Polimer Maddeler Ve Plastikler Giriş Çözüm Kitabı

CHAPTER 14
POLYMER STRUCTURES
PROBLEM SOLUTIONS
Hydrocarbon Molecules
Polymer Molecules
The Chemistry of Polymer Molecules
14.1 On the basis of the structures presented in this chapter, sketch repeat unit structures for the following
polymers: (a) polychlorotrifluoroethylene, and (b) poly(vinyl alcohol).
Solution
The repeat unit structures called for are sketched below.

(a) Polychlorotrifluoroethylene
(b) Poly(vinyl alcohol)
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Molecular Weight
14.2 Compute repeat unit molecular weights for the following: (a) poly(vinyl chloride), (b) poly(ethylene
terephthalate), (c) polycarbonate, and (d) polydimethylsiloxane.
Solution
(a) For poly(vinyl chloride), each repeat unit consists of two carbons, three hydrogens, and one chlorine
(Table 14.3). If AC, AH and ACl represent the atomic weights of carbon, hydrogen, and chlorine, respectively, then
m = 2(AC) + 3(AH) + (ACl)
= (2)(12.01 g/mol) + (3)(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol
(b) For poly(ethylene terephthalate), from Table 14.3, each repeat unit has ten carbons, eight hydrogens,
and four oxygens. Thus,
m = 10(AC) + 8(AH) + 4(AO)
= (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol
(c) For polycarbonate, from Table 14.3, each repeat unit has sixteen carbons, fourteen hydrogens, and
three oxygens. Thus,
m = 16(AC) + 14(AH) + 3(AO)
= (16)(12.01 g/mol) + (14)(1.008 g/mol) + (3)(16.00 g/mol)
= 254.27 g/mol
(d) For polydimethylsiloxane, from Table 14.5, each repeat unit has two carbons, six hydrogens, one
silicon and one oxygen. Thus,
m = 2(AC) + 6(AH) + (ASi) + (AO)
= (2)(12.01 g/mol) + (6)(1.008 g/mol) + (28.09 g/mol) + (16.00 g/mol) = 74.16 g/mol
14.3 The number-average molecular weight of a polypropylene is 1,000,000 g/mol. Compute the degree of
polymerization.
Solution
We are asked to compute the degree of polymerization for polypropylene, given that the number-average
molecular weight is 1,000,000 g/mol. The repeat unit molecular weight of polypropylene is just
m = 3(AC) + 6(AH)
= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol
Now it is possible to compute the degree of polymerization using Equation 14.6 as
M n 1, 000, 000 g/mol

DP = = = 23, 760
m 42.08 g/mol
14.4 (a) Compute the repeat unit molecular weight of polystyrene.
(b) Compute the number-average molecular weight for a polystyrene for which the degree of
polymerization is 25,000.
Solution
(a) The repeat unit molecular weight of polystyrene is called for in this portion of the problem. For
polystyrene, from Table 14.3, each repeat unit has eight carbons and eight hydrogens. Thus,
m = 8(AC) + 8(AH)
= (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol
(b) We are now asked to compute the number-average molecular weight. Since the degree of
polymerization is 25,000, using Equation 14.6
M n = (DP)m = (25, 000)(104.14 g/mol) = 2.60 × 10 6 g/mol
14.5 Below, molecular weight data for a polypropylene material are tabulated. Compute (a) the number-
average molecular weight, (b) the weight-average molecular weight, and (c) the degree of polymerization.
Molecular Weight
Range (g/mol) xi wi
8,000–16,000 0.05 0.02
16,000–24,000 0.16 0.10
24,000–32,000 0.24 0.20
32,000–40,000 0.28 0.30
40,000–48,000 0.20 0.27
48,000–56,000 0.07 0.11
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
8,000-16,000 12,000 0.05 600

16,000-24,000 20,000 0.16 3200
24,000-32,000 28,000 0.24 6720
32,000-40,000 36,000 0.28 10,080
40,000-48,000 44,000 0.20 8800
48,000-56,000 52,000 0.07 3640
____________________________
M n = ∑ xi M i = 33, 040 g/mol
(b) From the tabulated data, we are asked to compute M w , the weight-average molecular weight.
Molecular wt.
Range Mean Mi wi wiMi
8,000-16,000 12,000 0.02 240

16,000-24,000 20,000 0.10 2000
24,000-32,000 28,000 0.20 5600
32,000-40,000 36,000 0.30 10,800
40,000-48,000 44,000 0.27 11,880
48,000-56,000 52,000 0.11 5720
___________________________
M w = ∑ wi M i = 36,240 g/mol
(c) Now we are asked to compute the degree of polymerization, which is possible using Equation 14.6.
For polypropylene, the repeat unit molecular weight is just
m = 3(AC) + 6(AH)
= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol
And
Mn 33,040 g/mol
DP = = = 785
m 42.08 g/mol
14.6 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 710, which one of the polymers listed in Table 14.3 is this polymer? Why?
Molecular Weight
Range g/mol xi wi
15,000–30,000 0.04 0.01
30,000–45,000 0.07 0.04
45,000–60,000 0.16 0.11
60,000–75,000 0.26 0.24
75,000–90,000 0.24 0.27
90,000–105,000 0.12 0.16
105,000–120,000 0.08 0.12
120,000–135,000 0.03 0.05
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.
15,000-30,000 22,500 0.04 900

30,000-45,000 37,500 0.07 2625
45,000-60,000 52,500 0.16 8400
60,000-75,000 67,500 0.26 17,550
75,000-90,000 82,500 0.24 19,800
90,000-105,000 97,500 0.12 11,700
105,000-120,000 112,500 0.08 9000
120,000-135,000 127,500 0.03 3825
_________________________
Mn = ∑ xi M i = 73,800 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
15,000-30,000 22,500 0.01 225

30,000-45,000 37,500 0.04 1500
45,000-60,000 52,500 0.11 5775
60,000-75,000 67,500 0.24 16,200
75,000-90,000 82,500 0.27 22,275
90,000-105,000 97,500 0.16 15,600
105,000-120,000 112,500 0.12 13,500
120,000-135,000 127,500 0.05 6375
_________________________
Mw = ∑ wi M i = 81,450 g/mol
(c) We are now asked if the degree of polymerization is 710, which of the polymers in Table 14.3 is this
material? It is necessary to compute m in Equation 14.6 as
Mn 73,800 g/mol
m = = = 103.94 g/mol
DP 710
The repeat unit molecular weights of the polymers listed in Table 14.3 are as follows:
Polyethylene--28.05 g/mol
Poly(vinyl chloride)--62.49 g/mol
Polytetrafluoroethylene--100.02 g/mol
Polypropylene--42.08 g/mol
Polystyrene--104.14 g/mol
Poly(methyl 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, polystyrene is the material since its repeat unit molecular weight is closest to that calculated above.
14.7 Is it possible to have a poly(methyl methacrylate) homopolymer with the following molecular weight
data and a of polymerization of 527? 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
This problem asks if it is possible to have a poly(methyl methacrylate) homopolymer with the given
molecular weight data and a degree of polymerization of 527. The appropriate data are given below along with a
computation of the number-average molecular weight.
Molecular wt.
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 = ∑ xi M i = 47, 720 g/mol
For PMMA, from Table 14.3, each repeat unit has five carbons, eight hydrogens, and two oxygens. Thus,
m = 5(AC) + 8(AH) + 2(AO)
= (5)(12.01 g/mol) + (8)(1.008 g/mol) + (2)(16.00 g/mol) = 100.11 g/mol
Now, we will compute the degree of polymerization using Equation 14.6 as
Mn 47, 720 g/mol

DP = = = 477
m 100.11 g/mol
Thus, such a homopolymer is not possible since the calculated degree of polymerization is 477 (and not 527).
14.8 High-density polyethylene may be chlorinated by inducing the random substitution of chlorine atoms
for hydrogen.
(a) Determine the concentration of Cl (in wt%) that must be added if this substitution occurs for 5% of all
the original hydrogen atoms.
(b) In what ways does this chlorinated polyethylene differ from poly(vinyl chloride)?
Solution
(a) For chlorinated polyethylene, we are asked to determine the weight percent of chlorine added for 5%
Cl substitution of all original hydrogen atoms. Consider 50 carbon atoms; there are 100 possible side-bonding
sites. Ninety-five are occupied by hydrogen and five are occupied by Cl. Thus, the mass of these 50 carbon atoms,
mC, is just
mC = 50(AC) = (50)(12.01 g/mol) = 600.5 g
Likewise, for hydrogen and chlorine,
mH = 95(AH) = (95)(1.008 g/mol) = 95.76 g
mCl = 5(ACl) = (5)(35.45 g/mol) = 177.25 g
Thus, the concentration of chlorine, CCl, is determined using a modified form of Equation 4.3 as
mCl
CCl = x 100
mC + mH + mCl
177.25 g
= × 100 = 20.3 wt%
600.5 g + 95.76 g + 177.25 g
(b) Chlorinated polyethylene differs from poly(vinyl chloride), in that, for PVC, (1) 25% of the side-
bonding sites are substituted with Cl, and (2) the substitution is probably much less random.
Molecular Shape
14.9 For a linear polymer molecule, the total chain length L depends on the bond length between chain
atoms d, the total number of bonds in the molecule N, and the angle between adjacent backbone chain atoms θ, as
follows:
θ 
L = Nd sin   (14.11)
2
Furthermore, the average end-to-end distance for a series of polymer molecules r in Figure 14.6 is equal to
r = d N (14.12)
A linear polytetrafluoroethylene has a number-average molecular weight of 500,000 g/mol; compute average
values of L and r for this material.
Solution
This problem first of all asks for us to calculate, using Equation 14.11, the average total chain length, L, for
a linear polytetrafluoroethylene polymer having a number-average molecular weight of 500,000 g/mol. It is
necessary to calculate the degree of polymerization, DP, using Equation 14.6. For polytetrafluoroethylene, from
Table 14.3, each repeat unit has two carbons and four flourines. Thus,
m = 2(AC) + 4(AF)
= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol
and
Mn 500, 000 g/mol
DP = = = 5000
m 100.02 g/mol
which is the number of repeat units along an average chain. Since there are two carbon atoms per repeat unit, there
are two C—C chain bonds per repeat unit, which means that the total number of chain bonds in the molecule, N, is
just (2)(5000) = 10,000 bonds. Furthermore, assume that for single carbon-carbon bonds, d = 0.154 nm and θ =
109° (Section 14.4); therefore, from Equation 14.11
θ 
L = Nd sin  
2
  109° 
= (10,000)(0.154 nm) sin   = 1254 nm
  2 
It is now possible to calculate the average chain end-to-end distance, r, using Equation 14.12 as
r = d N = (0.154 nm) 10,000 = 15.4 nm
14.10 Using the definitions for total chain molecule length, L (Equation 14.11) and average chain end-to-
end distance r (Equation 14.12), for a linear polyethylene determine:
(a) the number-average molecular weight for L = 2500 nm;
(b) the number-average molecular weight for r = 20 nm.
Solution
(a) This portion of the problem asks for us to calculate the number-average molecular weight for a linear
polyethylene for which L in Equation 14.11 is 2500 nm. It is first necessary to compute the value of N using this
equation, where, for the C—C chain bond, d = 0.154 nm, and θ = 109°. Thus
L
N =
θ 
d sin  
2 
2500 nm
= = 19,940
 109° 
(0.154 nm) sin  
 2 
Since there are two C—C bonds per polyethylene repeat unit, there is an average of N/2 or 19,940/2 = 9970 repeat
units per chain, which is also the degree of polymerization, DP. In order to compute the value of M n using
Equation 14.6, we must first determine m for polyethylene. Each polyethylene repeat unit consists of two carbon
and four hydrogen atoms, thus
m = 2(AC) + 4(AH)
= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol
Therefore
M n = (DP)m = (9970)(28.05 g/mol) = 280,000 g/mol
(b) Next, we are to determine the number-average molecular weight for r = 20 nm. Solving for N from
Equation 14.12 leads to
r2 (20 nm) 2
N = = = 16,900
d2 (0.154 nm) 2
which is the total number of bonds per average molecule. Since there are two C—C bonds per repeat unit, then DP
= N/2 = 16,900/2 = 8450. Now, from Equation 14.6
M n = (DP)m = (8450)(28.05 g/mol) = 237,000 g/mol
Molecular Configurations
14.11 Sketch portions of a linear polystyrene molecule that are (a) syndiotactic, (b) atactic, and (c)
isotactic. Use two-dimensional schematics per footnote 8 of this chapter.
Solution
We are asked to sketch portions of a linear polystyrene molecule for different configurations (using two-
dimensional schematic sketches).
(a) Syndiotactic polystyrene
(b) Atactic polystyrene
(c) Isotactic polystyrene
14.12 Sketch cis and trans structures for (a) butadiene, and (b) chloroprene. Use two-dimensional
schematics per footnote 11 of this chapter.
Solution
This problem asks for us to sketch cis and trans structures for butadiene and chloroprene.
(a) The structure for cis polybutadiene (Table 14.5) is
The structure of trans butadiene is
(b) The structure of cis chloroprene (Table 14.5) is
The structure of trans chloroprene is
Thermoplastic and Thermosetting Polymers
14.13 Make comparisons of thermoplastic and thermosetting polymers (a) on the basis of mechanical
characteristics upon heating, and (b) according to possible molecular structures.
Solution
(a) Thermoplastic polymers soften when heated and harden when cooled, whereas thermosetting polymers,
harden upon heating, while further heating will not lead to softening.
(b) Thermoplastic polymers have linear and branched structures, while for thermosetting polymers, the
structures will normally be network or crosslinked.
14.14 (a) Is it possible to grind up and reuse phenol-formaldehyde? Why or why not?
(b) Is it possible to grind up and reuse polypropylene? Why or why not?
Solution
(a) It is not possible to grind up and reuse phenol-formaldehyde because it is a network thermoset polymer
and, therefore, is not amenable to remolding.
(b) Yes, it is possible to grind up and reuse polypropylene since it is a thermoplastic polymer, will soften
when reheated, and, thus, may be remolded.
Copolymers
14.15 Sketch the repeat structure for each of the following alternating copolymers: (a) poly(butadiene-
chloroprene), (b) poly(styrene-methyl methacrylate), and (c) poly(acrylonitrile-vinyl chloride).
Solution
This problem asks for sketches of the repeat unit structures for several alternating copolymers.
(a) For poly(butadiene-chloroprene)
(b) For poly(styrene-methyl methacrylate)
(c) For poly(acrylonitrile-vinyl chloride)
14.16 The number-average molecular weight of a poly(styrene-butadiene) alternating copolymer is
1,350,000 g/mol; determine the average number of styrene and butadiene repeat units per molecule.
Solution
Since it is an alternating copolymer, the number of both types of repeat units will be the same. Therefore,
consider them as a single repeat unit, and determine the number-average degree of polymerization. For the styrene
repeat unit, there are eight carbon atoms and eight hydrogen atoms, while the butadiene repeat consists of four
carbon atoms and six hydrogen atoms. Therefore, the styrene-butadiene combined repeat unit weight is just
m = 12(AC) + 14(AH)
= (12)(12.01 g/mol) + (14)(1.008 g/mol) = 158.23 g/mol
From Equation 14.6, the degree of polymerization is just
Mn 1,350,000 g/mol
DP = = = 8530
m 158.23 g/mol
Thus, there is an average of 8530 of both repeat unit types per molecule.
14.17 Calculate the number-average molecular weight of a random nitrile rubber [poly(acrylonitrile-
butadiene) copolymer] in which the fraction of butadiene repeat units is 0.30; assume that this concentration
corresponds to a degree of polymerization of 2000.
Solution
This problem asks for us to calculate the number-average molecular weight of a random nitrile rubber
copolymer. For the acrylonitrile repeat unit there are three carbon, one nitrogen, and three hydrogen atoms. Thus,
its repeat unit molecular weight is
mAc = 3(AC) + (AN) + 3(AH)
= (3)(12.01 g/mol) + 14.01 g/mol + (3)(1.008 g/mol) = 53.06 g/mol
The butadiene repeat unit is composed of four carbon and six hydrogen atoms. Thus, its repeat unit molecular
weight is
mBu = 4(AC) + 6(AH)
= (4)(12.01 g/mol) + (6)(1.008 g/mol) = 54.09 g/mol
From Equation 14.7, the average repeat unit molecular weight is just
m = f Ac mAc + f Bu mBu
= (0.70)(53.06 g/mol) + (0.30)(54.09 g/mol) = 53.37 g/mol
Since DP = 2000 (as stated in the problem), M n may be computed using Equation 14.6 as
M n = m (DP) = (53.37 g/mol)(2000) = 106,740 g/mol
14.18 An alternating copolymer is known to have a number-average molecular weight of 250,000 g/mol
and a degree of polymerization of 3420. If one of the repeat units is styrene, which of ethylene, propylene,
tetrafluoroethylene, and vinyl chloride is the other repeat unit? Why?
Solution
For an alternating copolymer which has a number-average molecular weight of 250,000 g/mol and a degree
of polymerization of 3420, we are to determine one of the repeat unit types if the other is styrene. It is first
necessary to calculate m using Equation 14.6 as
Mn 250,000 g/mol
m = = = 73.10 g/mol
DP 3420
Since this is an alternating copolymer we know that chain fraction of each repeat unit type is 0.5; that is fs = fx =
0.5, fs and fx being, respectively, the chain fractions of the styrene and unknown repeat units. Also, the repeat unit
molecular weight for styrene is
ms = 8(AC) + 8(AH)
= 8(12.01 g/mol) + 8(1.008 g/mol) = 104.14 g/mol
Now, using Equation 14.7, it is possible to calculate the repeat unit weight of the unknown repeat unit type, mx.
Thus
m − f s ms
mx =
fx
73.10 g/mol - (0.5)(104.14 g/mol)

= = 42.06 g/mol
0.5
Finally, it is necessary to calculate the repeat unit molecular weights for each of the possible other repeat
unit types. These are calculated below:
methylene = 2(AC) + 4(AH) = 2(12.01 g/mol) + 4(1.008 g/mol) = 28.05 g/mol

mpropylene = 3(AC) + 6(AH) = 3(12.01 g/mol) + 6(1.008 g/mol) = 42.08 g/mol
mTFE = 2(AC) + 4(AF) = 2(12.01 g/mol) + 4(19.00 g/mol) = 100.02 g/mol
mVC = 2(AC) + 3(AH) + (ACl) = 2(12.01 g/mol) + 3(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol
Therefore, propylene is the other repeat unit type since its m value is almost the same as the calculated mx.
14.19 (a) Determine the ratio of butadiene to styrene repeat units in a copolymer having a number-
average molecular weight of 350,000 g/mol and degree of polymerization of 4425.
(b) Which type(s) of copolymer(s) will this copolymer be, considering the following possibilities: random,
alternating, graft, and block? Why?
Solution
(a) This portion of the problem asks us to determine the ratio of butadiene to styrene repeat units in a
copolymer having a weight-average molecular weight of 350,000 g/mol and a degree of polymerization of 4425. It
first becomes necessary to calculate the average repeat unit molecular weight of the copolymer, m , using Equation
14.6 as
Mn 350,000 g/mol
m = = = 79.10 g/mol
DP 4425
If we designate fb as the chain fraction of butadiene repeat units, since the copolymer consists of only two repeat
unit types, the chain fraction of styrene repeat units fs is just 1 – fb. Now, Equation 14.7 for this copolymer may be
written in the form
m = f b mb + f s ms = f b mb + (1 − f b )ms
in which mb and ms are the repeat unit molecular weights for butadiene and styrene, respectively. These values are
calculated as follows:
mb = 4(AC) + 6(AH) = 4(12.01 g/mol) + 6(1.008 g/mol) = 54.09 g/mol
ms = 8(AC) + 8(AH) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.14 g/mol
Solving for fb in the above expression yields
m − ms 79.10 g/mol − 104.14 g/mol

fb = = = 0.50
mb − m s 54.09 g/mol − 104.14 g/mol
Furthermore, fs = 1 – fb = 1 – 0.50 = 0.50; or the ratio is just
fb 0.50
= = 1.0
fs 0.50
(b) Of the possible copolymers, the only one for which there is a restriction on the ratio of repeat unit types
is alternating; the ratio must be 1:1. Therefore, on the basis of the result in part (a), the possibilities for this
copolymer are not only alternating, but also random, graft, and block.
14.20 Crosslinked copolymers consisting of 60 wt% ethylene and 40 wt% propylene may have elastic
properties similar to those for natural rubber. For a copolymer of this composition, determine the fraction of both
repeat unit types.
Solution
For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine the
fraction of both repeat unit types.
In 100 g of this material, there are 60 g of ethylene and 40 g of propylene. The ethylene (C2H4) molecular
weight is
m(ethylene) = 2(AC) + 4(AH)
= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol
The propylene (C3H6) molecular weight is
m(propylene) = 3(AC) + 6(AH)
= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol
Therefore, in 100 g of this material, there are
60 g
= 2.14 mol of ethylene
28.05 g/mol
and
40 g
= 0.95 mol of propylene
42.08 g/mol
Thus, the fraction of the ethylene repeat unit, f(ethylene), is just
2.14 mol
f (ethylene) = = 0.69
2.14 mol + 0.95 mol
Likewise,
0.95 mol
f (propylene) = = 0.31
2.14 mol + 0.95 mol
14.21 A random poly(isobutylene-isoprene) copolymer has a number-average molecular weight of
200,000 g/mol and a degree of polymerization of 3000. Compute the fraction of isobutylene and isoprene repeat
units in this copolymer.
Solution
For a random poly(isobutylene-isoprene) copolymer in which M n = 200,000 g/mol and DP = 3000, we are
asked to compute the fractions of isobutylene and isoprene repeat units.

From Table 14.5, the isobutylene repeat unit has four carbon and eight hydrogen atoms. Thus,
mib = (4)(12.01 g/mol) + (8)(1.008 g/mol) = 56.10 g/mol
Also, from Table 14.5, the isoprene repeat unit has five carbon and eight hydrogen atoms, and
mip = (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol
From Equation 14.7
m = f ib mib + f ip mip
Now, let x = fib, such that
m = 56.10x + (68.11)(1 − x)
since fib + fip = 1. Also, from Equation 14.6
Mn
DP =
m
Or
200,000 g/mol
3000 =
[56.10 x + 68.11(1 − x)] g/mol
Solving for x leads to x = fib = f(isobutylene) = 0.12. Also,
f(isoprene) = 1 – x = 1 – 0.12 = 0.88
Polymer Crystallinity
14.22 Explain briefly why the tendency of a polymer to crystallize decreases with increasing molecular
weight.
Solution
The tendency of a polymer to crystallize decreases with increasing molecular weight because as the chains
become longer it is more difficult for all regions along adjacent chains to align so as to produce the ordered atomic
array.
14.23 For each of the following pairs of polymers, do the following: (1) state whether or not it is possible
to determine whether one polymer is more likely to crystallize than the other; (2) if it is possible, note which is the
more likely and then cite reason(s) for your choice; and (3) if it is not possible to decide, then state why.
(a) Linear and syndiotactic poly(vinyl chloride); linear and isotactic polystyrene.
(b) Network phenol-formaldehyde; linear and heavily crosslinked cis-isoprene.
(c) Linear polyethylene; lightly branched isotactic polypropylene.
(d) Alternating poly(styrene-ethylene) copolymer; random poly(vinyl chloride-tetrafluoroethylene)
copolymer.
Solution
(a) Yes, for these two polymers it is possible to decide. The linear and syndiotactic poly(vinyl chloride) is
more likely to crystallize; the phenyl side-group for polystyrene is bulkier than the Cl side-group for poly(vinyl
chloride). Syndiotactic and isotactic isomers are equally likely to crystallize.
(b) No, it is not possible to decide for these two polymers. Both heavily crosslinked and network polymers
are not likely to crystallize.
(c) Yes, it is possible to decide for these two polymers. The linear polyethylene is more likely to
crystallize. The repeat unit structure for polypropylene is chemically more complicated than is the repeat unit
structure for polyethylene. Furthermore, branched structures are less likely to crystallize than are linear structures.
(d) Yes, it is possible to decide for these two copolymers. The alternating poly(styrene-ethylene)
copolymer is more likely to crystallize. Alternating copolymers crystallize more easily than do random copolymers.
14.24 The density of totally crystalline polypropylene at room temperature is 0.946 g/cm3. Also, at room
temperature the unit cell for this material is monoclinic with lattice parameters
a = 0.666 nm α = 90°
b = 2.078 nm β = 99.62°
c = 0.650 nm γ = 90°
If the volume of a monoclinic unit cell, V mono , is a function of these lattice parameters as
V mono = abc sin β
determine the number of repeat units per unit cell.
Solution
For this problem we are given the density of polypropylene (0.946 g/cm3), an expression for the volume of
its unit cell, and the lattice parameters, and are asked to determine the number of repeat units per unit cell. This
computation necessitates the use of Equation 3.5, in which we solve for n. Before this can be carried out we must
first calculate VC, the unit cell volume, and A the repeat unit molecular weight. For VC
VC = abc sin β
= (0.666 nm)(2.078 nm)(0.650 nm) sin (99.62°)
= 0.8869 nm3 = 8.869 × 10-22 cm3
The repeat unit for polypropylene is shown in Table 14.3, from which the value of A may be determined as follows:
A = 3(AC) + 6(AH)
= 3(12.01 g/mol) + 6(1.008 g/mol)
= 42.08 g/mol
Finally, solving for n from Equation 3.5 leads to
ρVC N A
n =
A
(0.946 g/cm3)( 8.869 × 10 -22 cm3/unit cell)( 6.022 × 10 23 repeat units/mol)

=
42.08 g/mol
= 12.0 repeat unit/unit cell
14.25 The density and associated percent crystallinity for two polytetrafluoroethylene materials are as
follows:
ρ (g/cm3) kristalleşme (%)
2.144 51.3
2.215 74.2
(a) Compute the densities of totally crystalline and totally amorphous polytetrafluoroethylene.
(b) Determine the percent crystallinity of a specimen having a density of 2.26 g/cm3.
Solution
(a) We are asked to compute the densities of totally crystalline and totally amorphous
% crystallinity
polytetrafluoroethylene (ρc and ρa from Equation 14.8). From Equation 14.8 let C = , such that
100
ρc (ρ s − ρa )
C =
ρ s (ρc − ρa )
Rearrangement of this expression leads to
ρc (C ρ s − ρ s ) + ρcρa − Cρ s ρa = 0
in which ρc and ρa are the variables for which solutions are to be found. Since two values of ρs and C are specified
in the problem statement, two equations may be constructed as follows:
ρc (C1 ρ s1 − ρ s1 ) + ρcρa − C1 ρ s1 ρa = 0
ρc (C 2 ρ s2 − ρ s2 ) + ρcρa − C 2 ρ s2 ρa = 0
In which ρs1 = 2.144 g/cm3, ρs2 = 2.215 g/cm3, C1 = 0.513, and C2 = 0.742. Solving the above two equations for
ρa and ρc leads to
ρ s1 ρ s2 (C1 − C 2 )
ρa =
C1 ρ s1 − C 2 ρ s2
(2.144 g/cm3)( 2.215 g/cm3)(0.513 − 0.742)
= = 2.000 g/cm 3
(0.513) (2.144 g/cm 3) − (0.742) ( 2.215 g/cm3)
And
ρ s1 ρ s2 (C 2 − C1)
ρc =
ρ s2 (C 2 − 1) − ρ s1 (C1 − 1)
(2.144 g/cm3)( 2.215 g/cm3 )(0.742 − 0.513)

= = 2.301 g/cm 3
(2.215 g/cm3 )(0.742 − 1) − (2.144 g/cm3 )(0.513 − 1)
(b) Now we are to determine the % crystallinity for ρs = 2.26 g/cm3. Again, using Equation 14.8
ρ c (ρ s − ρ a )
% crystallinity = × 100
ρ s (ρ c − ρ a )
(2.301 g/cm3)( 2.260 g/cm3 − 2.000 g/cm3 )

= × 100
(2.260 g/cm3)( 2.301 g/cm3 − 2.000 g/cm 3)
= 87.9%
14.26 The density and associated percent crystallinity for two nylon 6,6 materials are as follows:
ρ (g/cm3) crystallinity (%)

1.188 67.3
1.152 43.7
(a) Compute the densities of totally crystalline and totally amorphous nylon 6,6.
(b) Determine the density of a specimen having 55.4% crystallinity.
Solution
(a) We are asked to compute the densities of totally crystalline and totally amorphous nylon 6,6 (ρc and ρa
% crystallinity
from Equation 14.8). From Equation 14.8 let C = , such that
100
ρc (ρ s − ρa )
C =
ρ s (ρc − ρa )
Rearrangement of this expression leads to
ρc (C ρ s − ρ s ) + ρcρa − C ρ sρa = 0
in which ρc and ρa are the variables for which solutions are to be found. Since two values of ρs and C are specified
in the problem, two equations may be constructed as follows:
ρ c (C1 ρ s1 − ρ s1) + ρ cρ a − C1ρ s1ρ a = 0
ρc (C 2 ρ s2 − ρ s2 ) + ρcρa − C 2ρ s2ρa = 0
In which ρs1 = 1.188 g/cm3, ρs2 = 1.152 g/cm3, C1 = 0.673, and C2 = 0.437. Solving the above two equations for
ρa and ρc leads to
ρ s1 ρ s2 (C1 − C 2 )
ρa =
C1 ρ s1 − C 2 ρ s2
(1.188 g/cm 3)(1.152 g/cm 3) (0.673 − 0.437)
= = 1.091 g/cm3
(0.673) (1.188 g/cm 3) − (0.437) (1.152 g/cm3 )
And
ρ s1 ρ s2 (C 2 − C1 )
ρc =
ρ s2 (C 2 − 1) − ρ s1(C1 − 1)
g/cm 3)(1.152 g/cm 3) (0.437 − 0.673)

(1.188
= = 1.242 g/cm3
(1.152 g/cm3) (0.437 − 1) − (1.188 g/cm3) (0.673− 1)
(b) Now we are asked to determine the density of a specimen having 55.4% crystallinity. Solving for ρs
from Equation 14.8 and substitution for ρa and ρc which were computed in part (a) yields
− ρc ρa
ρs =
C (ρc − ρa ) − ρc
− (1.242 g/cm3)(1.091 g/cm3 )

=
(0.554) (1.242 g/cm3 − 1.091 g/cm3 ) − 1.242 g/cm3
= 1.170 g/cm3
Diffusion in Polymeric Materials
14.27 Consider the diffusion of water vapor through a polypropylene (PP) sheet 2 mm thick. The
pressures of H2O at the two faces are 1 kPa and 10 kPa, which are maintained constant. Assuming conditions of
steady state, what is the diffusion flux [in [(cm3 STP)/cm2-s] at 298 K?
Solution
This is a permeability problem in which we are asked to compute the diffusion flux of water vapor through
a 2-mm thick sheet of polypropylene. In order to solve this problem it is necessary to employ Equation 14.9. The
permeability coefficient of H2O through PP is given in Table 14.6 as 38 × 10-13 (cm3 STP)-cm/cm2-s-Pa. Thus,
from Equation 14.9
∆P P −P
J = PM = PM 2 1
∆x ∆x
and taking P1 = 1 kPa (1,000 Pa) and P2 = 10 kPa (10,000 Pa) we get
 (cm3 STP)(cm)   10,000 Pa − 1,000 Pa 

=  38 × 10 -13  
 cm2 - s - Pa   0.2 cm 
(cm3 STP)
= 1.71 × 10 -7
cm2 - s
14.28 Argon diffuses through a high density polyethylene (HDPE) sheet 40 mm thick at a rate of 4.0 × 10–7
(cm3 STP)/cm2-s at 325 K. The pressures of argon at the two faces are 5000 kPa and 1500 kPa, which are
maintained constant. Assuming conditions of steady state, what is the permeability coefficient at 325 K?
Solution
This problem asks us to compute the permeability coefficient for argon through high density polyethylene
at 325 K given a steady-state permeability situation. It is necessary for us to Equation 14.9 in order to solve this
problem. Rearranging this expression and solving for the permeability coefficient gives
J ∆x J ∆x
PM = =
∆P P2 − P1
Taking P1 = 1500 kPa (1,500,000 Pa) and P2 = 5000 kPa (5,000,000 Pa), the permeability coefficient of Ar through
HDPE is equal to
 (cm3 STP) 
 4.0 × 10 -7 (4 cm)
 cm2 - s 
PM =
(5,000,000 Pa - 1,500,000 Pa)
(cm3 STP)(cm)
= 4.57 × 10 -13
cm2 - s - Pa
14.29 The permeability coefficient of a type of small gas molecule in a polymer is dependent on absolute
temperature according to the following equation:
 Qp 
PM = PM 0 exp − 
 RT 
where PM 0 and Q p are constants for a given gas-polymer pair. Consider the diffusion of hydrogen through a
poly(dimethyl siloxane) (PDMSO) sheet 20 mm thick. The hydrogen pressures at the two faces are 10 kPa and 1
kPa, which are maintained constant. Compute the diffusion flux [in (cm3 STP)/cm2 –s] at 350 K. For this diffusion
system
PM 0 = 1.45 × 10 −8 (cm 3 STP)(cm)/cm 2 - s - Pa
Qp = 13.7 kJ/mol
Also, assume a condition of steady state diffusion
Solution
This problem asks that we compute the diffusion flux at 350 K for hydrogen in poly(dimethyl siloxane)
(PDMSO). It is first necessary to compute the value of the permeability coefficient at 350 K. The temperature
dependence of PM is given in the problem statement, as follows:
 Q 
p
PM = PM exp − 

0  RT 
And, incorporating values provided for the constants PM and Qp, we get
0
 (cm3 STP)(cm)   13,700 J/mol 

PM = 1.45 × 10 -8  exp − 
 2
cm - s - Pa   (8.31 J/mol- K)(350 K) 
(cm3 STP)(cm)
= 1.31 × 10−10
cm2 - s - Pa
And, using Equation 14.9, the diffusion flux is equal to
∆P P −P
J = PM = PM 2 1
∆x ∆x
(cm3 STP)(cm)  10,000 Pa - 1,000 Pa 

= 1.31 × 10 -10  
cm2 - s - Pa  2.0 cm 
(cm3 STP)
= 5.90 × 10 -7
cm2 - s
CHAPTER 15
CHARACTERISTICS, APPLICATIONS, AND PROCESSING OF POLYMERS
PROBLEM SOLUTIONS
Stress-Strain Behavior
15.1 From the stress–strain data for poly(methyl methacrylate) shown in Figure 15.3, determine the
modulus of elasticity and tensile strength at room temperature [20°C (68°F)], and compare these values with those
given in Table 15.1.
Solution
From Figure 15.3, the elastic modulus is the slope in the elastic linear region of the 20°C curve, which is
∆ (stress) 30 MPa − 0 MPa

E = = = 3.3 GPa (483,000 psi)
∆ (strain) 9 × 10−3 − 0
The value range cited in Table 15.1 is 2.24 to 3.24 GPa (325,000 to 470,000 psi). Thus, the plotted value is a little
on the high side.
The tensile strength corresponds to the stress at which the curve ends, which is 52 MPa (7500 psi). This
value lies within the range cited in Table 15.1—48.3 to 72.4 MPa (7000 to 10,500 psi).
15.2 Compute the elastic moduli for the following polymers, whose stress-strain behaviors may be
observed in the “Tensile Tests” module of Virtual Materials Science and Engineering (VMSE): (a) high-density
polyethylene, (b) nylon, and (c) phenol-formaldehyde (bakelite). How do these values compare with those presented
in Table 15.1 for the same polymers?
Solution
The elastic modulus is the slope in the linear elastic region (Equation 6.10) as
∆σ σ − σ1
E = = 2
∆ε ε2 − ε1
Since all the stress-strain curves pass through the origin, we make take σ1 = 0 and ε1 = 0. Determinations of σ2 and
ε2 are possible by moving the cursor to some arbitrary point in the linear region of the curve and then reading
corresponding values in the “Stress” and “Strain” windows that are located below the plot.
(a) For high-density polyethylene, we selected σ2 = 6.0 MPa with its corresponding ε2 = 0.0152.
Therefore,
σ 2 − σ1 6.0 MPa − 0 MPa

E = = = 395 MPa = 0.395 GPa
ε2 − ε1 0.0152 − 0
The elastic modulus (average) for high-density polyethylene given in Table 15.1 is 1.08 GPa, which is
significantly higher than this value.
(b) For nylon, we selected σ2 = 24.3 MPa with its corresponding ε2 = 0.0085. Therefore,
σ 2 − σ1 24.3 MPa − 0 MPa

E = = = 2860 MPa = 2.86 GPa
ε2 − ε1 0.0085 − 0
The elastic modulus range for nylon 6,6 given in Table 15.1 is 1.58 GPa to 3.80 GPa; therefore, the value
for the VMSE nylon lies within this range.
(c) For phenol-formaldehyde (bakelite), we selected σ2 = 33.0 MPa with its corresponding ε2 = 0.0068.
Therefore,
σ 2 − σ1 33.0 MPa − 0 MPa

E = = = 4850 MPa = 4.85 GPa
ε2 − ε1 0.0068 − 0
The elastic modulus range for the phenol-formaldehyde given in Table 15.1 is 2.76 GPa to 4.83 GPa;
therefore, this value for the VMSE phenol-formaldehyde lies just above the maximum value for this range.
15.3 For the nylon polymer, whose stress strain behavior may be observed in the “Tensile Tests” module
of Virtual Materials Science and Engineering (VMSE), determine the following:
(a) the yield strength, and
(b) the approximate ductility, in percent elongation.
How do these values compare with those for the nylon material presented in Table 15.1?
Solution
(a) The yield strength corresponds to the first maximum (just beyond the initial linear-elastic region) of the
stress-strain curve. This reading in the stress window located below the plot as the curser point is dragged along the
stress-strain curve is 84 MPa.
(b) The approximate percent elongation corresponds to the strain at fracture multiplied by 100 (i.e.,
44.5%) minus the maximum elastic strain (i.e., value of strain at which the linearity of the curve ends multiplied by
100—in this case about 4%); this gives a value of about 40%EL.
For nylon 6,6, the range of values of yield strength presented in Table 15.1 is 44.8 MPa to 82.8 MPa;
therefore, the value for the VMSE nylon lies slightly above the upper value. The ductility range for nylon 6,6 is
15%EL to 300%EL; therefore, our value (40%EL) lies within this range.
15.4 For the phenol-formaldehyde (Bakelite) polymer, whose stress strain behavior may be observed in
the “Tensile Tests” module of Virtual Materials Science and Engineering (VMSE), determine the following:
(a) the tensile strength, and
(b) the approximate ductility, in percent elongation.
How do these values compare with those for the phenol-formaldehyde material presented in Table 15.1?
Solution
(a) The tensile strength corresponds to the stress at which fracture occurs. This reading in the stress
window located below the plot as the curser point is dragged along the stress-strain curve is 52 MPa.
(b) The approximate percent elongation corresponds to the strain at fracture multiplied by 100 (i.e.,
1.29%) minus the maximum elastic strain (i.e., value of strain at which the linearity of the curve ends multiplied by
100—in this case about 1%); this gives a value of about 0.3%EL.
For phenol-formaldehyde, the range of values of tensile strength presented in Table 15.1 is 34.5 MPa to
62.1 MPa; therefore, the value for the VMSE material (52 MPa) lies within this range. The ductility range for
phenol-formaldehyde is 1.5%EL to 2.0%EL; therefore, our value (0.3%EL) lies below the lower limit.
Viscoelastic Deformation
15.5 In your own words, briefly describe the phenomenon of viscoelasticity.
The explanation of viscoelasticity is given in Section 15.4.
15.6 For some viscoelastic polymers that are subjected to stress relaxation tests, the stress decays with
time according to
 t
σ(t) = σ(0) exp −  (15.10)
 τ
where σ(t) and σ(0) represent the time-dependent and initial (i.e., time = 0) stresses, respectively, and t and τ denote
elapsed time and the relaxation time; τ is a time-independent constant characteristic of the material. A specimen of
some viscoelastic polymer the stress relaxation of which obeys Equation 15.10 was suddenly pulled in tension to a
measured strain of 0.6; the stress necessary to maintain this constant strain was measured as a function of time.
Determine E r (10) for this material if the initial stress level was 2.76 MPa (400 psi), which dropped to 1.72 MPa
(250 psi) after 60 s.
Solution
This problem asks for a determination of the relaxation modulus of a viscoelastic material, which behavior
is according to Equation 15.10--i.e.,
 t
σ(t) = σ(0) exp − 
 τ
We want to determine σ(10), but it is first necessary to compute τ from the data provided in the problem statement.
Thus, solving for τ from the above expression,
−t − 60 s
τ = = = 127 s
 σ(t)   1.72 MPa 
ln   ln  2.76 MPa 
 σ(0) 
Therefore,
 10 s 
σ(10) = (2.76 MPa) exp −  = 2.55 MPa
 127 s 
Now, using Equation 15.1
σ (10) 2.55 MPa

Er (10) = = = 4.25 MPa (616 psi)
ε0 0.6
15.7 In Figure 15.28, the logarithm of E r (t) versus the logarithm of time is plotted for polyisobutylene at a
variety of temperatures. Make a plot of E r (10) versus temperature and then estimate its T g .
Solution
Below is plotted the logarithm of Er(10) versus temperature.
The glass-transition temperature is that temperature corresponding to the abrupt decrease in log Er(10), which for
this polyisobutylene material is about -60°C.
15.8 On the basis of the curves in Figure 15.5, sketch schematic strain–time plots for the following
polystyrene materials at the specified temperatures:
(a) Amorphous at 120°C
(b) Crosslinked at 150°C
(c) Crystalline at 230°C
(d) Crosslinked at 50°C
Solution
(a) Amorphous polystyrene at 120°C behaves a rubbery material (Figure 15.8, curve C); therefore, the
strain-time behavior would be as Figure 15.5c.
(b) Crosslinked polystyrene at 150°C behaves as a viscoelastic material (Figure 15.8, curve B); therefore,
the strain-time behavior will be as Figure 15.5c.
(c) Crystalline polystyrene at 230°C behaves as a viscous liquid (Figure 15.8, curve A); therefore, the
strain-time behavior will be as Figure 15.5d.
(d) Crosslinked polystyrene at 50°C behaves in a glassy manner (Figure 15.8, curve B); therefore, the
strain-time behavior will be as Figure 15.5b.
15.9 (a) Contrast the manner in which stress relaxation and viscoelastic creep tests are conducted.
(b) For each of these tests, cite the experimental parameter of interest and how it is determined.
Solution
(a) Stress relaxation tests are conducted by rapidly straining the material elastically in tension, holding the
strain level constant, and then measuring the stress as a function of time. For viscoelastic creep tests, a stress
(usually tensile) is applied instantaneously and maintained constant while strain is measured as a function of time.
(b) The experimental parameters of interest from the stress relaxation and viscoelastic creep tests are the
relaxation modulus and creep modulus (or creep compliance), respectively. The relaxation modulus is the ratio of
stress measured after 10 s and strain (Equation 15.1); creep modulus is the ratio of stress and strain taken at a
specific time (Equation 15.2).
15.10 Make two schematic plots of the logarithm of relaxation modulus versus temperature for an
amorphous polymer (curve C in Figure 15.8).
(a) On one of these plots demonstrate how the behavior changes with increasing molecular weight.
(b) On the other plot, indicate the change in behavior with increasing crosslinking.
Solution
(a) This portion of the problem calls for a plot of log Er(10) versus temperature demonstrating how the
behavior changes with increased molecular weight. Such a plot is given below. Increasing molecular weight
increases both glass-transition and melting temperatures.
(b) We are now called upon to make a plot of log Er(10) versus temperature demonstrating how the
behavior changes with increased crosslinking. Such a plot is given below. Increasing the degree of crosslinking
will increase the modulus in both glassy and rubbery regions.
Fracture of Polymers
Miscellaneous Mechanical Considerations
15.11 For thermoplastic polymers, cite five factors that favor brittle fracture.
Solution
For thermoplastic polymers, five factors that favor brittle fracture are as follows: (1) a reduction in
temperature, (2) an increase in strain rate, (3) the presence of a sharp notch, (4) increased specimen thickness, and
(5) modifications of the polymer structure.
15.12 (a) Compare the fatigue limits for polystyrene (Figure 15.11) and the cast iron for which fatigue
data are given in Problem 8.20.
(b) Compare the fatigue strengths at 106 cycles for poly(ethylene terephthalate) (PET, Figure 15.11) and
red brass (Figure 8.34).
Solution
(a) The fatigue limits for polystyrene and the cast iron are 10.5 MPa (1500 psi) and 193 MPa (28,000 psi),
respectively.
(b) At 106 cycles, the fatigue strengths of PET and red brass are 15 MPa (2175 psi) and 115 MPa (16,700
psi ), respectively.
Deformation of Semicrystalline Polymers
15.13 In your own words, describe the mechanisms by which semicrystalline polymers (a) elastically
deform and (b) plastically deform, and (c) by which elastomers elastically deform.
(a) and (b) The mechanisms by which semicrystalline polymers elastically and plastically deform are
described in Section 15.7.
(c) The explanation of the mechanism by which elastomers elastically deform is provided in Section 15.9.
Factors That Influence the Mechanical Properties of Semicrystalline
Polymers
Deformation of Elastomers
15.14 Briefly explain how each of the following influences the tensile modulus of a semicrystalline
polymer and why:
(a) Molecular weight
(b) Degree of crystallinity
(c) Deformation by drawing
(d) Annealing of an undeformed material
(f) Annealing of a drawn material
Solution
(a) The tensile modulus is not directly influenced by a polymer's molecular weight.
(b) Tensile modulus increases with increasing degree of crystallinity for semicrystalline polymers. This is
due to enhanced secondary interchain bonding which results from adjacent aligned chain segments as percent
crystallinity increases. This enhanced interchain bonding inhibits relative interchain motion.
(c) Deformation by drawing also increases the tensile modulus. The reason for this is that drawing
produces a highly oriented molecular structure, and a relatively high degree of interchain secondary bonding.
(d) When an undeformed semicrystalline polymer is annealed below its melting temperature, the tensile
modulus increases.
(e) A drawn semicrystalline polymer that is annealed experiences a decrease in tensile modulus as a result
of a reduction in chain-induced crystallinity, and a reduction in interchain bonding forces.
15.15 Briefly explain how each of the following influences the tensile or yield strength of a semicrystalline
polymer and why:
(a) Molecular weight
(b) Degree of crystallinity
(c) Deformation by drawing
(d) Annealing of an undeformed material
Solution
(a) The tensile strength of a semicrystalline polymer increases with increasing molecular weight. This
effect is explained by increased chain entanglements at higher molecular weights.
(b) Increasing the degree of crystallinity of a semicrystalline polymer leads to an enhancement of the
tensile strength. Again, this is due to enhanced interchain bonding and forces; in response to applied stresses,
interchain motions are thus inhibited.
(c) Deformation by drawing increases the tensile strength of a semicrystalline polymer. This effect is due
to the highly oriented chain structure that is produced by drawing, which gives rise to higher interchain secondary
bonding forces.
(d) Annealing an undeformed semicrystalline polymer produces an increase in its tensile strength.
15.16 Normal butane and isobutane have boiling temperatures of –0.5 and –12.3°C (31.1 and 9.9°F),
respectively. Briefly explain this behavior on the basis of their molecular structures, as presented in Section 14.2.
Solution
Normal butane has a higher melting temperature as a result of its molecular structure (Section 14.2). There
is more of an opportunity for van der Waals bonds to form between two molecules in close proximity to one another
than for isobutane because of the linear nature of each normal butane molecule.
15.17 The tensile strength and number-average molecular weight for two poly(methyl methacrylate)
materials are as follows:
Tensile Strength Number-Average

(MPa) Molecular Weight (g/mol)
107 40,000
170 60,000
Estimate the tensile strength at a number-average molecular weight of 30,000 g/mol.
Solution
This problem gives us the tensile strengths and associated number-average molecular weights for two
poly(methyl methacrylate) materials and then asks that we estimate the tensile strength for M n = 30,000 g/mol.
Equation 15.3 cites the dependence of the tensile strength on M n . Thus, using the data provided in the problem
statement, we may set up two simultaneous equations from which it is possible to solve for the two constants TS∞
and A. These equations are as follows:
A
107 MPa = TS∞ −
40, 000 g / mol
A
170 MPa = TS∞ −
60, 000 g / mol
Thus, the values of the two constants are: TS∞ = 296 MPa and A = 7.56 × 106 MPa-g/mol. Substituting these
values into Equation 15.3 for M n = 30,000 g/mol leads to
A
TS = TS∞ −
30, 000 g / mol
7.56 × 10 6 MPa - g / mol

= 296 MPa −
30,000 g / mol
= 44 MPa
15.18 The tensile strength and number-average molecular weight for two polyethylene materials are as
follows:
Tensile Strength Number-Average

(MPa) Molecular Weight (g/mol)
85 12,700
150 28,500
Estimate the number-average molecular weight that is required to give a tensile strength of 195 MPa.
Solution
This problem gives us the tensile strengths and associated number-average molecular weights for two
polyethylene materials and then asks that we estimate the M n that is required for a tensile strength of 195 MPa.
Equation 15.3 cites the dependence of the tensile strength on M n . Thus, using the data provided in the problem
statement, we may set up two simultaneous equations from which it is possible to solve for the two constants TS∞
and A. These equations are as follows:
A
85 MPa = TS∞ −
12, 700 g / mol
A
150 MPa = TS∞ −
28,500 g / mol
Thus, the values of the two constants are: TS∞ = 202 MPa and A = 1.489 × 106 MPa-g/mol. Solving for M n in
Equation 15.3 and substituting TS = 195 MPa as well as the above values for TS∞ and A leads to
A
Mn =
TS∞ − TS
1.489 × 10 6 MPa - g / mol

= = 213, 000 g/mol
202 MPa − 195 MPa
to decide whether one polymer has a higher tensile modulus than the other; (2) if this is possible, note which has the
higher tensile modulus and then cite the reason(s) for your choice; and (3) if it is not possible to decide, then state
why.
(a) Random acrylonitrile-butadiene copolymer with 10% of possible sites crosslinked; alternating
acrylonitrile-butadiene copolymer with 5% of possible sites crosslinked
(b) Branched and syndiotactic polypropylene with a degree of polymerization of 5000; linear and isotactic
polypropylene with a degree of polymerization of 3000
(c) Branched polyethylene with a number-average molecular weight of 250,000 g/mol; linear and isotactic
poly(vinyl chloride) with a number-average molecular weight of 200,000 g/mol
Solution
For each of four pairs of polymers, we are to do the following: (1) determine whether or not it is possible to decide
which has the higher tensile modulus; (2) if so, note which has the higher tensile modulus and then state the
reasons for this choice; and (3) if it is not possible to decide, then state why.
(a) No, it is not possible. The random acrylonitrile-butadiene copolymer will tend to a lower degree of
crystallinity than the alternating acrylonitrile-butadiene copolymer inasmuch as random copolymers don’t normally
crystallize. On this basis only, the alternating material would have a higher modulus inasmuch as tensile modulus
increases with degree of crystallinity. On the other hand, the random copolymer has a higher degree of crosslinking
(10% versus 5% for the alternating copolymer), and, on this basis only would have the higher tensile modulus—an
increase in crosslinking leads to an increase in E. Thus, this determination is not possible; with regard to degree of
crystallinity the alternating material has the higher E, whereas the random copolymer would have a higher E value
on the basis of degree of crosslinking.
(b) Yes, it is possible. The linear and isotactic polypropylene will have a greater tensile modulus. Linear
polymers are more likely to crystallize that branched ones. The likelihood of crystallization for both syndiotactic
and isotactic polypropylene is about the same, and, therefore, degree is crystallization is not a factor. Furthermore,
tensile modulus is relatively insensitive to degree of polymerization (i.e., molecular weight)—the fact that branched
PP has the higher molecular weight is not important.
(c) No, it is not possible. Linear polymers have higher degrees of crystallization (and higher tensile
moduli) than branched polymers—on this basis, the PVC material should have the higher value of E. On the other
hand, PVC has a more complex repeat unit structure than does polyethylene, which means that, on this basis, the PE
would have a higher degree of crystallinity and also a greater tensile modulus. Also, tensile modulus is relatively
independent of number-average molecular weight. Therefore, this determination is not possible since it is not
possible to determine which of the two materials has the greater degree of crystallinity.
to decide whether one polymer has a higher tensile strength than the other; (2) if this is possible, note which has the
higher tensile strength and then cite the reason(s) for your choice; and (3) if it is not possible to decide, then state
why.
(a) Syndiotactic polystyrene having a number-average molecular weight of 600,000 g/mol; atactic
polystyrene having a number-average molecular weight of 500,000 g/mol
(b) Random acrylonitrile-butadiene copolymer with 10% of possible sites crosslinked; block acrylonitrile-
butadiene copolymer with 5% of possible sites crosslinked
(c) Network polyester; lightly branched polypropylene
Solution
For each of three pairs of polymers, we are to do the following: (1) determine whether or not it is possible
to decide which has the higher tensile strength; (2) if it is possible, then note which has the higher tensile strength
and then state the reasons for this choice; and (3) if it is not possible to decide, to state why.
(a) Yes it is possible. The syndiotactic polystyrene has the higher tensile strength. Syndiotactic polymers
are more likely to crystallize than atactic ones; the greater the crystallinity, the higher the tensile strength.
Furthermore, the syndiotactic also has a higher molecular weight; increasing molecular weight also enhances the
strength.
(b) No it is not possible. The random acrylonitrile-butadiene copolymer has more crosslinking; increased
crosslinking leads to an increase in strength. However, the block copolymeric material will most likely have a
higher degree of crystallinity; and increasing crystallinity improves the strength.
(c) Yes it is possible. The network polyester will display a greater tensile strength. Relative chain motion
is much more restricted than for the lightly branched polypropylene since there are many more of the strong
covalent bonds for the network structure.
15.21 Would you expect the tensile strength of polychlorotrifluoroethylene to be greater than, the same as,
or less than that of a polytetrafluoroethylene specimen having the same molecular weight and degree of
crystallinity? Why?
Solution
The strength of a polychlorotrifluoroethylene having the repeat unit structure
will be greater than for a polytetrafluoroethylene having the same molecular weight and degree of crystallinity. The
replacement of one fluorine atom within the PTFE repeat unit with a chlorine atom leads to a higher interchain
attraction, and, thus, a stronger polymer. Furthermore, poly(vinyl chloride) is stronger than polyethylene (Table
15.1) for the same reason.
15.22 For each of the following pairs of polymers, plot and label schematic stress–strain curves on the
same graph [i.e., make separate plots for parts (a), (b), and (c)].
(a) Isotactic and linear polypropylene having a weight-average molecular weight of 120,000 g/mol; atactic
and linear polypropylene having a weight-average molecular weight of 100,000 g/mol
(b) Branched poly(vinyl chloride) having a degree of polymerization of 2000; heavily crosslinked
poly(vinyl chloride) having a degree of polymerization of 2000
(c) Poly(styrene-butadiene) random copolymer having a number-average molecular weight of 100,000
g/mol and 10% of the available sites crosslinked and tested at 20°C; poly(styrene-butadiene) random copolymer
having a number-average molecular weight of 120,000 g/mol and 15% of the available sites crosslinked and tested
at -85°C. Hint: poly(styrene-butadiene) copolymers may exhibit elastomeric behavior.
Solution
(a) Shown below are the stress-strain curves for the two polypropylene materials. These materials will
display the stress-strain behavior of a normal plastic, curve B in Figure 15.1. However, the isotactic/linear will have
a higher degree of crystallinity (since isotactic are more likely to crystallize than atactic/linear), and therefore, will
have a higher tensile modulus and strength. Furthermore, the isotactic/linear also has a higher molecular weight
which also leads to an increase in strength.
(b) Shown below are the stress-strain curves for the two polyvinyl chloride materials. The branched PVC
will probably display the stress-strain behavior of a plastic, curve B in Figure 15.1. However, the heavily
crosslinked PVC will undoubtedly have a higher tensile modulus, and, also a higher strength, and will most likely
fail in a brittle manner--as curve A, Figure 15.1; these are the typical characteristics of a heavily crosslinked
polymer.
(c) Shown below are the stress-strain curves for the two poly(styrene-butadiene) random copolymers. The
copolymer tested at 20°C will display elastomeric behavior (curve C of Figure 15.1) inasmuch as it is a random
copolymer that is lightly crosslinked; furthermore, the temperature of testing is above its glass transition
temperature. On the other hand, since -85°C is below the glass transition temperature of the poly(styrene-
butadiene) copolymer, the stress-strain behavior under these conditions is as curve A of Figure 15.1.
15.23 List the two molecular characteristics that are essential for elastomers.
Solution
Two molecular characteristics essential for elastomers are: (1) they must be amorphous, having chains that
are extensively coiled and kinked in the unstressed state; and (2) there must be some crosslinking.
15.24 Which of the following would you expect to be elastomers and which thermosetting polymers at
room temperature? Justify each choice.
(a) Epoxy having a network structure
(b) Lightly crosslinked poly(styrene-butadiene) random copolymer that has a glass-transition temperature
of -50°C
(c) Lightly branched and semicrystalline polytetrafluoroethylene that has a glass-transition temperature of
-100°C
(d) Heavily crosslinked poly(ethylene-propylene) random copolymer that has a glass-transition
temperature of 0°C
(e) Thermoplastic elastomer that has a glass-transition temperature of 75°C
Solution
This question asks us to choose from a list of materials those that would be expected to be elastomers and
those that would be thermosetting polymers.
(a) Epoxy having a network structure will be a thermoset polymer since it has a network structure. It
would not be an elastomer since it does not have a crosslinked chain structure.
(b) A lightly crosslinked poly(styrene-butadiene) random copolymer that has a glass-transition temperature
of -50°C will be an elastomer since it 1) is a random copolymer, 2) is lightly crosslinked, and 3) is being used at a
temperature above its glass transition. All three of these criteria are requisites for an elastomer.
(c) Lightly branched and semicrystalline PTFE would be neither an elastomer nor a thermoset. It is not
crosslinked nor does it have a network structure.
(d) A heavily crosslinked poly(ethylene-propylene) random copolymer would be a thermoset inasmuch as
it is heavily crosslinked.
(e) A thermoplastic elastomer that has a glass-transition temperature of 75°C is neither an elastomer nor a
thermoset. Since it is a thermoplastic it is not a thermoset. Furthermore, room temperature is below its glass-
transition temperature, and, therefore, it will not display elastomeric behavior.
15.25 Ten kilogram of polybutadiene is vulcanized with 4.8 kg sulfur. What fraction of the possible
crosslink sites is bonded to sulfur crosslinks, assuming that, on the average, 4.5 sulfur atoms participate in each
crosslink?
Solution
This problem asks that we compute the fraction of possible crosslink sites in 10 kg of polybutadiene when
4.8 kg of S is added, assuming that, on the average, 4.5 sulfur atoms participate in each crosslink bond. Given the
butadiene repeat unit in Table 14.5, we may calculate its molecular weight as follows:
A(butadiene) = 4(AC) + 6(AH)
= (4)(12.01 g/mol) + 6(1.008 g/mol) = 54.09 g/mol
10,000 g
Which means that in 10 kg of butadiene there are = 184.9 mol = nbuta .
54.09 g/mol
For the vulcanization polybutadiene, there are two possible crosslink sites per repeat unit--one for each of
the two carbon atoms that are doubly bonded. Furthermore, each of these crosslinks forms a bridge between two
repeat units. Therefore, we can say that there is the equivalent of one crosslink per repeat unit. Let us now
calculate the number of moles of sulfur (nsulfur) that react with the butadiene, by taking the mole ratio of sulfur to
butadiene, and then dividing this ratio by 4.5 atoms per crosslink; this yields the fraction of possible sites that are
crosslinked. Thus
4800 g
nsulfur = = 149.7 mol
32.06 g / mol
And
nsulfur 149.7 mol

n
fraction sites crosslinked = buta = 184.9 mol = 0.180
4.5 4.5
15.26 Compute the weight percent sulfur that must be added to completely crosslink an alternating
chloroprene-acrylonitrile copolymer, assuming that five sulfur atoms participate in each crosslink.
Solution
For an alternating chloroprene-acrylonitrile copolymer, we are asked to compute the weight percent sulfur
necessary for complete crosslinking, assuming that, on the average, five sulfur atoms participate in each crosslink.
The chloroprene and acrylonitrile repeat units are shown in Table 14.5, from which it may be noted that there are
two possible crosslink sites on each chloroprene repeat unit (one site at each of the two carbon atoms that are
doubly bonded), and no possible sites for acrylonitrile; also, since it is an alternating copolymer, the ratio of
chloroprene to acrylonitrile repeat units is 1:1. Thus, for each pair of combined chloroprene-acrylonitrile repeat
units that crosslink, ten sulfur atoms are required, or, for complete crosslinking, the sulfur-to-(chloroprene-
acrylonitrile) ratio is 5:1.
Now, let us consider as our basis, one mole of the combined chloroprene-acrylonitrile repeat unit. In order
for complete crosslinking, five moles of sulfur are required. Thus, for us to convert this composition to weight
percent, it is necessary to convert moles to mass. The acrylonitrile repeat unit consists of three carbon atoms, three
hydrogen atoms, and one nitrogen atom; the chloroprene repeat unit is composed of four carbons, five hydrogens,
and one chlorine. This gives a molecular weight for the combined repeat unit of
m(chloroprene-acrylonitrile) = 3(A ) + 3(A ) + A + 4(A ) + 5(A ) + A

C H N C H Cl
= 7(12.01 g/mol) + 8(1.008 g/mol) + 14.007 g/mol + 35.45 g/mol = 141.59 g/mol
Or, in one mole of this combined repeat unit, there are 141.59 g. Furthermore, for complete crosslinking 5.0 mol of
sulfur is required, which amounts to (5.0 mol)(32.06 g/mol) = 160.3 g. Thus, the concentration of S in weight
percent CS is just
160.3 g
CS = × 100 = 53.1 wt%
160.3 g + 141.59 g
15.27 The vulcanization of polyisoprene is accomplished with sulfur atoms according to Equation 15.4. If
57 wt% sulfur is combined with polyisoprene, how many crosslinks will be associated with each isoprene repeat
unit if it is assumed that, on the average, six sulfur atoms participate in each crosslink?
Solution
This problem asks for us to determine how many crosslinks form per isoprene repeat unit when 57 wt%
sulfur is added. If we arbitrarily consider 100 g of the vulcanized material, 57 g will be sulfur and 43 g will be
polyisoprene. Next, let us find how many moles of sulfur and isoprene correspond to these masses. The atomic
weight of sulfur is 32.06 g/mol, and thus,
57 g
# moles S = = 1.78 mol
32.06 g / mol
Now, in each isoprene repeat unit there are five carbon atoms and eight hydrogen atoms. Thus, the molecular
weight of a mole of isoprene units is
(5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol
Or, in 43 g of polyisoprene, the number of moles is equal to
43 g
# moles isoprene = = 0.631 mol
68.11 g / mol
Therefore, the ratio of moles of S to the number of moles of polyisoprene is
1.78 mol
:1 = 2.82 :1
0.631 mol
When all possible sites are crosslinked, the ratio of the number of moles of sulfur to the number of moles of
isoprene is 6:1; this is because there are two crosslink sites per repeat unit and each crosslink is shared between
repeat units on adjacent chains, and there are 6 sulfur atoms per crosslink. Finally, to determine the fraction of sites
that are crosslinked, we just divide the actual crosslinked sulfur/isoprene ratio by the completely crosslinked ratio.
Or,
2.82 /1
fraction of repeat unit sites crosslinked = = 0.470
6 /1
15.28 For the vulcanization of polyisoprene, compute the weight percent of sulfur that must be added to
ensure that 8% of possible sites will be crosslinked; assume that, on the average, three sulfur atoms are associated
with each crosslink.
Solution
We are asked what weight percent of sulfur must be added to polyisoprene in order to ensure that 8% of
possible sites are crosslinked, assuming that, on the average, three sulfur atoms are associated with each crosslink.
Table 14.5 shows the repeat unit for cis-isoprene. For each of these units there are two possible crosslink sites; one
site is associated with each of the two carbon atoms that are involved in the chain double bond. Since 8% of the
possible sites are crosslinked, for each 100 isoprene repeat units 8 of them are crosslinked; actually there are two
crosslink sites per repeat unit, but each crosslink is shared by two chains. Furthermore, on the average we assume
that each crosslink is composed of 3 sulfur atoms; thus, there must be 3 × 8 or 24 sulfur atoms added for every 100
isoprene repeat units. In terms of moles, it is necessary to add 24 moles of sulfur to 100 moles of isoprene. The
atomic weight of sulfur is 32.06 g/mol, while the molecular weight of isoprene is
A(isoprene) = 5(A ) + 8(A )

C H
= (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol
The mass of sulfur added (mS) is
mS = (24 mol)(32.06 g/mol) = 769.4 g
While for isoprene
mip = (100 mol)(68.11 g/mol) = 6811 g
Or, the concentration of sulfur in weight percent (Equation 4.3) is just
mS 769.4 g
CS = × 100 = × 100 = 10.1 wt%
mS + mip 769.4 g + 6811 g
15.29 Demonstrate, in a manner similar to Equation 15.4, how vulcanization may occur in a butadiene
rubber.
Solution
The reaction by which a butadiene rubber may become vulcanized is as follows:
Crystallization
15.30 Determine values for the constants n and k (Equation 10.17) for the crystallization of polypropylene
(Figure 15.17) at 160°C.
Solution
In this problem we are asked to determine the values of the constants n and k (Equation 10.17) for the
crystallization of polypropylene at 160°C (Figure 15.17). One way to solve this problem is to take two values of
percent recrystallization (which is just 100y, Equation 10.17) and their corresponding time values, then set up two
simultaneous equations, from which n and k may be determined. In order to expedite this process, we will rearrange
and do some algebraic manipulation of Equation 10.17. First of all, we rearrange as follows:
( )
1 − y = exp − kt n
Now taking natural logarithms
ln (1 − y) = − kt n
Or
− ln (1 − y) = kt n
which may also be expressed as
 1  n
ln   = kt
1 − y
Now taking natural logarithms again, leads to
  1 
ln  ln   = ln k + n ln t
  1 − y 
which is the form of the equation that we will now use. From the 160°C curve of Figure 15.17, let us arbitrarily
choose two percent crystallized values of 20% and 80% (i.e., y1 = 0.20 and y2 = 0.80). The corresponding time
values are t1 = 3400 min and t2 = 6700 min (realizing that the time axis is scaled logarithmically). Thus, our two
simultaneous equations become
  1 
ln  ln   = ln k + n ln (3400)
  1 − 0.20 
  1 
ln  ln   = ln k + n ln (6700)
  1 − 0.80 
from which we obtain the values n = 2.91 and k = 1.182 × 10-11.
Melting and Glass Transition Temperatures
15.31 Name the following polymer(s) that would be suitable for the fabrication of cups to contain hot
coffee: polyethylene, polypropylene, poly(vinyl chloride), PET polyester, and polycarbonate. Why?
Solution
This question asks us to name which, of several polymers, would be suitable for the fabrication of cups to
contain hot coffee. At its glass transition temperature, an amorphous polymer begins to soften. The maximum
temperature of hot coffee is probably slightly below 100°C (212°F). Of the polymers listed, only polystyrene and
polycarbonate have glass transition temperatures of 100°C or above (Table 15.2), and would be suitable for this
application.
15.32 Of those polymers listed in Table 15.2, which polymer(s) would be best suited for use as ice cube
trays? Why?
Solution
In order for a polymer to be suited for use as an ice cube tray it must have a glass-transition temperature
below 0°C. Of those polymers listed in Table 15.2 only low-density and high-density polyethylene, PTFE, and
polypropylene satisfy this criterion.
Factors That Influence Melting and Glass Transition Temperatures
15.33 For each of the following pairs of polymers, plot and label schematic specific volume versus
temperature curves on the same graph [i.e., make separate plots for parts (a), (b), and (c)].
(a) Spherulitic polypropylene, of 25% crystallinity, and having a weight-average molecular weight of
75,000 g/mol; spherulitic polystyrene, of 25% crystallinity, and having a weight-average molecular weight of
100,000 g/mol
(b) Graft poly(styrene-butadiene) copolymer with 10% of available sites crosslinked; random poly(styrene-
butadiene) copolymer with 15% of available sites crosslinked
(c) Polyethylene having a density of 0.985 g/cm3 and a degree of polymerization of 2500; polyethylene
having a density of 0.915 g/cm3 and a degree of polymerization of 2000
Solution
(a) Shown below are the specific volume-versus-temperature curves for the polypropylene and polystyrene
materials. Since both polymers are 25% crystalline, they will exhibit behavior similar to curve B in Figure 15.18.
However, polystyrene will have higher melting and glass transition temperatures due to the bulkier side group in its
repeat unit structure, and since it has a higher weight-average molecular weight.
(b) Shown below are the specific volume-versus-temperature curves for the graft and random poly(styrene-
butadiene) copolymers. Since these materials are graft and random copolymers, both will be highly noncrystalline,
and, thus, will display the behavior similar to curve A in Figure 15.18. However, since the random has the greater
degree of crosslinking, it will also have the higher glass transition temperature.
(c) Shown below are the specific volume-versus-temperature curves for the two polyethylene materials.
The polyethylene having a density of 0.985 g/cm3 will be highly crystalline, and, thus, will exhibit a behavior
similar to curve C in Figure 15.18. On the other hand, the other material, of lower density will have some branching
and also be semicrystalline; thus, its behavior will be similar to curve B of Figure 15.18. In addition, the melting
temperature of the higher density material will be greater since it has less branching and a higher degree of
polymerization.
to determine whether one polymer has a higher melting temperature than the other; (2) if it is possible, note which
has the higher melting temperature and then cite reason(s) for your choice; and (3) if it is not possible to decide,
then state why.
(a) Isotactic polystyrene that has a density of 1.12 g/cm3 and a weight-average molecular weight of
150,000 g/mol; syndiotactic polystyrene that has a density of 1.10 g/cm3 and a weight-average molecular weight of
125,000 g/mol
(b) Linear polyethylene that has a degree of polymerization of 5,000; linear and isotactic polypropylene
that has a degree of polymerization of 6,500
(c) Branched and isotactic polystyrene that has a degree of polymerization of 4,000; linear and isotactic
polypropylene that has a degree of polymerization of 7,500
Solution
(a) Yes, it is possible to determine which of the two polystyrenes has the higher Tm. The isotactic
polystyrene will have the higher melting temperature because it has a higher density (i.e., less branching) and also
the greater weight-average molecular weight.
(b) Yes, it is possible to determine which polymer has the higher melting temperature. The polypropylene
will have the higher Tm because it has a bulky phenyl side group in its repeat unit structure, which is absent in the
polyethylene. Furthermore, the polypropylene has a higher degree of polymerization.
(c) No, it is not possible to determine which of the two polymers has the higher melting temperature. The
polystyrene has a bulkier side group than the polypropylene; on the basis of this effect alone, the polystyrene
should have the greater Tm. However, the polystyrene has more branching and a lower degree of polymerization;
both of these factors lead to a lowering of the melting temperature.
15.35 Make a schematic plot showing how the modulus of elasticity of an amorphous polymer depends on
the glass transition temperature. Assume that molecular weight is held constant.
Solution
For an amorphous polymer, the elastic modulus may be enhanced by increasing the number of crosslinks
(while maintaining the molecular weight constant); this will also enhance the glass transition temperature. Thus,
the modulus-glass transition temperature behavior would appear as
Elastomers
Fibers
Miscellaneous Applications
15.36 Briefly explain the difference in molecular chemistry between silicone polymers and other polymeric
materials.
Solution
The backbone chain of most polymers consists of carbon atoms that are linked together. For the silicone
polymers, this backbone chain is composed of silicon and oxygen atoms that alternate positions.
15.37 List two important characteristics for polymers that are to be used in fiber applications.
Solution
Two important characteristics for polymers that are to be used in fiber applications are: (1) they must have
high molecular weights, and (2) they must have chain configurations/structures that will allow for high degrees of
crystallinity.
15.38 Cite five important characteristics for polymers that are to be used in thin-film applications.
Solution
Five important characteristics for polymers that are to be used in thin-film applications are: (1) low
density; (2) high flexibility; (3) high tensile and tear strengths; (4) resistance to moisture/chemical attack; and (5)
low gas permeability.
Polymerization
15.39 Cite the primary differences between addition and condensation polymerization techniques.
Solution
For addition polymerization, the reactant species have the same chemical composition as the monomer
species in the molecular chain. This is not the case for condensation polymerization, wherein there is a chemical
reaction between two or more monomer species, producing the repeating unit. There is often a low molecular
weight by-product for condensation polymerization; such is not found for addition polymerization.
15.40 (a) How much ethylene glycol must be added to 47.3 kg of terephthalic acid to produce a linear
chain structure of poly(ethylene terephthalate) according to Equation 15.9?
(b) What is the mass of the resulting polymer?
Solution
(a) This problem asks that we determine how much ethylene glycol must be added to 47.3 kg of
terephthalic acid to produce a linear chain structure of poly(ethylene terephthalate) according to Equation 15.9.
Since the chemical formulas are provided in this equation we may calculate the molecular weights of each of these
materials as follows:
MW(ethylene glycol) = 2( AC ) + 6( AH ) + 2( AO )
= 2(12.01 g/mol) + 6(1.008 g/mol) + 2(16.00 g/mol) = 62.07 g/mol
MW(terephthalic acid) = 8( AC ) + 6( AH ) + 4( AO )
= 8 (12.01 g/mol) + 6(1.008 g/mol) + 4(16.00 g/mol) = 166.13 g/mol
47,300 g
The 47.3 kg mass of terephthalic acid equals 47,300 g or = 284.72 mol. Since, according to
166.13 g / mol
Equation 15.9, each mole of terephthalic acid used requires one mole of ethylene glycol, which is equivalent to
(284.72 mol)(62.07 g/mol) = 17,673 g = 17.673 kg.
(b) Now we are asked for the mass of the resulting polymer. Inasmuch as one mole of water is given off
for every repeat unit produced, this corresponds to 284.72 moles or (284.72 mol)(18.02 g/mol) = 5130 g or 5.130 kg
since the molecular weight of water is 18.02 g/mol. The mass of poly(ethylene terephthalate) is just the sum of the
masses of the two reactant materials [as computed in part (a)] minus the mass of water released, or
mass [poly(ethylene terephthalate)] = 47.300 kg + 17.673 kg − 5.130 kg = 59.843 kg
15.41 Nylon 6,6 may be formed by means of a condensation polymerization reaction in which
hexamethylene diamine [NH 2 —(CH 2 ) 6 —NH 2 ] and adipic acid react with one another with the formation of water
as a byproduct. What masses of hexamethylene diamine and adipic acid are necessary to yield 37.5 kg of completely
linear nylon 6,6? (Note: the chemical equation for this reaction is the answer to Concept Check 15.12.)
Solution
This problem asks for us to calculate the masses of hexamethylene diamine and adipic acid necessary to
yield 37.5 kg of completely linear nylon 6,6. The chemical equation for this reaction is the answer to Concept
Check 15.12, which is as follows:
From this equation we may calculate the molecular weights of these molecules.
MW(adipic) = 6( AC ) + 10( AH ) + 4( AO )
= 6(12.01 g/mol) + 10(1.008 g/mol) + 4 (16.00 g/mol) = 146.14 g/mol
MW(hexamethylene) = 6( AC ) + 16( AH ) + 2( AN )
= 6(12.01 g/mol) + 16(1.008 g/mol) + 2 (14.01 g/mol) = 116.21 g/mol
MW(nylon) = 12( AC ) + 22( AH ) + 2( AN ) + 2( AO )
= 12(12.01 g/mol) + 22(1.008 g/mol) + 2(14.01 g/mol) + 2(16.00 g/mol)
= 226.32 g/mol
The mass of 37.5 kg of nylon 6,6 equals 37,500 g or
37,500 g
m(nylon) = = 165.7 mol
226.32 g / mol
Since, according to the chemical equation given above, each mole of nylon 6,6 that is produced requires one mole
each of adipic acid and hexamethylene diamine, with two moles of water as the by-product. The masses
corresponding to 165.7 moles of adipic acid and hexamethylene diamine are as follows:
m(adipic) = (165.7 mol)(146.14 g/mol) = 24, 215 g = 24.215 kg
m(hexamethylene) = (165.7 mol)(116.21 g/mol) = 19,256 g = 19.256 kg
Polymer Additives
15.42 What is the distinction between dye and pigment colorants?
Solution
The distinction between dye and pigment colorants is that a dye dissolves within and becomes a part of the
polymer structure, whereas a pigment does not dissolve, but remains as a separate phase.
Forming Techniques for Plastics
15.43 Cite four factors that determine what fabrication technique is used to form polymeric materials.
Solution
Four factors that determine what fabrication technique is used to form polymeric materials are: (1) whether
the polymer is thermoplastic or thermosetting; (2) if thermoplastic, the softening temperature; (3) atmospheric
stability; and (4) the geometry and size of the finished product.
15.44 Contrast compression, injection, and transfer molding techniques that are used to form plastic
materials.
Solution
This question requests that we compare polymer molding techniques. For compression molding, both heat
and pressure are applied after the polymer and necessary additives are situated between the mold members. For
transfer molding, the solid materials (normally thermosetting in nature) are first melted in the transfer chamber prior
to being forced into the die. And, for injection molding (normally used for thermoplastic materials), the raw
materials are impelled by a ram through a heating chamber, and finally into the die cavity.
Fabrication of Fibers and Films
15.45 Why must fiber materials that are melt spun and then drawn be thermoplastic? Cite two reasons.
Solution
Fiber materials that are melt spun must be thermoplastic because: (1) In order to be melt spun, they must
be capable of forming a viscous liquid when heated, which is not possible for thermosets. (2) During drawing,
mechanical elongation must be possible; inasmuch as thermosetting materials are, in general, hard and relatively
brittle, they are not easily elongated.
15.46 Which of the following polyethylene thin films would have the better mechanical characteristics: (1)
formed by blowing, or (2) formed by extrusion and then rolled? Why?
Solution
Of the two polymers cited, the one that was formed by extrusion and then rolled would have the higher
strength. Both blown and extruded materials would have roughly comparable strengths; however the rolling
operation would further serve to enhance the strength of the extruded material.
DESIGN QUESTIONS
15.D1 (a) List several advantages and disadvantages of using transparent polymeric materials for eyeglass
lenses.
(b) Cite four properties (in addition to being transparent) that are important for this application.
(c) Note three polymers that may be candidates for eyeglass lenses, and then tabulate values of the
properties noted in part (b) for these three materials.
Solution
(a) Several advantages of using transparent polymeric materials for eyeglass lenses are: they have
relatively low densities, and, therefore, are light in weight; they are relatively easy to grind to have the desired
contours; they are less likely to shatter than are glass lenses; wraparound lenses for protection during sports
activities are possible; and they filter out more ultraviolet radiation than do glass lenses.
The principal disadvantage of these types of lenses is that some are relatively soft and are easily scratched
(although antiscratch coatings may be applied). Plastic lenses are not as mechanically stable as glass, and, therefore,
are not as precise optically.
(b) Some of the properties that are important for polymer lens materials are: they should be relatively hard
in order to resist scratching; they must be impact resistant; they should be shatter resistant; they must have a
relatively high index of refraction such that thin lenses may be ground for very nearsighted people; and they should
absorb significant proportions of all types of ultraviolet radiation, which radiation can do damage to the eye tissues.
(c) Of those polymers discussed in this chapter and Chapter 14, likely lens candidates are polystyrene,
poly(methyl methacrylate), and polycarbonate; these three materials are not easily crystallized, and, therefore, are
normally transparent. Upon consultation of their fracture toughnesses (Table B.5 in Appendix B), polycarbonate is
the most superior of the three.
Commercially, the two plastic lens materials of choice are polycarbonate and allyl diglycol carbonate
(having the trade name CR-39). Polycarbonate is very impact resistant, but not as hard as CR-39. Furthermore, PC
comes in both normal and high refractive-index grades.
15.D2 Write an essay on polymeric materials that are used in the packaging of food products and drinks.
Include a list of the general requisite characteristics of materials that are used for these applications. Now cite a
specific material that is utilized for each of three different container types and the rationale for each choice.
Solution
There are three primary requirements for polymeric materials that are utilized in the packaging of food
products and drinks; these are: (1) sufficient strength, to include tensile, tear, and impact strengths; (2) barrier
protection--that is, being resistant to permeation by oxygen, water vapor, and carbon dioxide; and (3) being
nonreactive with the food/drink contents--such reactions can compromise the integrity of the packaging material, or
they can produce toxic by-products.
With regard to strength, poly(ethylene terephthalate) (PET or PETE) and oriented polypropylene (OPP)
have high tensile strengths, linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE) have
high tear strengths, while those polymers having the best impact strengths are PET and poly(vinyl chloride) (PVC).
Relative to barrier characteristics, ethylene vinyl alcohol (EVOH) and poly(vinylidene chloride) (PVDC)
copolymers are relatively impermeable to oxygen and carbon dioxide, whereas high-density polyethylene (HDPE),
PVDC, polypropylene, and LDPE are impervious to water vapor.
Most common polymers are relatively nonreactive with food products, and are considered safe; exceptions
are acrylonitrile and plasticizers used in PVC materials.
The aesthetics of packaging polymers are also important in the marketing of food and drink products.
Some will be colored, many are adorned with printing, others need to be transparent and clear, and many need to be
resistant to scuffing.
On the basis of the preceding discussion, examples of polymers that are used for specific applications are
as follows:
PET(E) for soda pop containers;
PVC for beer containers;
LDPE and HDPE films for packaging bread and bakery products.
15.D3 Write an essay on the replacement of metallic automobile components by polymers and composite
materials. Address the following issues: (1) Which automotive components (e.g., crankshaft) now use polymers
and/or composites? (2) Specifically what materials (e.g., high-density polyethylene) are now being used? (3) What
are the reasons for these replacements?
Solution
The primary reasons that the automotive industry has replaced metallic automobile components with
polymer and composite materials are: polymers/composites (1) have lower densities, and afford higher fuel
efficiencies; (2) may be produced at lower costs but with comparable mechanical characteristics; (3) are in many
environments more corrosion resistant; (4) reduce noise, and (5) are thermally insulating and thus reduce the
transference of heat.
These replacements are many and varied. Several are as follows:
Bumper fascia are molded from an elastomer-modified polypropylene.
Overhead consoles are made of poly(phenylene oxide) and recycled polycarbonate.
Rocker arm covers are injection molded of a glass- and mineral-reinforced nylon 6,6 composite.
Torque converter reactors, water outlets, pulleys, and brake pistons, are made from phenolic thermoset
composites that are reinforced with glass fibers.
Air intake manifolds are made of a glass-reinforced nylon 6,6.

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CHAPTER 14

The repeat unit structures called for are sketched below.

(b) Poly(vinyl alcohol)

m = 2(AC) + 3(AH) + (ACl)

= (2)(12.01 g/mol) + (3)(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol

m = 10(AC) + 8(AH) + 4(AO)

= (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol

m = 16(AC) + 14(AH) + 3(AO)

= (16)(12.01 g/mol) + (14)(1.008 g/mol) + (3)(16.00 g/mol)

m = 2(AC) + 6(AH) + (ASi) + (AO)

= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

Now it is possible to compute the degree of polymerization using Equation 14.6 as

M n 1, 000, 000 g/mol

= (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol

M n = (DP)m = (25, 000)(104.14 g/mol) = 2.60 × 10 6 g/mol

carried out below.

8,000-16,000 12,000 0.05 600

8,000-16,000 12,000 0.02 240

= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

30,000–45,000 0.07 0.04

45,000–60,000 0.16 0.11

60,000–75,000 0.26 0.24

75,000–90,000 0.24 0.27

90,000–105,000 0.12 0.16

105,000–120,000 0.08 0.12

120,000–135,000 0.03 0.05

carried out below.

15,000-30,000 22,500 0.04 900

determination is performed as follows:

15,000-30,000 22,500 0.01 225

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

8,000-20,000 14,000 0.05 700

m = 5(AC) + 8(AH) + 2(AO)

Now, we will compute the degree of polymerization using Equation 14.6 as

Mn 47, 720 g/mol

mC = 50(AC) = (50)(12.01 g/mol) = 600.5 g

Likewise, for hydrogen and chlorine,

mH = 95(AH) = (95)(1.008 g/mol) = 95.76 g

mCl = 5(ACl) = (5)(35.45 g/mol) = 177.25 g

= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol

r = d N = (0.154 nm) 10,000 = 15.4 nm

= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol

M n = (DP)m = (8450)(28.05 g/mol) = 237,000 g/mol

(b) Atactic polystyrene

(c) Isotactic polystyrene

The structure of trans butadiene is

(b) The structure of cis chloroprene (Table 14.5) is

The structure of trans chloroprene is

(b) For poly(styrene-methyl methacrylate)

(c) For poly(acrylonitrile-vinyl chloride)

= (12)(12.01 g/mol) + (14)(1.008 g/mol) = 158.23 g/mol

From Equation 14.6, the degree of polymerization is just

mAc = 3(AC) + (AN) + 3(AH)

= (3)(12.01 g/mol) + 14.01 g/mol + (3)(1.008 g/mol) = 53.06 g/mol

mBu = 4(AC) + 6(AH)