PLA-3052D 62 2050 3.5
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 13

Fig. 12. Material factors to consider in ME3DP (reprinted with permission from Ref. [7], Copyright with license number: 4692831280732).

polymer chains in a polymer significantly defines this property;

with stronger bonds leading to higher viscosities, and vice versa. In
another case of polymeric properties, the isoelectric point (pI) of a
polymer is defined as the pH at which the polymer has a net charge
of 0 (i.e. a neutral charge) [74]. Acidic polymers have a higher pI,
while basic polymers have a lower pI. This factor will also define the
electrostatic behavior of the polymer during a ME3DP process and
may affect the adhesion and separation properties with the mate-
rials and surfaces it comes in close proximity with during pro-
cessing. Flowability, as earlier highlighted, is a resulting property
that is strongly related to the viscosity of the polymeric material
[75]. More viscous materials have a limited level of flowability and
vice versa and will affect the polymer's ability to flow from the
heated nozzle head through to the print bed. Lastly, the glass
transition temperature (Tg) of a polymer is the temperature at
which the random molecular structure of amorphous polymers
begins to flow due to thermal energy input [73]. Similarly, the
melting temperature (Tm) follows the same principle but applies to
the flow-initiation of the ordered (crystalline) molecular structure
of a polymers.
The ability of the polymer to maintain an appropriate viscosity
value throughout the various stages of printing dictates the quality
of the polymer deposition control and sintering, which in turn, has
a direct impact on the mechanical properties of the printed com-
ponents. With the demand for greater sustainable developments
within financial, economic, and environmental areas amongst
others, there is a significant opportunity for ME3DP and materials
development projects to support ‘blue ocean’ strategies for busi-
nesses, while creating more efficient and sustainable supply chains.

Fig. 13. Desirable properties of innovative materials for ME3DP [7], Copyright with
3. Innovative polymers/nano-based materials, with research license number: 4692831280732.
developments in ME3DP

Despite the dominance of commodity plastics (i.e. PET, PP, PS, on the target industry for the polymer-based material, there are
some key properties (highlighted in Fig. 13) that must be innovated
PE, etc.), natural and synthetic, bio-based and biodegradable
polymer materials like polybutylene succinate (PBS), and poly- for enabling their successful adoption. For example, the biomedical
industry will require innovative polymers that are printable, and
hydroxyalkanoates (PHA), cellulose, and lignin have recently
emerged as a subject of important focus for the development of more importantly biocompatible; with acceptable degradation ki-
netics and degradation by-products. Meanwhile, in the automotive
polymer-based material systems with functionalities that are
significantly in demand by economies and the ecosystem [76]. industry, more emphasis may be on the printability and tailored
mechanical properties of the in-use polymer as is required for op-
Although these materials might not completely replace petroleum-
based plastics, there appears to be a lot they can do to minimize the timum applicability. Having highlighted these needs, the earlier-
mentioned innovative polymers will now be discussed; followed
carbon footprint of AM products and process life cycles. Depending
14 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

by a review of developments in the use of polymer-based systems 3.3. Lignin

for ME3DP.
Lignin is a biopolymer that is highly aromatic and is found
naturally in the fibrous part of plants and extracted as a by-product
of wood pulping industries during a delignification process [86].
3.1. Poly butylene succinate (PBS) Lignin properties such as its high abundance in nature, antimicro-
bial, lightweight, environmentally friendly, antioxidant, and
PBS is one of the most imperative biodegradable aliphatic biodegradable nature, along with a neutral CO2 footprint makes it a
polyester known commercially as Bionolle. It is a biopolymer ob- potential candidate for next generation materials. However, low-
tained via polycondensation of succinic acid and 1e4 butanediol; purity, heterogeneity, smell, and issues with color remain the
offering plastic producers an exciting building block for biopolymer existing problems with commercially available lignin products [86].
compounds and polymers [77,78]. It has properties similar to
polypropylene, polyethylene, etc. that are popularly used in 3.4. Cellulose and nanocellulose
extrusion, injection, compression or blow molding processes
[46,79,80], Importantly, Bionolle has a similar processing ability to Cellulose is an inexhaustible and sustainable polymer. This
conventional resins like the commodity plastics. Bionolle has been highly innovative polymeric material is synthesized by numerous
utilized for some applications; like in shopping bags, and agricul- living organisms and used extensively in the pharmaceutical and
tural products [46]. It is an emerging substitute for polypropylene food industries [87,88]. Its abundance is a consequence of the
(PP), polyethylene terephthalate, polyolefin, and polystyrene in constant photosynthetic cycles occurring within the cells of plants,
some applications; therefore it is possible to understand why other which can synthesize several tons a year [87,89]. They can be ob-
grades of this polymer have now been made to include PLA and tained from plants or agricultural waste; from husk fiber, bamboo,
starch [46,79,81]; used to develop eco-friendlier polymer com- wood, and sugar cane bagasse [87]. The main characteristics of
posites with tailored capabilities. Chemically, Bionolle™ is stable cellulose include its biodegradability, hydrophilicity, chirality,
under ordinary conditions but will become biodegradable in the broad chemical modifying capacity, and capability of forming ver-
presence of microorganisms that exist in composts, wet soil, satile semicrystalline fiber morphologies [88]. Most importantly, in
freshwater, seawater, and activated sludge [46,82]. It will decom- the context of this review, it has the potential to encounter the
pose completely into water and carbon dioxide, thereby making it cumulative demand for environmentally friendly, lightweight
an eco-friendly material. Polybutylene succinate adipate (PBSA), a products but, similar to lignin, it can be limited by its poor me-
copolymer of PBS, has been found to show more degradability due chanical properties [33,40].
to its lower level of crystallinity [46]. PBS is a promising biomaterial
that significantly lacks research and holds promising features that 3.5. Graphene
could significantly impact the development of high performing and
eco-sustainable material systems and products. Their most useful Graphene is a 2-dimensional (one atom thick sheet) carbon-
characteristics include [45,78]: based nanomaterial that has been a revolutionary finding and
sustainable. It was first synthesized in 2004, for which a Nobel prize
 Relatively high service temperature, which can be used for hot in physics was received in 2010 by Dr. Andre Geim and Dr. Kon-
beverage cups, boxes, and utensils; stantin Novoselov. Graphene is obtained from graphite or from
 High-performance heat-sealing ability; having at least the same carbon-containing gases like methane in a top-down (mechanical
level of seal strength as conventional petroleum plastic at a exfoliation) or bottom-up (chemical vapor deposition) processes.
lower temperature; Due its exceptional mechanical, chemical and physical properties,
 Lower environmental cost than most other polymeric materials this material holds great potential for various industries, and
available; currently plays an effective role in existing products for corrosive
 Good printability without significant treatment beforehand. barrier coatings. Pristine graphene is stronger than steel, stiffer
 Compatibility with natural fibers and biopolymers; and than diamond, elastic (up to 20%), and more conductive than cop-
 Excellent processing characteristics. per. Graphene is considered to either be made up of 1e10 atom
layers of carbon; known as pristine (1), few (2e5) or multi (3e10)
layers of carbon atoms bonded in a hexagonal structure.
Having discussed these innovative polymer/nano- based mate-
rials, it was observed that the properties of macropolymers (PBS
3.2. Poly hydroxy alkanoates (PHA) and PHA) were more quantifiable, available and reliable, and
therefore easily more comparable with PLA than for the nano-
PHAs consists a class of natural-based polyesters synthesized material (graphene), and natural fibers (cellulose and lignin).
using microbial fermentation of carbon-based feedstock; which are Hence, as seen in Fig. 14 below, the opportunities for developing
biodegradable and readily compostable thermoplastics, [83,84]. new polymer-based composite blends (and filaments) for ME3DP
PHAs are both bio-based and biodegradable, with physical and may include the development of PLA/PBS or PLA/PHA due to their
chemical properties similar to polypropylene, thereby making it a complementary mechanical and glass transition properties
good alternative to PLA and PBS in biopolymer system de- [90e92], which can be designed to suit a specific industry appli-
velopments. PHA is generally known to be: cation. On the other hand, although being more difficult to
compare, polymer composite material system developments;
 Insoluble in water, and relatively resistant to hydrolytic incorporating graphene, cellulose and/or lignin into PLA (e.g. PLA/
degradation; PBS/graphene) also signify great opportunities for innovating for
 Resistant to ultraviolet light, but with poor resistance to acids biomedical and structural applications amongst others. These
and bases. therefore set the right tone as we now go on to look at recent and
 Biocompatible and non-toxic, thereby making it suitable for state of the art research and developments that have been con-
biomedical and food packaging applications [83e85]. ducted in the area of ME3DP.
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 15

Fig. 14. Comparing the glass transition temperature and mechanical properties of the macropolymers (PLA, PBS and PHA); to support the development of new material (and
filament) systems fabrication for ME3DP.

3.6. State of the art research developments in polymer-based

ME3DP

These will focus on the use of ME3DP techniques as they offer

the most cost-efficient approach for AM product fabrication, with
great possibilities and convenience for users. Other promising
techniques; including BJ and MJ processes; despite their good range
of material compatibility, and process efficiency, will not be dis-
cussed further, and will enable a better focus on ME3DP processes.
Therefore, as we consider a vast range of ME3DP applications in
education, packaging, aerospace, medicine, etc., it is important to
reiterate that the most common polymers currently used in ME3DP
process are modifications, blends and composites of the ABS and
PLA polymers [42].
In a recent case using FDM-based technology, PLA and PBS
Fig. 15. Functional and eco-friendly material systems development (adapted with
pellets were dried in an oven at a temperature of 80  C for at least permission from Ref. [51] under the copyright creative commons attribution license).
12 h, then compounded with a twin-screw extruder to produce a
filament with a homogenous PLA/PBS blend. The barrel tempera-
ture, set at 140e165  C, with a screw speed set at 80 rpm were used available filament processed from PLA were tested for crystallinity
to control the process. Some ratios of PLA to PBS (PLA: PBS) by with X-ray diffraction (XRD); for tensile strength (following
weight ratio used in the blends were 90:10, 80:20, 70:30, 60:40 and American Society for Testing and Materials standards (ASTM
50:50 respectively. The PBS/PLA blends were then 3D printed; with D638)); and for the microstructural structure using a scanning
the result showing a white luster appearance, with no observable electron microscopy (SEM) machine [64]. The results reflected a
distortion (see Fig. 15) when the PBS content was no more than 60% strong relationship among tensile strength and percentage crys-
[51]. However, when the weight ratio of PBS exceeded 80%, sig- tallinity of a 3D printed sample; a strong relationship between the
nificant distortion was observed [51]. Q. Ou-Yang et al. [51] further percentage crystallinity and the extruding temperature [64]. The
identified that PBS40/PLA60 and PBS60/PLA40 were optimum emerging results ideally reflect on ways in which material choice
blends for the ME3DP process when trying to achieve optimum: and material processing route can, through slight changes, affect
the resulting part quality. It could also suggest the importance of
 Distortion behavior; consistency in experimentation in order to achieve a level of reli-
 Dimensional accuracy; ability and therefore potential standardization of processes when
 Interlayer bond strength; and attempting to obtain a specified part quality.
 Material toughness of polymer filament and part. Functionalized carbon-based nanomaterials (CBNs) developed
from carbon nanotubes (CNTs), have become significant players in
In another study by Wittbrodt and Pearce et al. [64], which the development of advanced material systems that are critically
aimed to determine the effect of color and processing temperature for various high-performance applications [93]. This is ultimately
on the material properties of PLA (using a Lulzbot TAZ 3D Printer), due to their unique combinations of physical/chemical properties
five colors (grey, white, blue, black, and natural) of commercially as defined by their electrical/thermal conductivity, optical
16 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

properties and high mechanical strength. Cha et al. [93] predicted The electrical, electrochemical properties and flexibility of the
that although CNTs have been the focus of research efforts, other resulting composite was further controlled respectively with the
types of carbon-based nanomaterials; especially graphene, that has use of fillers (carbon nanofibers and carbon black), and plasticizers
gained significant recognition in recent years; is expected to receive (e.g. polyethylene glycol (PEG)). The formed composite was then
more interest in the near future as various industrial applications tape casted to form homogenous films, before being extruded and
can benefit from their extensive research, for applications in high- printed as the anode material for a lithium ion battery; with
strength materials, thermally stable materials and electronic 60e70 wt% graphite loading. Consequently, the reversible capacity
products. The beneficial properties of CBNs are also being investi- was found to be capable of reaching 200 mAh/g of active material
gated in potential areas for biomedical engineering applications. mA/g at current density of 18.6 mA/g (C/20) after six cycles.
They have gained strong traction in biomedical research for appli- In the case of DIW, several composite inks have been designed
cations in cellular sensors, drug delivery systems, and tissue scaf- and developed to address multifunctional applications; graphene-
fold reinforcements [93]. Despite the fact that it usually takes based inks mostly. This is due to their potential for achieving
significant research and numerous validation steps to meet regu- enhanced electrical, mechanical and biological properties that can
lations of good manufacturing practices (GMPs), such a develop- deliver improved functionalities for numerous 3D printing appli-
ment is highly promising for the prospects of future healthcare cations [95]. As seen in Fig. 17, Jakus et al. [96] successfully
systems. demonstrated a 3D printable graphene composite consisting
Wei et al. [94] were the first to show the possibility of printing mostly of graphene, mixed in dichloromethane with a much lesser
graphene composites using the FDM method. In their work, gra- amount of polylactide-co-glycolide [96]. The ink solution was then
phene oxide and ABS were dissolved in N-Methyl-2-pyrrolidone stored for several months before being loaded for rapid fabrication
solution to achieve a good dispersion of graphene and ABS. via a DIW process as per the user design specifications. A high-fi-
following this, the graphene oxide/ABS powder was precipitated delity scaffold was obtained after printing and following a
from the solution to obtain powder that was loaded into an controlled solvent evaporation process. Importantly, the resulting
extruder to obtain a filament for FDM printing. These were then composite scaffold was self-supporting and considered potentially
used to print freestanding structure with graphene content at no suitable for electronic, bioelectronic, and biomedical applications.
more than 7.4 wt%. In another aspect, Matsuzaki et al. [8] experimented with
In another experiment, Maurel et al. [94] used dichloromethane composite fiber materials; i.e. fibers infused into PLA for 3D
as a solvent to dissolve PLA before mixing it with graphite to obtain printing, targeting improved mechanical properties for the printed
a graphite/PLA composite disc for lithium ion batteries (see Fig. 16). parts [8]. A modified FDM printer was developed to help

Fig. 16. Elaboration process of the 3DP fabrication of graphite/PLA composite disc for Lithium-ion batteries. Adapted with permission from Ref. [94]. Copyright 2018, American
Chemistry Society.
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 17

Fig. 17. Use of DIW for fabrication of graphene-based composite for medical and electronic applications. Adapted with permission from Ref. [96], Copyright 2015, American
Chemical Society.

impregnate the filament with composite fibers before extrusion. In protrusion lengths that are comparable to samples fabricated with
this experiment, the reinforcing fiber was heated using a nichrome a compression molding technique [99].
wire before it entered the nozzle head; to enable and enhance the There have also been growing studies that use a fiber alignment
permeation of the fiber bundles into the thermoplastic resin technique in ME3DP to functionalize composites for biological
structure. The heater inside the nozzle, further helps to consolidate purposes [100]. An example is in a study by Bakarich et al. [97],
the heating and promote better mixing of the fibers and the resin in where 3D printed fiber reinforced hydrogel composites with
the heating chamber. Critically, the results showed superior particular fiber orientation, i.e. in the direction of loading, was used
Young's modulus and strengths compared with other materials to simulate and replicate the structure and loading conditions of
fabricated using commercial 3D printers [8]. The safety of such the meniscus cartilage in bones [7,36]. Other studies that printed
higher temperature processes and process designs may be a replicas of biological products like scaffolds, using the ME3DP, were
concern for use in certain environment with kids, etc. however, this such as in the work by Woodfield et al. [97], which involved the use
seems highly controllable. The 3D printed PLA-based composite of fiber alignment techniques to fabricate 3D scaffold samples [97].
blend displayed an elastoplastic and orthotropic mechanical. In an This gives rise to the potential for using fiber alignment in AM for
important and similar experiment of 3D printing biocomposites, Le several commercial biomedical applications in the future; to create
Duigou et al. [10] used a continuous flax fiber composites filament more dimensionally accurate, biocompatible and functionalized
(within PLA matrix) for ME3DP, which suggested that the obtained prints. Two of such applications in the biomedical industry includes
part showed considerably higher tensile strength and tensile surface texturing, and scaffold printing amongst others [97,101]. In
modulus performance when compared to other 3D printed com- a case for biomedical applications, it was found that stiffer, denser
posites (with short and continuous fiber) e see Fig. 18. polymeric networks resulted in better printable bio-inks but led to
In a recent study by Chris et al. [97], 3D printed thermoplastic a poor cell culture microenvironment. Hence, as depicted in Fig. 19,
polyurethane (TPU) with differing percentages of multiwalled bio-inks are being designed to compensate for poor cell culture
carbon nanotubes (MWCNT) were fabricated using the ME3DP environment and poor shape fidelity [36].
technique. In a study by J. Luo et al. [98], PLA/MWCNT composites In summary, these scenarios give good coverage of the recent
were found suitable for printing by FDM. In this research, high experiments, and key observations that highlight the challenges
conductivity was realized in the 3D printed products containing 5% and opportunities for further justification and improvement of
MWCNTs. The conductivity was 0.4 ± 0.2 S/cm, its tensile strength ME3DP techniques for a good range of material and composites
was 78.4 ± 12.4 MPa, and its elongation at break was 94.4% ± 14.3% systems. Polymer system design, additives or fillers, and processing
[98]. In another study by Tekinalp et al. [97], they investigated fiber parameters as they relate to improving functionality, build speed,
alignment in carbon-fiber/ABS composite when the FDM technol- mechanical properties, accuracy, surface finish, stability, and
ogy was used for printing [58,99]. They identified that using porosity of final parts; are therefore aspects that require critical
ME3DP; they were able to achieve tensile properties and fiber
18 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

Fig. 18. Mechanical properties of a 3D printed composite of flax fiber filament (in PLA) e Adapted with permission from Ref. [57] under the copyright creative commons attribution
license.

Fig. 19. Developing scaffolds for improved bioactivity and bio fabrication window in extrusion-based 3DP (Adapted with permission from Ref. [36], with copyright license number:
4693320664349).
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 19

review and research in order to support the development of

industrially effective polymer-based ME3DP processes.

4. 3DP of multifunctional material systems: a concept of 4D

printing (4DP)

This is a good point to refresh the readers’ minds, recapitulate

various aspects of three-dimensional printing (3DP) to enlarge to
the concept of multifunctional materials systems (MFMS), essen-
tially the concept of 4D printing that was first discussed in the
introduction section of this review paper. Essentially, MFMS is an
easily understood concept of material systems that reflects on how
composites can possess time-dependent multifunctional properties
and capabilities [102,103], thereby enabling products to be more
effective in their functional requirements while retaining or
improving their life-cycle efficiency. More specifically in this review
case, multifunctional polymer composites are extensively
employed in various industrial applications to offer properties of
low density, non-corrosiveness, high specific strength and
modulus, with requirements for good thermal expansion, and Fig. 20. Current and future (potential) industrial applications of 3DP [116].

thermal insulation properties [104e107]. Multifunctional polymer

composite materials meeting such stipulations have been identified
multifunctional products. According to an Ernst & Young report on
to be material systems that are nanophased, active (smart/bio-
3DP, the developments will likely be focused on the industries as
mimetic), and/or advanced (i.e. with advanced textiles and
presented in Fig. 20 below.
matrices, and eco-sustainable features) [24]. In another perspec-
The aerospace and defense industries are shown to have the
tive, Narayana & Burela. et al. [108] define MFMS as material sys-
most current applications of 3DP, but also with the highest op-
tems that utilize a combination of structural (e.g. strength, stiffness,
portunities for using newly developed 3DP technologies and con-
toughness, etc.) and non-structural (e.g. actuation, energy har-
structs. Furthermore, according to this chart, mechanical and plant
vesting, self-healing, sensing, etc.) properties to deliver specific
engineering applications will potentially see great adoptions of 3DP
functionalities for the user, such as those highlighted by Yogendra
technologies and products; based on the low number of applica-
et al. [109], Javaid & Azvaid [107], Yogendra & Rainer [110], So €ren
tions they currently employ. Some recently 4D printed products are
et al. [111], An et al. [112], and Florian et al. [113] in their work.
depicted in Fig. 21 to aid with visualizing some of this revolutionary
With these in mind, the concept of 4D printing (4DP) is born,
development that is poised to improve future possibilities of
directly having a strong relation to the fabrication of MFMS. 4DP
product and service systems within the identified industries.
concept is currently invoked from among the three paradigms of
capabilities for product fabrication [114]; They include:
5. Major challenges and future perspectives
1. using an individual smart 1D, 2D, or 3D material that changes its
shape based on stimuli (such as humidity and temperature); ME3DP techniques utilizing polymer-based systems have an
2. using 3DP to construct polymer-based parts that support cell/ unprecedented range of opportunities for growth and development
tissue growth (i.e. bioprinting); or especially in the use of biocompatible and biodegradable bio-
3. using microsized smart particles to self-assemble composites or materials, including fiber-reinforced polymers. The automotive,
structures, which can alter their pattern following stimulation. aerospace, biomedical, and packaging industries appear to be the
industries most likely to benefit from these potentially eco-
From these paradigms, we can more comprehensively explain sustainable and multifunctional developments. However,
4DP as the formation of complex material systems, composites and although ME3DP was found to generally offer better potential for
structures (with the back-up of features of 3DP that have the ability achieving cost-efficient, scalable and environmentally sustainable
to adopt different functions, shapes and forms when subjected to 3DP processes, they were, alongside other AM techniques found to
varying environmental stimuli). Researchers simply view 4DP as an lack well-established processes, standards, and build-material
extension of 3DP, with the added constraint of time [114], when systems; which are important aspects limiting the reliable adop-
considering the mechanical, physical, and chemical constraints that tion of AM for the production of parts and products for the above-
already exist within 3DP. mentioned industries. Another challenge that will benefit the in-
This brief discussion on 4DP/MFMS fabrication is an attempt to terests of investors and users of AM technologies is the security of
help highlight and validate the need for wider material adoptions 3DP systems; considering that several developed 3DP softwares are
in AM (more specifically, in ME3DP); as a push towards capitalizing open-source systems. This should come across to regulators and
on the advantages of AM techniques and any supporting compu- 3DP system developers as key subjects to consider when designing
tational frameworks capable of adding to the realization potential and creating 3DP systems for the future. Furthermore, in the in-
of more unique, robust, and multifunctional product systems. terest of developing more sustainable supply chains in AM; it was
Shape memory polymers (SMPs) like polyurethanes and hydrogels thought that the level and effectiveness of ‘informing and
have been known for their shape changing, multifunctional capa- educating’ the masses would remain a challenge for maintaining
bilities [114]ez. Using FDM, self-folding metamaterials have been and improving the global awareness of individuals, businesses and
successfully printed; and while using UV-supported DIW, the organizations in their decisions that relate to waste management
printing of highly stretchable self-healing shape memory elasto- and socio-economic demands.
mers have also been achieved for the biomedical industry [114,115]; With regards to future perspectives; it was thought that
highlighting the possibilities with ME3DP techniques for future following the assessment of operational factors including energy,
20 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

Fig. 21. Showing 4D printed devices for different applications. (a) An actuator system made from porous silicon elastomer, filled with ethanol, (b) A thermo-responsive
(30  Ce90  C) liquid crystal elastomer applicable in adaptive optics, (c) A braided tube preform of PLA-based polymer showing shape memory effect over time, (d) A gripper
using shape memory behavior; for potential applications in adaptive manufacturing and robotic systems, (e) A 3D-printed hydraulic robot, using liquid support for bellow actuators.
Adapted with permission from Ref. [117] under the copyright creative commons attribution license.

speed, resolution, functionality, and material options for ME3DP Acknowledgment

techniques; the most useful and prospective area for future
research and development surrounds the use of more eco-friendly; In this work, first author would like to acknowledge the huge
bio-based and biodegradable material options that are capable of support of his family, and the guidance of students and staff col-
multifunctionality; with a further consideration of standardizing leagues at the Cranfield University's School of Aerospace, Transport
and improving the speed of ME3DP processes. Already, the wide and Manufacturing, not excluding the wider Cranfield University
adoption of PLA suggests a positive development so far and a good network; for its role in developing future leaders in the domains of
starting point. However, materials like PBS, lignin, cellulose, gra- engineering and management. The authors would also like to
phene (and other nano-based materials) further serve as great acknowledge the UK Engineering and Physical Sciences Research
candidates for the development of advanced polymer composite Council funded project, STRAINcomp (Ref.No.EP/R016828/1) and
material systems for use in a broad range of industrial areas. Royal Academy of Engineering (Grant No. IAPP18-19\295).
Eventually, the hope is to move industries closer to the successful
adoption of ME3DP strategies that achieve eco-friendly production
of functional/multifunctional and sustainable parts/products for References
our society at large.
[1] U. Scheithauer, A. Bergner, E. Schwarzer, H.-J. Richter, T. Moritz, Studies on
thermoplastic 3D printing of steelezirconia composites, J. Mater. Res. 29 (17)
(2014) 1931e1940, https://doi.org/10.1557/jmr.2014.209.
Declaration of competing interest [2] T.D. Ngo, A. Kashani, G. Imbalzano, K.T.Q. Nguyen, D. Hui, Additive
manufacturing (3D printing): a review of materials, methods, applications
and challenges, Compos. B Eng. 143 (2018) 172e196, https://doi.org/
The authors declare no conflict of interest. 10.1016/j.compositesb.2018.02.012.
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 21

[3] J.R.C. Dizon, A.H. Espera, Q. Chen, R.C. Advincula, Mechanical characterization [28] Multifunctional Materials and Their Impact on Sustainability | EME 807.
of 3D-printed polymers, Addit. Manuf. 20 (2018) 44e67, https://doi.org/ [Online]. Available: https://www.e-education.psu.edu/eme807/node/698.
10.1016/j.addma.2017.12.002. [Accessed: 21 Oct 2019].
[4] S.A.M. Tofail, E.P. Koumoulos, A. Bandyopadhyay, S. Bose, L. O'Donoghue, [29] K.W.A.B. Spierings, M. Voegtlin, T. Bauer, Materials testing standards for
C. Charitidis, Additive manufacturing: scientific and technological challenges, additive manufacturing of polymer materials, Prog. Addit. Manuf. 1 (2015)
market uptake and opportunities, Mater. Today 21 (1) (2018) 22e37, https:// 9e20, https://doi.org/10.6028/NIST.IR.8059.
doi.org/10.1016/j.mattod.2017.07.001. [30] D. Ortiz-Acosta, T. Moore, Functional 3D printed polymeric materials, in:
[5] K. Bryll, E. Piesowicz, P. Szyman  ˛ czka, M. Pijanowski, Polymer
 ski, W. Sla Functional Materials [Working Title], 2018.
composite manufacturing by FDM 3D printing technology, MATEC Web Conf. [31] S. Buchholz, Factories of the future, Manuf. Chem. 82 (3) (2011) 27e29,
237 (2018), https://doi.org/10.1051/matecconf/201823702006, p. 02006. https://doi.org/10.1007/978-3-319-94358-9.
[6] S.C. Ligon, R. Liska, J. Stampfl, M. Gurr, R. Mülhaupt, Polymers for 3D printing [32] D.G. Bekas, Y. Hou, Y. Liu, A. Panesar, 3D printing to enable multifunctionality
and customized additive manufacturing, Chem. Rev. 117 (15) (Aug. 2017) in polymer-based composites: a review, Compos. B Eng. 179 (October)
10212e10290, https://doi.org/10.1021/acs.chemrev.7b00074. (2019) 107540, https://doi.org/10.1016/j.compositesb.2019.107540.
[7] J. Liu, L. Sun, W. Xu, Q. Wang, S. Yu, J. Sun, Current advances and future [33] V.C.F. Li, X. Kuang, C.M. Hamel, D. Roach, Y. Deng, H.J. Qi, Cellulose nano-
perspectives of 3D printing natural-derived biopolymers, Carbohydr. Polym. crystals support material for 3D printing complexly shaped structures via
207 (2019) 297e316, https://doi.org/10.1016/j.carbpol.2018.11.077. multi-materials-multi-methods printing, Addit. Manuf. 28 (November 2018)
[8] R. Matsuzaki, et al., Three-dimensional printing of continuous-fiber com- 14e22, https://doi.org/10.1016/j.addma.2019.04.013, 2019.
posites by in-nozzle impregnation, Sci. Rep. 6 (March 2016), https://doi.org/ [34] Q. Wang, et al., Investigation of condensation reaction during phenol
10.1038/srep23058. liquefaction of waste woody materials, Int. J. Sustain. Dev. Plann. vol. 9 (5)
[9] R.A. Buswell, W.R. Leal de Silva, S.Z. Jones, J. Dirrenberger, 3D printing using (2014).
concrete extrusion: a roadmap for research, Cement Concr. Res. 112 (October [35] J.U. Pucci, B.R. Christophe, J.A. Sisti, E.S. Connolly, Three-dimensional print-
2017) (2018) 37e49, https://doi.org/10.1016/j.cemconres.2018.05.006. ing: technologies, applications, and limitations in neurosurgery, Biotechnol.
[10] A. Le Duigou, A. Barbe , E. Guillou, M. Castro, 3D printing of continuous flax Adv. 35 (5) (01 Sep 2017) 521e529, https://doi.org/10.1016/j.bio-
fibre reinforced biocomposites for structural applications, Mater. Des. 180 techadv.2017.05.007. Elsevier Inc.
(2019), https://doi.org/10.1016/j.matdes.2019.107884. [36] S. Kyle, Z.M. Jessop, A. Al-Sabah, I.S. Whitaker, ‘Printability’ of candidate
[11] I.T. Ozbolat, M. Hospodiuk, Current advances and future perspectives in biomaterials for extrusion based 3D printing: state-of-the-art, Adv. Healthc.
extrusion-based bioprinting, Biomaterials 76 (2016) 321e343, https:// Mater. 6 (16) (2017) 1e16, https://doi.org/10.1002/adhm.201700264.
doi.org/10.1016/j.biomaterials.2015.10.076. [37] J.K. Placone, A.J. Engler, Recent advances in extrusion-based 3D printing for
[12] L. Serex, A. Bertsch, P. Renaud, Microfluidics: a new layer of control for biomedical applications, Adv. Healthc. Mater. 7 (8) (2018) 1e11, https://
extrusion-based 3D printing, Micromachines 9 (2018) 2, https://doi.org/ doi.org/10.1002/adhm.201701161.
10.3390/mi9020086. [38] B. Panda, C. Unluer, M.J. Tan, Investigation of the rheology and strength of
[13] A.W. Gebisa, H.G. Lemu, Investigating effects of Fused-deposition modeling geopolymer mixtures for extrusion-based 3D printing, Cement Concr.
(FDM) processing parameters on flexural properties of ULTEM 9085 using Compos. 94 (September) (2018) 307e314, https://doi.org/10.1016/
designed experiment, Materials (Basel) 11 (4) (March 2018), https://doi.org/ j.cemconcomp.2018.10.002.
10.3390/ma11040500. [39] C. Myant, J. Li, B. Wu, The Current Landscape for Additive Manufacturing
[14] M. Lille, A. Nurmela, E. Nordlund, S. Metsa €-Kortelainen, N. Sozer, Applica- Research, 2016, p. 83, 2016 ICL AMN Rep.
bility of protein and fiber-rich food materials in extrusion-based 3D printing, [40] L. Dai, et al., 3D printing using plant-derived cellulose and its derivatives: a
J. Food Eng. 220 (2018) 20e27, https://doi.org/10.1016/ review, Carbohydr. Polym. 203 (2019) 71e86, https://doi.org/10.1016/
j.jfoodeng.2017.04.034. j.carbpol.2018.09.027.
[15] Protecting a New World of 3D-printed Products e ASME. [Online]. Available: [41] M. Faes, H. Valkenaers, F. Vogeler, J. Vleugels, E. Ferraris, Extrusion-based 3D
https://www.asme.org/topics-resources/content/protecting-new-world- printing of ceramic components, Procedia CIRP 28 (2015) 76e81, https://
3dprinted-products. [Accessed: 27 Sep 2019]. doi.org/10.1016/j.procir.2015.04.028.
[16] The Security Issues 3D Printing Should Solve Before Going Mainstream e [42] C.R. Rocha, A.R. Torrado Perez, D.A. Roberson, C.M. Shemelya, E. Macdonald,
Help Net Security. [Online]. Available: https://www.helpnetsecurity.com/ R.B. Wicker, Novel ABS-based binary and ternary polymer blends for mate-
2018/08/08/security-issues-3d-printing/. [Accessed: 27 Sep 2019]. rial extrusion 3D printing, J. Mater. Res. 29 (17) (2014) 1859e1866, https://
[17] Data Privacy and Security e 3D Printing: A Cybersecurity Concern. [Online]. doi.org/10.1557/jmr.2014.158.
Available: https://dataprivacyblog.com/3d-printing-a-cybersecurity- [43] L.G. Blok, M.L. Longana, H. Yu, B.K.S. Woods, An investigation into 3D printing
concern/. [Accessed: 27 Sep 2019]. of fibre reinforced thermoplastic composites, Addit. Manuf. 22 (March)
[18] U. Scheithauer, E. Schwarzer, H.J. Richter, T. Moritz, Thermoplastic 3D (2018) 176e186, https://doi.org/10.1016/j.addma.2018.04.039.
printing - an additive manufacturing method for producing dense ceramics, [44] R.H. Hambali, H.K. Celik, P.C. Smith, A.E.W. Rennie, M. Ucar, Effect of Build
Int. J. Appl. Ceram. Technol. 12 (1) (2015) 26e31, https://doi.org/10.1111/ Orientation on FDM Parts: A Case Study for Validation of Deformation
ijac.12306. Behaviour by FEA, 2010.
[19] C. Gonz alez, J.J. Vilatela, J.M. Molina-Aldareguía, C.S. Lopes, J. LLorca, Struc- [45] P. Faibunchan, S. Pichaiyut, W. Chueangchayaphan, C. Kummerlo € we,
tural composites for multifunctional applications: current challenges and N. Venneman, C. Nakason, Influence type of natural rubber on properties of
future trends, Prog. Mater. Sci. 89 (2017) 194e251, https://doi.org/10.1016/ green biodegradable thermoplastic natural rubber based on poly(butylene
j.pmatsci.2017.04.005. succinate), Polym. Adv. Technol. 30 (4) (2019) 1010e1026, https://doi.org/
[20] W. Gao, et al., The status, challenges, and future of additive manufacturing in 10.1002/pat.4534.
engineering, CAD Comput. Aided Des. 69 (2015) 65e89, https://doi.org/ [46] M. Puchalski, G. Szparaga, T. Biela, A. Gutowska, S. Sztajnowski, I. Krucin  ska,
10.1016/j.cad.2015.04.001. Molecular and supramolecular changes in polybutylene succinate (PBS) and
[21] J. Christ, N. Aliheidari, A. Ameli, P. Po €tschke, 3D printed highly elastic strain polybutylene succinate adipate (PBSA) copolymer during degradation in
sensors of multiwalled carbon nanotube/thermoplastic nanocomposites, in: various environmental conditions, Polymers (Basel) 10 (3) (2018) 1e12,
Annu. Tech. Conf. - ANTEC, Conf. Proc., vol. 2017, May 2017, pp. 1e6, https:// https://doi.org/10.3390/polym10030251.
doi.org/10.1016/j.matdes.2017.06.011. [47] E. Gkartzou, E.P. Koumoulos, C.A. Charitidis, Production and 3D printing
[22] A. Pappu, V.K. Thakur, R. Patidar, S.R. Asolekar, M. Saxena, Recycling marble processing of bio-based thermoplastic filament, Manuf. Rev. 4 (2017) 1,
wastes and Jarosite wastes into sustainable hybrid composite materials and https://doi.org/10.1051/mfreview/2016020.
validation through Response Surface Methodology, J. Clean. Prod. 240 (2019) [48] S.H. Ahn, M. Montero, D. Odell, S. Roundy, P.K. Wright, Anisotropic material
118249, https://doi.org/10.1016/j.jclepro.2019.118249. properties of fused deposition modeling ABS, Rapid Prototyp. J. 8 (4) (2002)
[23] A.K. Thakur, A. Pappu, V.K. Thakur, Synthesis and characterization of new 248e257, https://doi.org/10.1108/13552540210441166.
class of geopolymer hybrid composite materials from industrial wastes, [49] K. Formela, Zedler, A. Hejna, A. Tercjak, Reactive extrusion of bio-based
J. Clean. Prod. 230 (2019) 11e20, https://doi.org/10.1016/ polymer blends and compositesecurrent trends and future developments,
j.jclepro.2019.05.081. Express Polym. Lett. 12 (1) (2018) 24e57, https://doi.org/10.3144/
[24] K. Salonitis, J. Pandremenos, J. Paralikas, G. Chryssolouris, Multifunctional expresspolymlett.2018.4.
materials: engineering applications and processing challenges, Int. J. Adv. [50] J.W. Stansbury, M.J. Idacavage, 3D printing with polymers: challenges among
Manuf. Technol. 49 (5e8) (2010) 803e826, https://doi.org/10.1007/s00170- expanding options and opportunities, Dent. Mater. 32 (1) (2016) 54e64,
009-2428-6. https://doi.org/10.1016/j.dental.2015.09.018.
[25] A.D.B.L. Ferreira, P.R.O. No  voa, A.T. Marques, Multifunctional material sys- [51] Q. Ou-Yang, B. Guo, J. Xu, Preparation and characterization of poly(butylene
tems: a state-of-the-art review, Compos. Struct. 151 (2016) 3e35, https:// succinate)/polylactide blends for fused deposition modeling 3D printing, ACS
doi.org/10.1016/j.compstruct.2016.01.028. Omega 3 (10) (Oct. 2018) 14309e14317, https://doi.org/10.1021/
[26] C.H. Kim, H.M. Cho, M.E. Lee, Synthesis and physical property of multi- acsomega.8b02549.
functional siloxane protective coating materials applicable for electronic [52] E.G. Gordeev, A.S. Galushko, V.P. Ananikov, Improvement of quality of 3D
components, Bull. Kor. Chem. Soc. 35 (6) (2014) 1665e1669, https://doi.org/ printed objects by elimination of microscopic structural defects in fused
10.5012/bkcs.2014.35.6.1665. deposition modeling, PloS One 13 (6) (Jun. 2018), https://doi.org/10.1371/
[27] E.M. Palmero, et al., Composites based on metallic particles and tuned filling journal.pone.0198370.
factor for 3D-printing by Fused Deposition Modeling, Compos. Part A Appl. [53] A. Melocchi, F. Parietti, A. Maroni, A. Foppoli, A. Gazzaniga, L. Zema, Hot-melt
Sci. Manuf. 124 (2019), https://doi.org/10.1016/j.compositesa.2019.105497. extruded filaments based on pharmaceutical grade polymers for 3D printing
22 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248

by fused deposition modeling, Int. J. Pharm. 509 (1e2) (2016) 255e263, [80] L. Meng, et al., Preparation, microstructure and performance of poly (lactic
https://doi.org/10.1016/j.ijpharm.2016.05.036. acid)-Poly (butylene succinate-co-butyleneadipate)-starch hybrid compos-
[54] V. Mazzanti, L. Malagutti, F. Mollica, FDM 3D printing of polymers containing ites, Compos. B Eng. 177 (May) (2019) 107384, https://doi.org/10.1016/
natural fillers: a review of their mechanical properties, Polymers 11 (7) j.compositesb.2019.107384.
(2019), https://doi.org/10.3390/polym11071094. MDPI AG. [81] O. Platnieks, S. Gaidukovs, A. Barkane, G. Gaidukova, L. Grase, V.K. Thakur,
[55] M. Harris, J. Potgieter, K. Arif, R. Archer, Large scale 3D printing: feasibility of Inese Filipova, Velta Fridrihsone, Marite Skute, Highly loaded cellulose/poly
novel extrusion based process and requisite materials, in: 2017 24th Int. (butylene succinate) sustainable composites for woody-like advanced ma-
Conf. Mechatronics Mach. Vis. Pract. M2VIP 2017, vol. 2017 Dec, 2017, terials application, Molecules 25 (1) (2020) 121, https://doi.org/10.3390/
pp. 1e6, https://doi.org/10.1109/M2VIP.2017.8211519. molecules25010121.
[56] A.W. Gebisa, H.G. Lemu, Influence of 3D printing FDM process parameters on [82] H. Shirali, M. Rafizadeh, F. Afshar Taromi, E. Jabbari, Fabrication of in situ
tensile property of ultem 9085, Procedia Manuf. 30 (2019) 331e338, https:// polymerized poly(butylene succinate-co-ethylene terephthalate)/hydroxy-
doi.org/10.1016/j.promfg.2019.02.047. apatite nanocomposite to fibrous scaffolds for enhancement of osteogenesis,
[57] A. Le Duigou, A. Barbe , E. Guillou, M. Castro, 3D printing of continuous flax J. Biomed. Mater. Res. 105 (9) (2017) 2622e2631, https://doi.org/10.1002/
fibre reinforced biocomposites for structural applications, Mater. Des. 180 jbm.a.36115.
(2019) 107884, https://doi.org/10.1016/j.matdes.2019.107884. [83] C. Atom, L.W. Mckeen, Polyhydroxyalkanoate Learn More about Poly-
[58] H.K. Sezer, O. Eren, FDM 3D printing of MWCNT re-inforced ABS nano- hydroxyalkanoate Renewable Resource and Biodegrad- Able Polymers, 2013.
composite parts with enhanced mechanical and electrical properties, [84] Phil Van Trump, “Why 2019 May Be a Promising Year for PHA,” plastic-
J. Manuf. Process. 37 (July 2018) (2019) 339e347, https://doi.org/10.1016/ stoday.Com, 2019 [Online]. Available: https://bioplasticsnews.com/2019/01/
j.jmapro.2018.12.004. 21/pha-bioplastics-2019/. (Accessed 11 October 2019).
[59] S. Wang, J.M. Lee, W.Y. Yeong, Int. J. Bioprinting 1 (1) (2015) 3e14. [85] Creative Mechanism Staff, Everything You Need to Know about PHA,” Cre-
[60] A. Shen, D. Caldwell, A.W.K. Ma, S. Dardona, Direct write fabrication of high- ative Mechanism Website, 2017 [Online]. Available: https://www.
density parallel silver interconnects, Addit. Manuf. 22 (2018) 343e350, creativemechanisms.com/blog/everything-you-need-to-know-about-pha-
https://doi.org/10.1016/j.addma.2018.05.010. polyhydroxyalkanoates. (Accessed 13 October 2019).
[61] M. Ojansivu, et al., Knitted 3D scaffolds of polybutylene succinate support [86] V.K. Thakur, M.K. Thakur, P. Raghavan, M.R. Kessler, Progress in green
human mesenchymal stem cell growth and osteogenesis, Stem Cell. Int. 2018 polymer composites from lignin for multifunctional applications: a review,
(2018) 1e11, https://doi.org/10.1155/2018/5928935. ACS Sustain. Chem. Eng. 2 (5) (May 2014) 1072e1092, https://doi.org/
[62] A.C. Abbott, G.P. Tandon, R.L. Bradford, H. Koerner, J.W. Baur, Process- 10.1021/sc500087z.
structure-property effects on ABS bond strength in fused filament fabrica- [87] M. Drahansky, et al., We are IntechOpen, the world’s leading publisher of
tion, Addit. Manuf. 19 (2018) 29e38, https://doi.org/10.1016/ open access books built by scientists , for Scientists TOP 1%, Intech i (tourism)
j.addma.2017.11.002. (2016) 13, https://doi.org/10.5772/57353.
[63] Y. Song, Y. Li, W. Song, K. Yee, K.Y. Lee, V.L. Tagarielli, Measurements of the [88] D. Klemm, B. Heublein, H.P. Fink, A. Bohn, Cellulose: fascinating biopolymer
mechanical response of unidirectional 3D-printed PLA, Mater. Des. 123 and sustainable raw material, Angew. Chem. Int. Ed. 44 (22) (2005)
(2017) 154e164, https://doi.org/10.1016/j.matdes.2017.03.051. 3358e3393, https://doi.org/10.1002/anie.200460587.
[64] B. Wittbrodt, J.M. Pearce, The effects of PLA color on material properties of 3- [89] Cellulose e An Overview | ScienceDirect Topics. [Online]. Available: https://
D printed components, Addit. Manuf. 8 (Oct. 2015) 110e116, https://doi.org/ www.sciencedirect.com/topics/earth-and-planetary-sciences/cellulose.
10.1016/j.addma.2015.09.006. [Accessed: 12 Oct 2019].
[65] T. Letcher, M. Waytashek, Material property testing of 3D-printed specimen [90] S. Kamthai, R. Magaraphan, Thermal and mechanical properties of polylactic
in pla on an entry-level 3D printer, in: ASME International Mechanical En- acid (PLA) and bagasse carboxymethyl cellulose (CMCB) composite by adding
gineering Congress and Exposition, Proceedings (IMECE) vol. 2A, 2014, isosorbide diesters, AIP Conf. Proc. 1664 (2015) (2015), https://doi.org/
https://doi.org/10.1115/IMECE2014-39379. 10.1063/1.4918424.
[66] H. Baqasah, et al., In-situ dynamic response measurement for damage [91] X. Hu, T. Su, W. Pan, P. Li, Z. Wang, Difference in solid-state properties and
quantification of 3D printed ABS cantilever beam under thermomechanical enzymatic degradation of three kinds of poly(butylene succinate)/cellulose
load, Polymer (Guildf). (2019). blends, RSC Adv. 7 (56) (2017) 35496e35503, https://doi.org/10.1039/
[67] J.T. Belter, A.M. Dollar, Strengthening of 3D printed fused deposition man- c7ra04972b.
ufactured parts using the fill compositing technique, PloS One 10 (4) (Apr [92] P.K. Sharma, et al., Synthesis and physical properties of poly-
2015), https://doi.org/10.1371/journal.pone.0122915. hydroxyalkanoate polymers with different monomer compositions by re-
[68] J. Suganuma, H. Alexander, Biological response of intramedullary bone to combinant Pseudomonas putida LS46 expressing a novel PHA SYNTHASE
poly-L-lactic acid, J. Appl. Biomater. 4 (1) (1993) 13e27, https://doi.org/ (PhaC116) enzyme, Appl. Sci. 7 (3) (2017), https://doi.org/10.3390/
10.1002/jab.770040103. app7030242.
[69] R. Song, M. Murphy, C. Li, K. Ting, C. Soo, Z. Zheng, Current development of [93] C. Cha, S.R. Shin, N. Annabi, M.R. Dokmeci, A. Khademhosseini, Carbon-based
biodegradable polymeric materials for biomedical applications, Drug Des. nanomaterials: multifunctional materials for biomedical engineering, ACS
Dev. Ther. 12 (2018) 3117e3145, https://doi.org/10.2147/DDDT.S165440. Nano 7 (4) (2013) 2891e2897, https://doi.org/10.1021/nn401196a.
[70] P. Dudek, FDM 3D printing technology in manufacturing composite ele- [94] A. Maurel, et al., Highly loaded graphite-polylactic acid composite-based
ments, Arch. Metall. Mater. 58 (4) (2013) 1415e1418, https://doi.org/ filaments for lithium-ion battery three-dimensional printing, Chem. Mater.
10.2478/amm-2013-0186. 30 (21) (2018) 7484e7493, https://doi.org/10.1021/acs.chemmater.8b02062.
[71] X. Li, Y. Jiang, Z. Jiang, Y. Li, C. Wen, J. Lian, Reversible wettability transition [95] F. Torrisi, J.N. Coleman, Electrifying inks with 2D materials, Nat. Nanotechnol.
between superhydrophilicity and superhydrophobicity through alternate 9 (10) (2014) 738e739, https://doi.org/10.1038/nnano.2014.218.
heating-reheating cycle on laser-ablated brass surface, Appl. Surf. Sci. 492 [96] A.E. Jakus, E.B. Secor, A.L. Rutz, S.W. Jordan, M.C. Hersam, R.N. Shah, Three-
(Oct. 2019) 349e361, https://doi.org/10.1016/j.apsusc.2019.06.145. dimensional printing of high-content graphene scaffolds for electronic and
[72] Polymer engineering science and viscoelasticity, “characteristics, applica- biomedical applications, ACS Nano 9 (4) (2015) 4636e4648, https://doi.org/
tions and properties of polymers, in: Polymer Engineering Science and 10.1021/acsnano.5b01179.
Viscoelasticity, Springer US, 2008, pp. 55e57. [97] A. Anwer, H.E. Naguib, Multi-functional flexible carbon fiber composites with
[73] K. Balani, V. Verma, A. Agarwal, R. Narayan, Physical, thermal, and me- controlled fiber alignment using additive manufacturing, Addit. Manuf. 22
chanical properties of polymers, Biosurfaces (2015) 329e344. John Wiley & (July 2017) (2018) 360e367, https://doi.org/10.1016/j.addma.2018.05.013.
Sons, Inc. [98] J. Luo, H. Wang, D. Zuo, A. Ji, Y. Liu, Research on the application of MWCNTs/
[74] P.G. Righetti, Determination of the isoelectric point of proteins by capillary PLA composite material in the manufacturing of conductive composite
isoelectric focusing, J. Chromatogr. A 1037 (1e2) (28 May 2004) 491e499, products in 3D printing, Micromachines 9 (12) (Nov 2018), https://doi.org/
https://doi.org/10.1016/j.chroma.2003.11.025. 10.3390/mi9120635.
[75] J.K. Prescott, R.A. Barnum, On powder flowability: Part I, Pharmaceut. [99] H.L. Tekinalp, et al., Highly oriented carbon fiber-polymer composites via
Technol. Eur. 13 (1) (2001) 37e39. additive manufacturing, Compos. Sci. Technol. 105 (Dec 2014) 144e150,
[76] W. Amass, A. Amass, B. Tighe, A review of biodegradable polymers: uses, https://doi.org/10.1016/j.compscitech.2014.10.009.
current developments in the synthesis and characterization of biodegradable [100] G.K. Eleftheriadis, et al., Unidirectional drug release from 3D printed
polyesters, blends of biodegradable polymers and recent advances in mucoadhesive buccal films using FDM technology: in vitro and ex vivo
biodegradation studies, Polym. Int. 47 (2) (1998) 89e144, https://doi.org/ evaluation, Eur. J. Pharm. Biopharm. 144 (April) (2019) 180e192, https://
10.1002/(SICI)1097-0126(1998100)47:2<89::AID-PI86>3.0.CO;2-F. doi.org/10.1016/j.ejpb.2019.09.018.
[77] E. Adamopoulou, Poly(butylene succinate): A Promising Biopolymer, 2012, [101] J. An, J.E.M. Teoh, R. Suntornnond, C.K. Chua, Design and 3D printing of
p. 137. scaffolds and tissues, Engineering 1 (2) (2015) 261e268, https://doi.org/
[78] Nova-Institue, Biobased Polybutylene Succinate (PBS) e An Attractive Poly- 10.15302/j-eng-2015061.
mer for Biopolymer Compounds Polybutylene Succinate e an Interesting [102] S.E. Bakarich, R. Gorkin, M. In, Het Panhuis, G.M. Spinks, 4D printing with
Building Block for Biopolymer Compounds Based on Biobased Succinic Acid, mechanically robust, thermally actuating hydrogels, Macromol. Rapid
2015, pp. 1e11. Commun. 36 (12) (2015) 1211e1217, https://doi.org/10.1002/
[79] T. Fujimaki, Processability and properties of aliphatic polyesters, ‘BIONOLLE’, marc.201500079.
synthesized by polycondensation reaction, Polym. Degrad. Stabil. 59 (1e3) [103] Z.X. Khoo, et al., 3D printing of smart materials: a review on recent pro-
(1998) 209e214. gresses in 4D printing, Virtual Phys. Prototyp. 10 (3) (2015) 103e122,
https://doi.org/10.1080/17452759.2015.1097054.
 S.C. Daminabo et al. / Materials Today Chemistry 16 (2020) 100248 23

[104] P.S.M. Rajesh, F. Sirois, D. Therriault, Damage response of composites coated [111] S.B. Gutekunst, et al., 3D hydrogels containing interconnected microchannels
with conducting materials subjected to emulated lightning strikes, Mater. of subcellular size for capturing human pathogenic acanthamoeba castella-
Des. 139 (2018) 45e55, https://doi.org/10.1016/j.matdes.2017.10.017. nii, ACS Biomater. Sci. Eng. 5 (4) (2019) 1784e1792, https://doi.org/10.1021/
[105] M. Raimondo, et al., Electrical conductivity of carbon nanofiber reinforced acsbiomaterials.8b01009.
resins: potentiality of Tunneling Atomic Force Microscopy (TUNA) technique, [112] D. An, et al., Ultra-thin electrospun nanofibers for development of damage-
Compos. B Eng. 143 (January) (2018) 148e160, https://doi.org/10.1016/ tolerant composite laminates, Mater. Today Chem. 14 (2019), https://doi.org/
j.compositesb.2018.02.005. 10.1016/j.mtchem.2019.100202.
[106] L. Guadagno, et al., Influence of carbon nanoparticles/epoxy matrix interac- [113] F. Rasch, et al., Wet-chemical assembly of 2D nanomaterials into lightweight,
tion on mechanical, electrical and transport properties of structural microtube-shaped, and macroscopic 3D networks, ACS Appl. Mater. In-
advanced materials, Nanotechnology 28 (9) (2017), https://doi.org/10.1088/ terfaces (2019), https://doi.org/10.1021/acsami.9b16565 p. acsami.9b16565.
1361-6528/aa583d. [114] S. Joshi, et al., 4D printing of materials for the future: opportunities and
[107] A. Javaid, A. Afzal, Carbon fiber reinforced modified bisphenol-a diglycidy- challenges, Appl. Mater. Today (Oct 2019) 100490, https://doi.org/10.1016/
lether epoxy composites for flame retardant applications, Mater. Res. Ex- j.apmt.2019.100490.
press 5 (6) (2018), https://doi.org/10.1088/2053-1591/aaca71. [115] A. Rayate, P.K. Jain, A review on 4D printing material composites and their
[108] Prateek, V.K. Thakur, R.K. Gupta, Recent progress on ferroelectric polymer- applications, Mater. Today Proc. 5 (9) (2018) 20474e20484, https://doi.org/
based nanocomposites for high energy density capacitors: synthesis, 10.1016/j.matpr.2018.06.424.
dielectric properties, and future aspects, Chem. Rev. 116 (7) (2016) [116] F. Thewihsen, S. Karevska, A. Czok, C. Jones-Pateman, D. Krauss, If 3D Printing
4260e4317, https://doi.org/10.1021/acs.chemrev.5b00495. Has Changed the Industries of Tomorrow , How Can Your Organization Get
[109] Y.K. Mishra, et al., Fabrication of macroscopically flexible and highly porous Ready Today? Ernst and Young, 2016, p. 24.
3D semiconductor networks from interpenetrating nanostructures by a [117] Z. Zhang, K.G. Demir, G.X. Gu, Developments in 4D-printing: a review on
simple flame transport approach, Part. Part. Syst. Char. 30 (9) (2013) current smart materials, technologies, and applications, Int. J. Smart Nano
775e783, https://doi.org/10.1002/ppsc.201300197. Mater. 10 (3) (2019) 205e224, https://doi.org/10.1080/
[110] Y.K. Mishra, R. Adelung, ZnO tetrapod materials for functional applications, 19475411.2019.1591541.
Mater. Today 21 (6) (2018) 631e651, https://doi.org/10.1016/
j.mattod.2017.11.003.