YILDIZ TECHNICAL UNIVERSITY

DEPARTMENT OF CHEMICAL ENGINEERING

Materials Science for Chemical

Engineers (KMM2622)
Crystallographic Points, Directions, and Planes
CHAPTER-3

2024-2025 Spring Semester

1
 For a crystalline solid, when the periodic
and repeated arrangement of atoms is
perfect or extends throughout the
entirety of the specimen without
Crystalline and interruption, the result is a single crystal.
All unit cells interlock in the same way
Noncrystalline and have the same orientation. Single
Materials crystals exist in nature, but they may also
be produced artificially.
SINGLE CRYSTALS
They are ordinarily difficult to grow,
because the environment must be
carefully controlled.
POLYCRYSTALLINE
MATERIALS
Photograph of a
single crystal
found in Tongbei,
Most crystalline solids are composed of a Fujian Province,
collection of many small crystals or grains; such
China.
materials are termed polycrystalline.
ANISOTROPY
The physical properties of single crystals of some substances
depend on the crystallographic direction in which
measurements are taken. This directionality of properties is
termed anisotropy, and it is associated with the variance of
atomic or ionic spacing with crystallographic direction.
Substances in which measured properties are independent of
the direction of measurement are isotropic. The extent and
magnitude of anisotropic effects in crystalline materials are
functions of the symmetry of the crystal structure; the
degree of anisotropy increases with decreasing structural
symmetry.
 Historically, much of our understanding regarding
X-RAY DIFFRACTION: the atomic and molecular arrangements in solids
DETERMINATION has resulted from x-ray diffraction investigations;
furthermore, x-rays are still very important in
OF CRYSTAL developing new materials.
STRUCTURES
The Diffraction Phenomenon

Diffraction occurs when a wave encounters a series of regularly

spaced obstacles that are capable of scattering the wave, and
have spacings that are comparable in magnitude to the
wavelength.
 X-Ray Diffraction and
Bragg’s Law

X-rays are a form of electromagnetic radiation that

have high energies and short wavelengths—
wavelengths on the order of the atomic spacings for
solids. When a beam of x-rays impinges on a solid
material, a portion of this beam is scattered in all
directions by the electrons associated with each
atom or ion that lies within the beam’s path.
 Diffraction of x-rays
by planes of atoms
(A–Aand B–B).

The equation is known as Bragg’s law; also, n is the order of reflection, which may be any integer (1, 2, 3, . . . )
consistent with sin θ not exceeding unity. Thus, we have a simple expression relating the x-ray wavelength and
interatomic spacing to the angle of the diffracted beam.
NONCRYSTALLINE SOLIDS

It has been mentioned that noncrystalline solids lack a

systematic and regular arrangement of atoms over
relatively large atomic distances.
Sometimes such materials are also called amorphous
(meaning literally without form) or supercooled liquids,
inasmuch as their atomic structure resembles that of a
liquid.
 YILDIZ TECHNICAL UNIVERSITY
DEPARTMENT OF CHEMICAL ENGINEERING

Materials Science for Chemical

Engineers (KMM2622)
Polymer Structures
CHAPTER-4

2024-2025 Spring Semester

10
WHY STUDY Polymer Structures?
A relatively large number of chemical and structural characteristics affect the
properties and behaviors of polymeric materials.

INTRODUCTION
Naturally occurring polymers—those derived from plants and animals—have been
used for many centuries; these materials include wood, rubber, cotton, wool, leather,
and silk. Other natural polymers such as proteins, enzymes, starches, and cellulose are The detailed images
important in biological and physiological processes in plants and animals. Modern can be seen from
scientific research tools have made possible the determination of the molecular Transmission
structures of this group of materials and the development of numerous polymers, which electron
are synthesized from small organic molecules. micrograph.
HYDROCARBON MOLECULES
Since most polymers are organic in origin, we briefly review some of the basic
concepts relating to the structure of their molecules.
First, many organic materials are hydrocarbons; that is, they are composed of
hydrogen and carbon. Furthermore, the intramolecular bonds are covalent.
Each carbon atom has four electrons that may participate in covalent bonding,
whereas every hydrogen atom has only one bonding electron.
A single covalent bond exists when each of the two bonding atoms contributes
one electron, for a molecule of methane (CH4).
Double and triple bonds between two carbon atoms involve the sharing of two
and three pairs of electrons, respectively.
For example, in ethylene, which has the chemical formula C2H4, the two
carbon atoms are doubly bonded together, and each is also singly bonded to
two hydrogen atoms, as represented by the structural formula:
where and denote single and double covalent bonds, respectively. An example of a triple bond is found in
acetylene, C2H2:

Molecules that have double and triple covalent bonds are termed unsaturated. That is, each carbon atom is not
bonded to the maximum (four) other atoms; as such, it is possible for another atom or group of atoms to become
attached to the original molecule. Furthermore, for a saturated hydrocarbon, all bonds are single ones, and no new
atoms may be joined without the removal of others that are already bonded.
 • The molecules in polymers are gigantic in comparison to the
hydrocarbon molecules already discussed; because of their
size they are often referred to as macromolecules.

POLYMER
MOLECULES
These long molecules are composed of structural entities called
repeat units, monomer which are successively repeated along the
chain. The term monomer refers to the small molecule from which a
polymer is synthesized.
THE CHEMISTRY OF POLYMER MOLECULES
Consider again the hydrocarbon ethylene (C2H4), which is a gas at
ambient temperature and pressure and has the following molecular
structure:

Here the repeat units are enclosed in parentheses, and the subscript n indicates the number of times it
repeats. Polyethylene chain structure can also be represented as:

When R represents a CH3 group, it may be straight chain or cycle form.

When all the repeating units along a chain are of the same type,
the resulting polymer is called a homopolymer. Chains may be
composed of two ormore different repeat units, in what are
termed copolymers.

The monomers discussed thus far have an active bond that may
react to form two covalent bonds with other monomers forming a
two-dimensional chain-like molecular structure. Such a monomer
is termed bifunctional. In general, the functionality is the number
of bonds that a given monomer can form.

For example, monomers such as phenol–formaldehyde, are

trifunctional:

They have three active bonds, from which a three-dimensional

molecular network structure results.
MOLECULAR WEIGHT
Extremely large molecular weights are observed in polymers with very long chains.
There are several ways of defining average molecular weight. The number average
molecular weight Mn is obtained by dividing the chains into a series of size ranges
and then determining the number fraction of chains within each size range. The
number-average molecular weight is expressed as:

where Mi represents the mean (middle) molecular weight of size range i, and xi is the fraction of the total number
of chains within the corresponding size range. A weight-average molecular weight Mw is based on the weight
fraction of molecules within the various size ranges. It is calculated according to:

where, again, Mi is the mean molecular weight within a size range, whereas wi denotes the weight fraction of
molecules within the same size interval.
A typical molecular weight distribution along with these molecular weight
averages is shown in Figure.

Distribution of molecular
weights for a typical polymer.
• An alternative way of expressing average chain size of a polymer is as
the degree of polymerization, DP, which represents the average
number of repeat units in a chain. DP is related to the number-
average molecular weight Mn by the equation:

where m is the repeat unit molecular weight.

 • The physical characteristics of a polymer
depend not only on its molecular weight and
shape but also on differences in the structure of
the molecular chains.

MOLECULAR Linear Polymers

STRUCTURE Linear polymers are those in which the repeat
units are joined together end to end in single
chains. These long chains are flexible and may be
thought of as a mass of spaghetti.
Branched Polymers
Polymers may be synthesized in which side-branch chains are connected to
the main ones; these are fittingly called branched polymers.

Crosslinked Polymers
In crosslinked polymers, adjacent linear chains are joined one to another at
various positions by covalent bonds. The process of crosslinking is achieved
either during synthesis or by a nonreversible chemical reaction.
 Network Polymers
Multifunctional monomers forming three or more active covalent bonds
make three dimensional networks and are termed network polymers.

Schematic representations of (a) linear, (b) branched, (c) crosslinked, and (d) network (three-dimensional)
molecular structures. Circles designate individual repeat units.
MOLECULAR CONFIGURATIONS
• For polymers having more than one side atom or group of atoms
bonded to the main chain, the regularity and symmetry of the side
group arrangement can significantly influence the properties.

Stereoisomerism
Stereoisomerism denotes the situation in which atoms are linked
together in the same order (head-to-tail) but differ in their spatial
arrangement. For one stereoisomer, all the R groups are situated on the
same side of the chain as follows:
This is called an isotactic configuration. This diagram shows the zigzag pattern of the carbon chain atoms.
In a syndiotactic configuration, the R groups alternate sides of the chain:

and for random positioning

the term atactic configuration is used.

Geometrical Isomerism
Other important chain configurations, or geometrical isomers, are
possible within repeat units having a double bond between chain
carbon atoms. Bonded to each of the carbon atoms participating in the
double bond is a side group, which may be situated on one side of the
chain or its opposite. Consider the isoprene repeat unit having the
structure

in which the CH3 group and the H atom are positioned on the same side of the double bond. This is termed a cis
structure, and the resulting polymer, cis-polyisoprene, is natural rubber. For the alternative isomer:
the trans structure, the CH3 and H reside on opposite sides of the double bond.
Classification scheme
for the characteristics
of polymer
molecules
 YILDIZ TECHNICAL UNIVERSITY
DEPARTMENT OF CHEMICAL ENGINEERING

Materials Science for Chemical

Engineers (KMM2622)
THERMOPLASTIC AND THERMOSETTING POLYMERS
CHAPTER-4
2023-2024 Spring Semester
 THERMOPLASTIC AND THERMOSETTING POLYMERS
• The response of a polymer to mechanical forces at elevated temperatures is
related to its dominant molecular structure. In fact, one classification scheme for
these materials is according to behavior with rising temperature.
• Thermoplastics (or thermoplastic polymers) and thermosets (or thermosetting
polymers) are the two subdivisions. Thermoplastics soften when heated (and
eventually liquefy) and harden when cooled—processes that are totally reversible
and may be repeated.
• On a molecular level, as the temperature is raised, secondary bonding forces are
diminished (by increased molecular motion) so that the relative movement of
adjacent chains is facilitated when a stress is applied. Irreversible degradation
results when a molten thermoplastic polymer is raised to too high a temperature.
In addition, thermoplastics are relatively soft.
• Most linear polymers and those having some branched structures with flexible
chains are thermoplastic.
 THERMOPLASTIC AND THERMOSETTING POLYMERS
• These materials are normally fabricated by the simultaneous application of
heat and pressure. Examples of common thermoplastic polymers include
polyethylene, polystyrene, poly(ethylene terephthalate), and poly(vinyl
chloride).
• Thermosetting polymers are network polymers. They become permanently
hard during their formation, and do not soften upon heating. Network
polymers have covalent crosslinks between adjacent molecular chains.
During heat treatments, these bonds anchor the chains together to resist
the vibrational and rotational chain motions at high temperatures. Thus,
the materials do not soften when heated. Crosslinking is usually extensive,
in that 10 to 50% of the chain repeat units are crosslinked. Only heating to
excessive temperatures causes severance of these crosslink bonds and
polymer degradation.
THERMOPLASTIC AND THERMOSETTING POLYMERS
Thermoset polymers are generally harder and stronger than thermoplastics and
have better dimensional stability. Most of the crosslinked and network polymers,
which include vulcanized rubbers, epoxies, and phenolics and some polyester
resins, are thermosetting.
 COPOLYMERS
• Consider a copolymer that is composed of two repeat units. Depending on the
polymerization process and the relative fractions of these repeat unit types, different
sequencing arrangements along the polymer chains are possible. For one, the two
different units are randomly dispersed along the chain in what is termed a random
copolymer. In an alternating copolymer, as the name suggests, the two repeat units
alternate chain positions.
• A block copolymer is one in which identical repeat units are clustered in blocks along the
chain. Finally, homopolymer side branches of one type may be grafted to homopolymer
main chains that graft copolymer are composed of a different repeat unit; such a
material is termed a graft copolymer. When calculating the degree of polymerization for
a copolymer, the value m in Equation is replaced with the average value m determined
from

• In this expression, fj and mj are, respectively, the mole fraction and molecular weight of
repeat unit j in the polymer chain.
Schematic representations of (a) random, (b)
alternating, (c) block, and (d) graft copolymers.
The two different repeat unit types are
designated by blue and red circles. Styrene–
butadiene rubber (SBR) is a common random
copolymer from which automobile tires are
made.
POLYMER CRYSTALLINITY
The crystalline state may exist in polymeric materials. However, since it involves
molecules instead of just atoms or ions, as with metals and ceramics, the atomic
arrangements will be more complex for polymers. We think of polymer crystallinity
as the packing of molecular chains to produce an ordered atomic array.

Crystal structures may be specified in terms of unit cells, which are often quite
complex. The degree of crystallinity may range from completely amorphous to
almost entirely (up to about 95%) crystalline; in contrast, metal specimens are
almost always entirely crystalline, whereas many ceramics are either totally
crystalline or totally noncrystalline.
 Semicrystalline polymers are, in a sense, analogous to two-phase metal alloys,
discussed in subsequent chapters. The density of a crystalline polymer will be greater
than an amorphous one of the same material and molecular weight, since the chains
are more closely packed together for the crystalline structure. The degree of
crystallinity by weight may be determined from accurate density measurements,
according to:

• where ρs is the density of a specimen for which the percent crystallinity is to be

determined, ρa is the density of the totally amorphous polymer, and ρc is the
density of the perfectly crystalline polymer. The values of ρa and ρc must be
measured by other experimental means.
PROBLEMS…