POLYMER STRUCTURE • Rotational flexibility is diminished when double
• Most polymeric materials are composed of very chain bonds are present and also when bulky side
large molecular chains with side groups of various
atoms (O, Cl, etc.) or organic groups such as methyl,
Polymer ethyl, or phenyl
Molecules groups.
s • Four different polymer molecular chain structures
• These macromolecules are composed of repeat
units, smaller structural entities,
which are repeated along the chain.
• Repeat units for some of the chemically simple
polymers[polyethylene,polytetrafluoroethylene,poly
The (vinyl chloride), polypropylene, etc.] are presented in
chemistry Table 14.3.
of Polymer
Molecules • A homopolymer is one for which all of the repeat
units are the same type. The chainsfor copolymers
are composed of two or more kinds of repeat units.
• Repeat units are classified according to the
number of active bonds (i.e., functionality):
For bifunctional monomers, a two-dimensional
chainlike structure results from a monomer that has
two active bonds.
Trifunctional monomers have three active bonds,
from which three-dimensionalnetwork structures
form.
• Molecular weights for high polymers may be in
Molecular excess of a million. Because all molecules are not of
Weight the same size, there is a distribution of molecular
weights.
• Molecular weight is often expressed in terms of
number and weight averages; valuesfor these
parameters may be determined using Equations
14.5a and 14.5b, respectively.
• Chain length may also be specified by degree of
polymerization—the number of repeat units per
average molecule (Equation 14.6).
• Molecular entanglements occur when the chains
Molecular
assume twisted, coiled, and kinked shapes or
Shape
contours as a consequence of chain bond rotations.
groups are part of the repeat unit.
Molecular Structure
are possible: linear (Figure 14.7a),branched (Figure
14.7b), crosslinked (Figure 14.7c), and network
(Figure 14.7d).
Molecular Configurations
• For repeat units that have more than one side
atom or groups of atoms bonded to the main chain:
Head-to-head and head-to-tail configurations are
possible.
Differences in spatial arrangements of these side
atoms or groups of atoms lead to isotactic,
syndiotactic, and atactic stereoisomers.
• When a repeat unit contains a double chain bond,
both cis and trans geometrical isomers are possible.
Thermoplastics and Thermosetting Polymers
• With regard to behavior at elevated temperatures,
polymers are classified as either thermoplastic or
thermosetting.
Thermoplastic polymers have linear and branched
structures; they soften when heated and harden
when cooled.
In contrast, thermosetting polymers, once they have
hardened, will not soften upon heating; their
structures are crosslinked and network.
Copolymers
• The copolymers include random (Figure 14.9a),
alternating (Figure 14.9b), block(Figure 14.9c), and
graft (Figure 14.9d) types.
• Repeat units that are employed in copolymer
rubber materials are presented in Table 14.5.
 • When the molecular chains are aligned and packed coefficient and solubility in the polymer (Equation
Polymer
in an ordered atomic arrangement,the condition of 14.10).
Crystallinity
crystallinity is said to exist.
• Permeation flow rates are expressed using a
• Amorphous polymers are also possible wherein the modified form of Fick’s first law (Equation 14.9).
chains are misaligned and disordered.

• In addition to being entirely amorphous, polymers

may also exhibit varying degrees of crystallinity—
that is, crystalline regions are interdispersed within
amorphous areas.

• Crystallinity is facilitated for polymers that are

chemically simple and that have regular and
symmetrical chain structures.

• The percent crystallinity of a semicrystalline

polymer is dependent on its density, as well as the
densities of the totally crystalline and totally
amorphous materials, according to Equation 14.8.

• Crystalline regions (or crystallites) are plate-shape

Polymer and have a chain-folded structure(Figure 14.12)—
Crystals chains within the platelet are aligned and fold back
and forth on themselves, with folds occurring at the
faces.

• Many semicrystalline polymers form spherulites;

each spherulite consists of a collection of ribbon-like
chain-folded lamellar crystallites that radiate
outward from its center.

• Although the point defect concept in polymers is

Defects in different than in metals and ceramics,vacancies,
Polymers interstitial atoms, and impurity atoms/ions and
groups of atoms/ions as interstitials have been
found to exist in crystalline regions.

• Other defects include chain ends, dangling and

loose chains, and dislocations (Figure14.15).

• With regard to diffusion in polymers, small

Diffusion
molecules of foreign substances diffuse between
in
molecular chains by an interstitial-type mechanism
Polymeric
from one void to an adjacent one.
Materials
• Diffusion (or permeation) of gaseous species is
often characterized in terms of the permeability
coefficient, which is the product of the diffusion