Polymers Engineering University of Technology Dr.

Sihama Essa Salih

Class 3th year Materials Engineering Department Assistant professor

Ch. 5
Effect of Temperature on Thermoplastics
Properties of thermoplastics change depending upon temperature. We need to
know how these changes occur because this can help us (a) better design
components and (b) guide the type of processing techniques that need to be
used. Several critical temperatures and structures, summarized in Figures 1 and 2,
may be observed.
Thermoplastics can be amorphous or crystalline once they cool below the
melting temperature (Figure 1). Most often, engineered thermoplastics have both
amorphous and crystalline regions. The crystallinity in thermoplastics can be
introduced by temperature (slow cooling) or by the application of stress that
can untangle chains (stress-induced crystallization). Similar to dispersion
strengthening of metallic materials, the formation of crystalline regions in an
otherwise amorphous matrix helps
increase the strength of thermoplastics. In typical thermoplastics, bonding
within the chains is covalent, but the long coiled chains are held to one
another by weak van der Waals bonds and by entanglement. When a tensile
stress is applied to the thermoplastic, the weak bonding between the chains
can be overcome, and the chains can rotate and slide relative to one another.
The ease with which the chains slide depends on both temperature and the
polymer structure.

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

Figure 1 The effect of temperature on the structure and behavior of ermoplastics.

Figure 2 The effect of temperature on the modulus of elasticity for an amorphous

thermoplastic. ( Note that Tg and Tm are not fixed. )
Degradation Temperature
At very high temperatures, the covalent bonds between the atoms in the
linear chain may be destroyed, and the polymer may burn or char. In

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

thermoplastics, decomposition occurs in the liquid state; in thermosets, the

decomposition occurs in the solid state. This temperature Td (not shown in Figure
2), is the degradation (or decomposition) temperature. When plastics burn, they
create smoke, which is dangerous. Some materials (such as limestone, talc,
alumina, etc.) added to thermoplastics are thermal or heat stabilizers. They
absorb heat and protect the polymer matrix. Fire retardant additives include
hydrated alumina, antimony compounds, and halogen compounds (e.g.,
MgBr, PCl5). Some additives retard fire by excluding oxygen but generate
dangerous gases and are not appropriate for certain applications.
Exposure to other forms of chemicals or energy (e.g., oxygen, ultraviolet radiation,
and attack by bacteria) also cause a polymer to degrade or age slowly, even at low
temperatures. Carbon black (up to ~ 3%) is one of the commonly used additives
that helps improve the resistance of plastics to ultraviolet degradation.
Liquid Polymers
Thermoplastics usually do not melt at a precise temperature. Instead there is
a range of temperatures over which melting occurs. The approximate melting
ranges of typical polymers are included in Table 1. At or above the melting
temperature Tm, bonding between the twisted and intertwined chains is weak. If a
force is applied, the chains slide past one another, and the polymer flows with
virtually no elastic strain. The strength and modulus of elasticity are nearly
zero, and the polymer is suitable for casting and many forming processes.
Most thermoplastic melts are shear thinning (i.e., their apparent viscosity decreases
within an increase in the steady-state shear rate).
Rubbery and Leathery States

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

Below the melting temperature, the polymer chains are still twisted and
intertwined. These polymers have an amorphous structure. Just below the melting
temperature, the polymer behaves in a rubbery manner.
When stress is applied, both elastic and plastic deformation of the polymer
occurs. When the stress is removed, the elastic deformation is quickly recovered,
but the polymer is permanently deformed due to the movement of the chains.
Large permanent elongations can be achieved, permitting the polymer to be formed
into useful shapes by molding and extrusion.
At lower temperatures, bonding between the chains is stronger, the polymer
becomes stiffer and stronger, and a leathery behavior is observed. Many of the
commercial polymers, including polyethylene, have a useable strength in this
condition.

Glassy State
Below the glass-transition temperature Tg, the linear amorphous polymer becomes
hard, brittle, and glass-like. This is again not a fixed temperature but a range of
temperatures. When the polymer cools below the glass-transition temperature,
certain properties—such as density or modulus of elasticity—change at a different
rate (Figure 3).

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

Figure 3 The relationship between the density and temperature of a polymer

shows the melting and glass-transition temperatures. Note that Tg and Tm are not
fixed; rather, they are ranges of temperatures.

Although glassy polymers have poor ductility and formability, they do

have good strength, stiffness, and creep resistance. A number of important
polymers, including polystyrene and polyvinyl chloride, have glass-transition
temperatures above room temperature (Table 1).
The glass-transition temperature is typically about 0.5 to 0.75 times the
absolute melting temperature Tm. Polymers such as polyethylene, which have no
complicated side groups attached to the carbon backbone, have low glass-transition
temperatures (even below room temperature) compared with polymers such as
polystyrene, which have more complicated side groups.
Many thermoplastics become brittle at lower temperatures. The brittleness of
the polymer used for some of the O-rings ultimately caused the 1986 Challenger
disaster. The lower temperatures that existed during the launch time caused the
embrittlement of the rubber O-rings used for the booster rockets.
TABLE 1 Melting, glass-transition, and processing temperature ranges (°C)
for selected thermoplastics and elastomers

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

Polymer Melting Glass- Processing

Temperature Transition Temperature
Range Temperature Range
Range (Tg)
Addition polymers
Low-density (LD) polyethylene 98-115 -90 to -25 149–232
High-density (HD) polyethylene 130-137 -110 177–260
Polyvinyl chloride 175-212 87
Polypropylene 160–180 -25 to -20 190–288
Polystyrene 240 85-125
Polyacrylonitrile 320 107
Polytetrafluoroethylene (Teflon) 327 -
Polychlorotrifluoroethylene 220 -
Polymethyl methacrylate (acrylic) - 90-105
Acrylonitrile butadiene styrene (ABS) 110- 125 100 177–260
Condensation polymers
Acetal 180 -85 -
6,6-nylon 243-260 49 260-327
Celluloseacetate 230 - -
Polycarbonate 230 149 271-300
Polyester 255 75 -
Polyethylene terephthalate (PET) 212-265 66-80 227-349
Elastomers
Silicone - -123 -
Polybutadiene 120 -90 -
Polychloroprene 80 -50 -
Polyisoprene 30 -73 30 -73 -

Observing and Measuring Crystallinity in Polymers

Many thermoplastics partially crystallize when cooled below the melting
temperature, with the chains becoming closely aligned over appreciable distances.
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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

A sharp increase in the density occurs as the coiled and intertwined chains in
the liquid are rearranged into a more orderly, close-packed structure (Figure
3).
One model describing the arrangement of the chains in a crystalline polymer is
shown in Figure 4. In this folded chain model, the chains loop back on themselves,
with each loop being approximately 100 carbon atoms long. The folded chain
extends in three dimensions, producing thin plates or lamellae.

Figure 4 The folded chain model for crystallinity in polymers, shown in (a) two
dimensions nd (b) three dimensions.

The crystals can take various forms, with the spherulitic shape shown in Figure
5(a) being particularly common. The crystals have a unit cell that describes the
regular packing of the chains. The crystal structure for polyethylene, shown in
Figure 5(b), describes one such unit cell. Crystal structures for several polymers
are listed in Table 2. Some polymers are polymorphic, having more than one
crystal structure.
Even in crystalline polymers, there are always thin regions between the
lamellae, as well as between spherulites, that are amorphous transition zones.

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

Figure 5 (a) Photograph of spherulitic crystals in an amorphous matrix of nylon (*

200). (b) The unit cell of crystalline polyethylene.

The weight percentage of the structure that is crystalline can be calculated from the
density of the polymer:

where ρ is the measured density of the polymer, ρa is the density of amorphous

polymer, and ρc is the density of completely crystalline polymer. Similarly, x-ray
diffraction (XRD) can be used to measure the level of crystallinity and determine
lattice constants for single crystal polymers.

TABLE 2 Crystal structures of several polymers

Polymer Crystal Structure Lattice Parameters (nm)

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

rPolyethylene Orthorhombic a0 = 0.741 b0 = 0.495 c0 = 0.255

Polypropylene Orthorhombic a0 = 1.450 b0 = 0.569 c0 = 0.740
Polyvinyl chloride Orthorhombic a0 = 1.040 b0 = 0.530 c0 = 0.510
Polyisoprene (cis) Orthorhombic a = 1.246 b0 = 0.886 c0 = 0.810

As the side groups get more complex, it becomes harder to crystallize

thermoplastics. For example, polyethylene (H as side group) can be crystallized
more easily than polystyrene (benzene ring as side group). High-density
polyethylene (HDPE) has a higher level of crystallinity and, therefore, a higher
density (0.97 g/cm3) than low-density polyethylene (LDPE), which has a density
of 0.92 g/cm3. The crystallinity and, hence, the density in LDPE is lower, since the
polymer is branched. Thus, branched polymers show lower levels of crystallinity.
A completely crystalline polymer would not display a glass-transition temperature;
however, the amorphous regions in semicrystalline polymers do transform
to a glassy material below the glass-transition temperature (Figure 16-13). Such
polymers as acetal, nylon, HDPE, and polypropylene are referred to as crystalline
even though the level of crystallinity may be moderate. The following examples
show how properties of plastics can be accounted for in different applications.

Example… A new grade of flexible, impact resistant polyethylene for use as a thin film
requires a density of 0.88 to 0.915 g/cm3. Design the polyethylene required to produce these
properties. The density of amorphous polyethylene is about 0.87 g/cm3.

SOLUTION
To produce the required properties and density, we must control the percent
crystallinity of the polyethylene. We can use Equation (1) to determine the
crystallinity that corresponds to the required density range. To do so, however, we

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

must know the density of completely crystalline polyethylene. We can use the data
in Figure 5 and Table 2 to calculate this density if we recognize that there are two
polyethylene repeat units in each unit cell.

(𝟒𝒄)(𝟏𝟐 𝒈/ 𝒎𝒐𝒍)+(𝟖 𝑯)(𝟏 𝒈/𝒎𝒐𝒍)

ρc =
�𝟕.𝟒𝟏 × 𝟏𝟎−𝟖 𝒄𝒎��𝟒.𝟗𝟓×𝟏𝟎−𝟖 𝒄𝒎��𝟐.𝟓𝟓×𝟏𝟎−𝟖 𝒄𝒎�� 𝟔.𝟎𝟐𝟐×𝟏𝟎𝟐𝟑 𝒂𝒕𝒐𝒎𝒔/𝒎𝒐𝒍�

ρc = 0.9942 g/cm3
We know that and that ρc = 0.87 g/cm3 varies from 0.88 to 0.915 g/cm3. The
required crystallinity then varies from
(𝟎.𝟗𝟗𝟒𝟐)(𝟎.𝟖𝟖−𝟎.𝟖𝟕 )
% crystalline =
(𝟎.𝟖𝟖)( 𝟎.𝟗𝟗𝟒𝟐−𝟎.𝟖𝟕 )
× 100 = 9.1

( 𝟎.𝟗𝟗𝟒𝟐)( 𝟎.𝟗𝟏𝟓−𝟎.𝟖𝟕)
% crystalline =
( 𝟎.𝟗𝟏𝟓)(𝟎.𝟗𝟗𝟒𝟐 −𝟎.𝟖𝟕)
× 100 = 39.4

Therefore, we must be able to process the polyethylene to produce a range of

crystallinity between 9.2 and 39.4%.

Q1// The crystalline density of polypropylene is 0.946 g/cm3, and its amorphous density

is 0.855 g/cm3. What is the weight percent of the structure that is crystalline in a polypropylene
that has a density of 0.9 g/cm3?

Q2// The density and associated percent crystallinity for two poly(ethyleneterephthalate)
materials are as follows:
(g/cm3) Crystallinity (%)
1.408 74.3
1.343 31.2

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

(a) Compute the densities of totally crystalline and totally amorphous poly(ethylene
terephthalate). (b) Determine the percent crystallinity of a specimen having a density of 1.382
g/cm3.
Ex.2// Calculate the amount of benzoyl peroxide [(C6H5CO)2O2] initiator required to produce 1
kg of polyethylene with an average molecular weight of 200,000 g>mol. Each
benzoyl peroxide molecule produces two free radicals that are each capable of initiating
a polyethylene chain. Assume that 20% of the initiator actually is effective and that all
termination occurs by the combination mechanism.

SOLUTION
One benzoyl peroxide molecule produces two free radicals that initiate two chains that then
combine to form one polyethylene chain. Thus, there is a 1:1 ratio between benzoyl peroxide
molecules and polyethylene chains. If the initiator were 100% effective, one molecule of benzoyl
peroxide would be required per polyethylene chain.
To determine the amount of benzoyl peroxide required, the number of chains with an average
molecular weight of 200,000 g/mol in 1 kg of polyethylene must be calculated.
The molecular weight of ethylene = (2 C atoms)(12 g/mol) + (4 H atoms)(1 g/mol)
The molecular weight of ethylene = 28 g /mol.
The number of molecules per chain (also known as the degree of polymerization) (n) is given by

𝐚𝐯𝐞𝐫𝐚𝐠𝐞 𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐰𝐞𝐢𝐠𝐡𝐭 𝟐𝟎𝟎,𝟎𝟎𝟎 𝒈/𝒎𝒐𝒍

n= = = 7143 ethylene molecules/chain
𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐦𝐞𝐫 𝟐𝟖 𝒈/𝒎𝒐𝒍
The total number of monomers required to form 1 kg of polyethylene is
�(𝟏𝟎𝟎𝟎𝒈) (𝟔.𝟎𝟐𝟐×𝟏𝟎𝟐𝟑 𝒎𝒐𝒏𝒐𝒎𝒆𝒓𝒔/𝒎𝒐𝒍) �
= 215 × 1023 monomers
𝟐𝟖𝒈/𝒎𝒐𝒍
Thus, the number of polyethylene chains in 1 kg is
𝟐𝟏𝟓× 𝟏𝟎𝟐𝟑 𝒆𝒕𝒉𝒚𝒍𝒆𝒏𝒆 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔
= 3.0 × 1021 chains
𝟕𝟏𝟒𝟑 𝒆𝒕𝒉𝒚𝒍𝒆𝒏𝒆 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔/ 𝒄𝒉𝒂𝒊𝒏
Since the benzoyl peroxide initiator is only 20% effective, 5(3.0 × 1021) = 1.5 × 1022 benzoyl
peroxide molecules are required to initiate 3.0 × 1021 chains.
The molecular weight of benzoyl peroxide is
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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

(14 C atoms)(12 g/mol) + (10 H atoms) (1 g/mol) + (4 O atoms)(16 g /mol) = 242 gmol.
Therefore, the amount of initiator required is
𝟏.𝟓×𝟏𝟎𝟐𝟐 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 ( 𝟐𝟒𝟐 𝒈 /𝒎𝒐𝒍)
= 6.0 g
𝟔.𝟎𝟐𝟐× 𝟏𝟎𝟐𝟑 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔/𝒎
Example 16-3
Ex.3// Nylon was first reported by Wallace Hume Carothers, of du Pont in about 1934.
In 1939, Charles Stine, also from du Pont, reported the discovery of this first synthetic fiber to a
group of 3000 women gathered for the New York World’s Fair. The first application was nylon
stockings. Today nylon is used in hundreds of applications. Prior to nylon, Carothers had
discovered neoprene (an elastomer).

The linear polymer 6,6-nylon is to be produced by combining 1000 g of hexamethylene diamine

with adipic acid. A condensation reaction then produces the polymer. The molecular structures
of the monomers are shown below. The linear nylon chain is produced when a hydrogen atom
from the hexamethylene diamine combines with an OH group from adipic acid to form a water
molecule.

Note that the reaction can continue at both ends of the new molecule; consequently,

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

long chains may form. This polymer is called 6,6-nylon because both monomers contain six
carbon atoms. How many grams of adipic acid are needed, and how much 6,6-nylon is produced,
assuming 100% efficiency?
SOLUTION
The molecular weights of hexamethylene diamine, adipic acid, and water are 116, 146, and 18
g/mol, respectively. The number of moles of hexamethylene diamine is equal to
the number of moles of adipic acid:
1000𝑔 𝑥𝑔
= 8.62 𝑚𝑜𝑙𝑒𝑠 =
116 𝑔/ 𝑚𝑜 146 𝑔/𝑚𝑜𝑙

x = 1259 g of adipic acid required

One water molecule is lost when hexamethylene diamine reacts with adipic acid.
Each time a monomer is added to the chain, one molecule of water is lost. Thus,
when a long chain forms, there are (on average) two water molecules released for
each repeat unit of the chain (each repeat unit being formed from two monomers).
Thus, the number of moles of water lost is 2 (8.62 moles) = 17.24 moles or
17.24 moles H2O (18 g/mol ) = 310g H2O
The total amount of nylon produced is
1000g + 1259g – 310g = 1949g.

Ex.4// Molecular weight data for some polymer are tabulated here. Compute (a) the number
average molecular weight, and (b) the weight-average molecular weight. (c) If it is known that
this material’s degree of polymerization is 477, which one of the polymers
listed in Table 1.1 is this polymer? Why? (d) What the weight-average degree of polymerization

Molecular Weight
Range (g/mol) xi wi
8,000–20,000 0.05 0.02
20,000–32,000 0.15 0.08
32,000–44,000 0.21 0.17
44,000–56,000 0.28 0.29
56,000–68,000 0.18 0.23

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

68,000–80,000 0.10 0.16

80,000–92,000 0.03 0.05

Table 1.1 A Listing of Repeat Units for 10 of the More Common Polymeric Materials

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

SOLUTION
(a) From the tabulated data, we are asked to compute M n, the number-average molecular
weight. This is carried out below.
Molecular wt.
Range Mean Mi xi xiMi
8,000-20,000 14,000 0.05 700
20,000-32,000 26,000 0.15 3900
32,000-44,000 38,000 0.21 7980
44,000-56,000 50,000 0.28 14,000
56,000-68,000 62,000 0.18 11,160
68,000-80,000 74,000 0.10 7400
80,000-92,000 86,000 0.03 2580
_________________________
Mn = ΣxiMi = 47,720 g/mol

(b) From the tabulated data, we are asked to compute M w, the weight- average molecular
weight. This determination is performed as follows:

Molecular wt.
Range Mean Mi wi wiMi

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

8,000-20,000 14,000 0.02 280

20,000-32,000 26,000 0.08 2080
32,000-44,000 38,000 0.17 6460
44,000-56,000 50,000 0.29 14,500
56,000-68,000 62,000 0.23 14,260
68,000-80,000 74,000 0.16 11,840
80,000-92,000 86,000 0.05 4300
_________________________
MW = ΣwiMi = 53,720 g/mol

(c) We are now asked if the number-average degree of polymerization is 477, which of the
polymers in Table 1.1 is this material?

It is necessary to compute m in Equation (1) as

𝑴𝒏
𝒎 = -------------- 1
𝒏𝒏

𝟒𝟕,𝟕𝟐𝟎 𝒈/𝒎𝒐𝒍
𝒎= = 100.04 g/mol
𝟒𝟕𝟕

The mer molecular weights of the polymers listed in Table 1.1 are as follows:
Polyvinyl chloride------------------------- 62.49 g/mol
Polyethylene--------------------------------28.05 g/mol
Polytetrafluoroethylene --------------100.02 g/mol
Polypropylene----------------------------- 42.08 g/mol
Polystyrene---------------------------------104.14 g/mol
Polymethyl methacrylate----------------100.11 g/mol
Phenol-formaldehyde--------------------133.16 g/mol
Nylon 6,6 -------------------------------226.32 g/mol
PET ----------------------------------------192.16 g/mol
Polycarbonate-----------------------------254.27 g/mol
Therefore, polytetrafluoroethylene is the material since its mer molecular weight is losest to
that calculated above.
(d) The weight-average degree of polymerization may be calculated using equation (2), since
MW and m were computed in portions (b) and (c) of this problem. Thus

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

𝑀𝑊
nW = −−−−−−−2
𝑚
𝟓𝟑,𝟕𝟐𝟎 𝒈/𝒎𝒐𝒍
nW = = 537
𝟏𝟎𝟎.𝟎𝟒 𝒈/𝒎𝒐𝒍

Q4/ Is it possible to have a poly(vinyl chloride) homopolymer with the following molecular
weight data, and a degree of polymerization of 1120? Why or why not?
Molecular Weight
Range (g/mol) wi xi
8,000–20,000 0.02 0.05
20,000–32,000 0.08 0.15
32,000–44,000 0.17 0.21
44,000–56,000 0.29 0.28
56,000–68,000 0.23 0.18
68,000–80,000 0.16 0.10
80,000–92,000 0.05 0.03

SOLUTION

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Polymers Engineering University of Technology Dr. Sihama Essa Salih
Class 3th year Materials Engineering Department Assistant professor

This problem asks if it is possible to have a polyvinyl chloride homopolymer with the given
molecular weight data and a number-average degree of polymerization of 1120. The appropriate
data are given below along with a computation of the number-average molecular weight.
Molecular wt.
Range Mean Mi xi xiMi
8,000-20,000 14,000 0.05 700
20,000-32,000 26,000 0.15 3900
32,000-44,000 38,000 0.21 7980
44,000-56,000 50,000 0.28 14,000
56,000-68,000 62,000 0.18 11,160
68,000-80,000 74,000 0.10 7440
80,000-92,000 86,000 0.03 2580
_________________________
MWw = xi Σ Mi = 47, 720 g/mol

For PVC, from Table 1.1, each mer unit has two carbons, three hydrogens, and one chlorine.
Thus,
m = 2(AC) + 3(AH) + (ACl)
m = (2)(12.01 g/mol) + (3)(1.008 g/mol) + (35.45 g/mol) = 62.49 g/mol
Now, we will compute nn from Equation (1) as

𝑴𝒏
𝒏𝒏 = −−−−−𝟏
𝒎

𝟒𝟕, 𝟕𝟐𝟎 𝒈/𝒎𝒐𝒍

𝒏𝒏 = = 𝟕𝟔𝟒
𝟔𝟐. 𝟒𝟗 𝒈/𝒎𝒐𝒍
Thus, such a homopolymer is not possible since the calculated nn is 764 not 1120.

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