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

8,00016,000

0.05

0.02

16,00024,000

0.16

0.10

24,00032,000

0.24

0.20

32,00040,000

0.28

0.30

40,00048,000

0.20

0.27

48,00056,000

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

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

wiMi

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
DP =

Mn
33,040 g/mol
=
= 785
m
42.08 g/mol

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)
8,00020,000

wi
0.02

xi
0.05

20,00032,000

0.08

0.15

32,00044,000

0.17

0.21

44,00056,000

0.29

0.28

56,00068,000

0.23

0.18

68,00080,000

0.16

0.10

80,00092,000

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.
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 =

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

DP =

Mn
47,720 g/mol
=
= 477
m
100.11 g/mol

Thus, such a homopolymer is not possible since the calculated degree of polymerization is 477 (and not 527).

14.25 The density and associated percent crystallinity for two polytetrafluoroethylene materials are as follows:
(g/cm3)

crystallinity (%)

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 (c and a from Equation 14.8). From Equation 14.8 let C =
, such that
100

C =

c ( s a )
s (c a )

Rearrangement of this expression leads to

c (C s s ) + ca C s a = 0

in which c and a are the variables for which solutions are to be found. Since two values of s and C are specified

in the problem statement, two equations may be constructed as follows:

c (C1 s1 s1 ) + ca C1 s1 a = 0

c (C2 s2 s2 ) + ca C2 s2 a = 0

In which s1 = 2.144 g/cm3, s2 = 2.215 g/cm3, C1 = 0.513, and C2 = 0.742. Solving the above two equations for

a and c leads to

a =

s1 s2 (C1 C2 )
C1 s1 C2 s2

(2.144 g/cm 3)( 2.215 g/cm 3)(0.513 0.742)

= 2.000 g/cm3
(0.513)(2.144 g/cm3) (0.742)(2.215 g/cm3)

And

c =

s1 s2 (C 2 C1)
s2 (C 2 1) s1 (C1 1)

(2.144 g/cm 3)( 2.215 g/cm3)(0.742 0.513)

= 2.301 g/cm3
(2.215g/cm3)(0.742 1) (2.144 g/cm3)(0.513 1)

(b) Now we are to determine the % crystallinity for s = 2.26 g/cm3. Again, using Equation 14.8

% crystallinity =

c ( s a )
100
s ( c a )

(2.301 g/cm3)( 2.260 g/cm3

(2.260 g/cm3)( 2.301 g/cm3
= 87.9%

2.000 g/cm3)
100
2.000 g/cm3)

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

PM

J x
J x

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)

4.57 10-13

(cm 3 STP)(cm)
cm2 - s - Pa

15.17 The tensile strength and number-average molecular weight for two poly(methyl methacrylate) materials are
as follows:
Tensile Strength
(MPa)

Number-Average
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:

107 MPa = TS

A
40,000 g / mol

170 MPa = TS

A
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

TS = TS

= 296 MPa

A
30, 000 g / mol

7.56 106 MPa- g / mol

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
(MPa)
85

Number-Average
Molecular Weight (g/mol)
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:

85 MPa = TS

150 MPa = TS

A
12,700 g / mol
A
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
Mn =

A
TS TS

1.489 106 MPa- g / mol

MPa 195 MPa = 213,000 g/mol
202

16.10 For a continuous and oriented fiber-reinforced composite, the moduli of elasticity in the longitudinal and
transverse directions are 19.7 and 3.66 GPa (2.8 106 and 5.3 105 psi), respectively. If the volume fraction of
fibers is 0.25, determine the moduli of elasticity of fiber and matrix phases.
Solution
This problem asks for us to compute the elastic moduli of fiber and matrix phases for a continuous and
oriented fiber-reinforced composite. We can write expressions for the longitudinal and transverse elastic moduli
using Equations 16.10b and 16.16, as

Ecl = Em(1 V f

And

+ Ef Vf

19.7 GPa = Em (1 0.25) + E f (0.25)

Ect =

(1

3.66 GPa =

EmE f

V f ) E f V f Em

Em E f
(1 0.25)E f 0.25Em

Solving these two expressions simultaneously for Em and Ef leads to

Em = 2.79 GPa (4.04 105 psi)

E f = 70.4 GPa (10.2 106 psi)

16.14 A continuous and aligned fiber-reinforced composite having a cross-sectional area of 1130 mm2 (1.75 in.2) is
subjected to an external tensile load. If the stresses sustained by the fiber and matrix phases are 156 MPa (22,600
psi) and 2.75 MPa (400 psi), respectively, the force sustained by the fiber phase is 74,000 N (16,600 lb f) and the
total longitudinal strain is 1.25 10-3, determine
(a) the force sustained by the matrix phase
(b) the modulus of elasticity of the composite material in the longitudinal direction, and
(c) the moduli of elasticity for fiber and matrix phases.
Solution
(a) For this portion of the problem we are asked to calculate the force sustained by the matrix phase. It is
first necessary to compute the volume fraction of the matrix phase, Vm. This may be accomplished by first
determining Vf and then Vm from Vm = 1 Vf. The value of Vf may be calculated since, from the definition of stress
(Equation 6.1), and realizing Vf = Af/Ac as

f =

Or, solving for Vf

Af

Ff
V f Ac

Vf =

Also

Ff

Ff
f Ac

(156

106

N / m2

74,000 N
= 0.420
)(1130 mm2 )(1 m/1000 mm) 2

Vm = 1 V f = 1 0.420 = 0.580
And, an expression for m analogous to the one for f above is

m =

From which

Fm
Am

Fm
Vm Ac

Fm = Vm m Ac = (0.580)(2.75 106 N/m2 )(1.13 10-3 m2 ) = 1802 N (406 lbf )

(b) We are now asked to calculate the modulus of elasticity in the longitudinal direction. This is possible
Fm F f

realizing that Ec = c (from Equation 6.5) and that c =

(from Equation 6.1). Thus

Ac

Ec = c

(1.25

Fm F f
Ac

Fm F f
Ac

1802 N 74, 000 N

= 53.7 109 N/m 2 = 53.7 GPa (7.77 106 psi)
103)(1130mm2 )(1 m /1000 mm) 2

(c) Finally, it is necessary to determine the moduli of elasticity for the fiber and matrix phases. This is

possible assuming Equation 6.5 for the matrix phasei.e.,

Em =

m
m

and, since this is an isostrain state, m = c = 1.25 10-3. Thus

Em =

m
2.75 106 N / m2
=
= 2.2 109 N/m2
c
1.25 103
= 2.2 GPa (3.2 105 psi)

The elastic modulus for the fiber phase may be computed in an analogous manner:

Ef =

f
f

f
c

156 106 N / m2
= 1.248 1011 N/m2
1.25 103

= 124.8 GPa (18.1 106 psi)

16.15 Compute the longitudinal strength of an aligned carbon fiber-epoxy matrix composite having a 0.25
volume fraction of fibers, assuming the following: (1) an average fiber diameter of 10 10-3 mm (3.94 10-4 in.),
(2) an average fiber length of 5 mm (0.20 in.), (3) a fiber fracture strength of 2.5 GPa (3.625 105 psi), (4) a fibermatrix bond strength of 80 MPa (11,600 psi), (5) a matrix stress at fiber failure of 10.0 MPa (1450 psi), and (6) a
matrix tensile strength of 75 MPa (11,000 psi).
Solution
It is first necessary to compute the value of the critical fiber length using Equation 16.3. If the fiber length
is much greater than l , then we may determine the longitudinal strength using Equation 16.17, otherwise, use of
c

either Equation 16.18 or Equation 16.19 is necessary. Thus, from Equation 16.3

lc =

f d
2 c

(2.5

103 MPa)(10 103 mm)

= 0.16 mm
2 (80 MPa)

Inasmuch as l >> lc (5.0 mm >> 0.16 mm), then use of Equation 16.17 is appropriate. Therefore,

= ' (1 V
cl
m
f

) + f V f

= (10 MPa)(1 0.25) + (2.5 103 MPa)(0.25)

= 633 MPa (91,700 psi)