Materials 100B Homework #3 Solution Set

Problem 1
You wish to produce a fiber reinforced composite (fibers aligned) with a Young's modulus E
along the fiber direction of 150 GPa. You have available glass fibers with an E of 75.9 GPa,
graphite fibers with an E of 552 GPa, and various polymer matrix materials, all with E ~ 3 GPa.
Since the glass fibers are significantly cheaper ~$10 m-3 than the carbon fibers ~$1000 m-3, your
boss wants you to make the composite from glass fibers and polymer matrix if possible. (At least
30% matrix is necessary to prevent the composite from being too brittle).
a)

Predict the largest E that can be obtained for a non-brittle composite of glass fibers and
polymer matrix.
Ans: The answer to this question is given by the rule of mixtures.
E|| = VfEf + VmEm
0.7*75.9 + 0.3*3 = 54 GPa

b)

Quantitatively suggest a minimum cost solution to obtain a composite with an E of 200

GPa along the fiber direction.
Ans: The answer to this question is to find the minimum amount of carbon fibers that will
give a total Youngs modulus of 200 GPa. The rest of the fibers (to make up 70 wt%) will
be glass. By generalizing the rule of mixtures, we find
E|| = VcfEcf + VgfEgf + VmEm
0.3*3 + 75.9*x + 552*y = 200
x + y = 0.70
So 39.3% glass fiber and 30.7% carbon fiber give a modulus of 200 GPa.
The cost can be computed from the given numbers for 1 m3
0.393*10 + 0.307*1000 = $311/m3

Problem 2
a) If the temperature is increased, which way (up or down) does the pointer move and why?
Ans: The pointer will move up. The stretching of the rubber band has decreased the its
entropy by causing the chain segments (mers) to align partially along the stretch
direction (entropy decrease => more order). The entropy decrease on stretching causes
the slope of the stress-strain curve (Young's modulus) to be directly proportional to the
absolute temperature, T.

T2 > T1

T1

Stress produced in rubber

band by steel spring

If we look at the steel spring as producing a constant

force (and thus a constant stress) in
the rubber band as the system is heated, it is clear from the figure that the rubber band
shrinks when heated (i.e. strain decreases). This shrinkage causes the pointer to go up.
b) What limits the temperature range within which this device will successfully operate as a
thermometer?
Ans: This device will work fine as a thermometer as long as the temperature does not
exceed the rubber band's decomposition temperature (where the mers in the strands in
the network break into small fragments) or drop below the rubber band's glass transition
temperature.
c) Will the pointer move in the direction you specified in (a) if the knife edge is lowered such
that both the steel spring and the rubber band are their original length? Why?
Ans: No, the pointer will hardly move and in the opposite direction (down). As
discussed for part (a), the driving force behind the rubber band contracting is entropy.
The movement depends on its being stretched. Under zero stretch, rubber expands when
heated like any other material.

Problem 3
Two non-crystalline, crosslinked polymers A and B (the network strand density of A is 3 times
that of B) are stretched in tension at room temperature, 300 K. By measuring the change in
internal energy U and entropy S of both upon stretching by the same factor, it is found that
U for polymer B is positive and S = 0, whereas U = 0 for polymer A and S is negative. At
400 K polymer B behaves like polymer A.
a) Describe the elastic properties of the two polymers at room temperature. Why does the
entropy of polymer A change when it is stretched?
Ans: Polymer A, upon stretching, shows no change in internal energy and a decrease
in entropy. This behavior is characteristic of rubber elastic or elastomeric
materials. The applied stress acts to straighten the polymer chains, increasing order
(S is negative), without supplying energy to the polymer bonds (U = 0).

Polymer B exhibits a positive U and no change in entropy upon stretching. This is

characteristic of an elastic materials in which the applied stress acts to stretch atomic
bonds without disrupting the atomic arrangement. Thus the entropy change is zero.
This behavior is typical of a glass and thus 300K is below Tg of polymer B. At 400K it
has U = 0 and S negative. Therefore, it is an elastomer like polymer A. For
polymer B, 300K < Tg < 400K.
b) Describe quantitatively the change in Youngs modulus E of polymer A as it is heated from
300 to 400 K.
Ans: Polymer A is an elastomer at both 300K and 400K. For such an elastomer,
E = 3xkBT.
So,
E400 = (400/300)E300 = (4/3)E300
c) Polymer A is stretched 100% at 300 K and held at constant length while it is heated. What is
the ratio of the force necessary to maintain the stretch at 400 K to that at 300 K?
Ans: The force is given by the expression
F = -T(dS/dL)
where T is the temperature and the term in parentheses is the change in entropy with
respect to polymer length. In this case, the length of the chain is fixed so the term in
parentheses is constant; therefore the ratio of the forces is simply the ratio of
temperatures.
F400/F300 = 400/300 = 4/3

Problem 4
Suggest a method to produce a shrinkable tubing which would have an initial large diameter so
that the wires could thread easily into it, but which upon heating with a hot air gun to 393K
would shrink down onto the wires. On cooling to room temperature the tubing must become
rigid and hold its shrunken dimensions.
Ans. Produce a crosslinked polymer tube with a Tg between RT (300K) and 393K.
Expand the tube circumference by passing it over a large diameter cylinder. Then cool to
room temperature without allowing the tube diameter to shrink. The strands will be
unable to coil back to their random walk shape because the coiling time in now very long
(T < Tg). On heating the tube above Tg, the coiling time is less than one second and the
tube shrinks onto the wire.

Problem 5
Design a new pole for pole vaulting which will have a Young's modulus of 138 GPa in the
longitudinal direction using 70% volume fraction of a polymer matrix (E = 7 GPa) and 30%
volume fraction of aligned fiber.
a) What minimum Young's modulus of the fiber is needed?
Ans: We consider a pole that has the fibers aligned along the length of the pole, the
stress will be in the direction parallel to the fibers, thus the relevant equation is
Ec|| = VfEf + (1-Vf)Em
we calculate the Ef, the minimum Young's modulus of the fiber to be
Ef = 444 GPa
b) A cap is force fit in the hollow shaft at each end of the pole. Is the circumferential modulus of
the pole the same as the modulus along the length of the pole? If not, estimate the
circumferential modulus. Also, give some fibers that have low densities and high moduli.
Ans:
i) This capping of the pole creates a stress that is perpendicular (or transverse) to the
direction of the fibers. Since a material containing aligned fibers is anisotropic the
modulus in the transverse direction will not be equal to that in the longitudinal direction.
We must use a different equation.
Ecircumferential ~ {(Vf / Ef) + [(1-Vf) / Em]}-1
Ecirc = 9.93 GPa
This value is much less than the longitudinal modulus which shows the inherent
anisotropy of composites with aligned fibers, particularly, that the materials have a
higher modulus parallel to the grain of the fibers than perpendicular to the grain of the
fibers. This anisotropy can be easily seen in natural composites such as wood.
ii) Viewgraph 6 of lecture 6 shows a chart of common fibers, their densities, and moduli.
Also table 25.1 in Ashby and Jones 2, pg. 264. Some good candidates are:
Kevlar - E = 185 GPa, d = 1.47 g/cm3 ; Carbon Fibers - E = 725 GPa, d = 2.15 g/cm3 ;
Boron Fibers - E = 415 GPa, d = 2.5 g/cm3 ; Also silicon carbide and silicon nitride
fibers.

Problem 6
Mark each of the following statements true or false: If the statement is true, say so. If it is false,
say why it is false and correct it. Less than half the credit will be given for the correct true or
false without correct reasoning as part of your answer.
a) Statement: An elastomer has no glass transition temperature because it is 100% crystalline.
Ans: False.
All polymers have a glass transition temperature (Tg) because polymers can never be
100% crystalline. The Tg is well below room temperature for a material that is a good
elastomer at room temperature. In addition, elastomers must be nearly 100%
amorphous. Otherwise, they would have energy elasticity, not entropy elasticity.
b) Statement: The glass transition temperature of a polyvinylchloride (PVC) garden hose is
usually well below room temperature, much less than the 80C Tg of a rigid PVC cold water
pipe, but the higher Tg of the water pipe is due to its higher number of crosslinks per unit
volume.
Ans: False.
The Tg of the PVC garden hose is below the room temperature because plasticisers are
added to it. These plasticisers, which are relatively small molecular weight organic
liquids, work by dissolving into the solid polymer and forcing the chains apart hence
making the chains easier to slide relative to one another and decreasing the coiling time.
The addition of plasticisers does not affect the cross-link density.
c) Statement: Viscoelasticity of polymers is caused by the time dependent breaking and
reforming of cross-links.
Ans: False.
Viscoelasticity is due to the time dependent coiling and recoiling of polymer chains and
does not involve the breaking or the reforming of cross-links.