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1. The following table lists molecular weight data for some polymer. Compute

(a) the number-average molecular weight,

(b) the weight-average molecular weight.

(c) If it is known that this material's degree of polymerization is 1165, which one of the polymers listed

in Table 14.3 is this polymer? Why?

Molecular Weight

Range g/mol

15,00030,000

30,00045,000

45,00060,000

60,00075,000

75,00090,000

90,000105,000

105,000120,000

120,000135,000

xi

0.05

0.07

0.16

0.24

0.26

0.12

0.08

0.02

wi

0.02

0.04

0.11

0.20

0.27

0.16

0.12

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.

Range

Mean Mi

xi

xiMi

15,000-30,000

22,500

0.05

1125

30,000-45,000

37,500

0.07

2625

45,000-60,000

52,500

0.16

8400

60,000-75,000

67,500

0.24

16,200

75,000-90,000

82,500

0.26

21,450

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

0.02

2250

_________________________

M n = xi M i = 72,750 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.

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MANE/ENGR 2220

Range

Mean Mi

wi

wiMi

15,000-30,000

22,500

0.02

450

30,000-45,000

37,500

0.04

1500

45,000-60,000

52,500

0.11

5775

60,000-75,000

67,500

0.20

13,500

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

_________________________

M w = wi M i = 78,975 g/mol

(c) We are now asked if the degree of polymerization is 1165, which of the polymers in Table 14.3 is this material?

It is necessary to compute m in Equation 14.6 as

m=

Mn

72,750 g/mol

=

= 62.45 g/mol

DP

1165

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, Poly(vinyl chloride) is the material since its repeat unit molecular weight is closest to that calculated above.

2. The density and associated percent crystallinity for two polymer materials are as follows:

(g/cm3)

1.132

crystallinity (%)

51.3

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MANE/ENGR 2220

1.215

64.2

(a) Compute the densities of totally crystalline and totally amorphous polymer.

(b) Determine the density of a specimen having 53.8% crystallinity.

Solution

(a) We are asked to compute the densities of totally crystalline and totally amorphous polymer (c and a from

Equation 14.8). From Equation 14.8 let C =

% crystallinity

, such that

100

C =

c ( s a )

s (c a )

c (C s s ) + ca C sa = 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

c (C1 s1 s1) c a C1 s1 a 0

c (C2 s2 s2 ) ca C2 s2a 0

In which s1 = 1.132 g/cm3, s2 = 1.215 g/cm3, C1 = 0.513, and C2 = 0.642. Solving the above two equations for a and

c leads to

(C C2 )

a s1 s2 1

C1 s1 C2 s2

= 0.89 g/cm 3

3

3

And

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MANE/ENGR 2220

c =

s1 s2 (C 2 C1)

s2 (C 2 1) s1(C1 1)

= 1.525 g/cm 3

(1.215 g/cm 3 )(

0.642 1) (1.132 g/cm 3 )(0.513 1)

(b) Now we are asked to determine the density of a specimen having 53.8% crystallinity. Solving for s from

Equation 14.8 and substitution for a and c which were computed in part (a) yields

s =

c a

C (c a ) c

= 1.147 g/cm3

3. 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

30,000

170

60,000

Estimate the number-average molecular weight that is required to give a tensile strength of 185 MPa.

Solution

This problem gives us the tensile strengths and associated number-average molecular weights for two poly(methyl

methacrylate) materials.

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:

170 MPa = TS

A

30,000 g / mol

A

60,000 g / mol

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MANE/ENGR 2220

Thus, the values of the two constants are: TS = 233 MPa and A = 3.78 106 MPa-g/mol. Substituting these values into

Equation 15.3 leads to

185 =TS

= 233 MPa

Mn

A

g / mol

M n g / mol

M n = 78750 g/mol

4. In a continuous and aligned fiber-reinforced composite, the fibers are to carry 84% of a load

Aramid fiber

Polycarbonate

Modulus of Elasticity

[GPa (psi)]

Tensile

Strength

[MPa (psi)]

2.4 (3.5 105)

3600 (520,000)

65 (9425)

(b) The stress on the polycarbonate matrix when the aramid fibers fail is 45 MPa (6500 psi).

Compute the tensile strength of this composite.

Solution

(a) Given some data for an aligned and continuous fiber-reinforced composite, we are asked to compute the

volume fraction of fibers that are required such that the fibers carry 84% of a load applied in the longitudinal direction.

From Equation 16.11

Ff

Fm

Ef Vf

EmVm

Ef Vf

Em (1 V f

Ff

Fm

0.84

= 5.25

0.16

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MANE/ENGR 2220

And when we substitute the given values for Ef and Em into the first equation leads to

Ff

= 5.25 =

Fm

(131GPa )V f

( 2.4 GPa )(1V f )

(b) We are now asked for the tensile strength of this composite. From Equation 16.17,

= ' (1 V

cl

m

f

+ f V f

= (45 MPa)(1

0.087) + (3600 MPa)(0.087)

= 354.285 MPa

since values for

(3600 MPa) and 'm (45 MPa) are given in the problem statement.

5. Compute

the volume fraction of fibers of an aligned glass fiber-epoxy matrix in which the average

are 1.2 10-2 mm and 1 mm, respectively and longitudinal tensile strength is

fiber diameter and length

750 MPa. Assume that (1) the fiber fracture strength is 5000 MPa; (2) the fiber-matrix bond strength is

25 MPa; and (3) the matrix stress at fiber failure is 10 MPa.

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 lc, then we may determine Vf using Equation 16.17, otherwise, use of either Equation 16.18 or Equation 16.19

is necessary. Thus,

lc =

f d

2 c

= 1.20 mm

2 (25 MPa)

Inasmuch as l < lc (1.0 mm < 1.20 mm), then use of Equation 16.19 is required. Therefore,

=

cd'

750 MPa =

l c

d

V f + m' (1 V f )

0.012 103 m

(V f )

+ (10 MPa)(1 V f )

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MANE/ENGR 2220

Solving this expression for Vf leads to Vf = 0.357.

6. A continuous and aligned fiber-reinforced composite having a cross sectional area of 940 mm 2 is

subjected to an external tensile load. If the volume fraction of fibers is 0.37, determine the moduli of

elasticity of fiber and matrix phases. The moduli of elasticity in the longitudinal and transverse

directions are 19.7 and 3.66 GPa, respectively.

Solution

This problem asks for us to compute the elastic moduli of fiber and matrix phases for a continuous and aligned

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

+ Ef Vf

And

Ect =

3.66

GPa =

(1

EmE f

V f ) E f V f Em

Em E f

(1 0.37 ) E f 0.37 E m

E m = 6.4 GPa

E f = 42.34 GPa

7. Using the definitions for total chain molecule length, L, ( L = Nd sin , where d is the bond

2

length between chain atoms, N is the total number of bonds in the molecule and is the angle between

adjacent backbone chain atoms) and average chain end-to-end distance r, ( r = d N ), for a linear

polyethylene determine:

(a) the number-average molecular weight for L = 1500 nm;

(b) the number-average molecular weight for r = 15 nm.

7 of 9

MANE/ENGR 2220

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 1500 nm. It is first necessary to compute the value of N using this equation,

where, for the CC chain bond, d = 0.154 nm, and = 109. Thus

N =

L

d sin

2

1500 nm

=

= 11,964

(0.154 nm) sin 109

2

Since there are two CC bonds per polyethylene repeat unit, there is an average of N/2 or 11,964/2 = 5982 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)

Therefore

(b) Next, we are to determine the number-average molecular weight for r = 15 nm. Solving for N from Equation

14.12 leads to

N=

r2

(15 nm) 2

=

= 9487

d 2 (0.154 nm) 2

which is the total number of bonds per average molecule. Since there are two CC bonds per repeat unit, then DP = N/2 =

9487/2 = 4743. Now, from Equation 14.6

8. Compute repeat unit molecular weights for the following: (a) polystyrene, (b) poly(ethylene

terephthalate), (c) polycarbonate, and (d) polydimethylsiloxane, (e) polypropylene.

8 of 9

MANE/ENGR 2220

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) 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

(e) 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

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