MECH340

Materials Science and Engineering

Prof. Darwish, M.

Homework 7

Mirvat Shamseddine (201010644)

Section: 02

Problem 14.3:
Given: the number-average molecular weight:

M n 1,000,000 g/mol
We have to find the degree of polymerization DP. The degree of polymerization is given by the equation:

DP =

Mn m

, where m is the repeat unit molecular weight

For polypropylene each repeat unit consists of three carbon atoms and 6 hydrogen atoms. Thus, the repeat unit molecular weight of polypropylene is given by: m = 3(atomic weight of carbon) + 6(atomic weight of hydrogen) = (3)(12.01 g/mol) + (6)(1.01 g/mol) = 42.09 g/mol

Hence DP will be equal to:

DP =

M n 1,000,000 g/mol = = 23,759 m 42.09 g/mol

Problem 14.5:
Given: Molecular weight table list for a polypropylene material and we have to find: a) Mn , the number-average molecular weight b) M w , the weight-average molecular weight c) DP, the degree of polymerization Parts: a, b)

Molecular wt Range 8,000-16,000 16,00024,000 24,00032,000 32,00040,000 40,00048,000 48,00056,000 a)

Mean Mi 12,000 20,000 28,000 36,000 44,000 52,000

xi 0.05 0.16 0.24 0.28 0.20 0.07

wi 0.02 0.10 0.20 0.30 0.27 0.11

xiMi 600 0.05 3200 6720 10,080 8800 3640

wiMi 600 240 2000 5600 10,800 11,800 5720

Mn , the number-average molecular weight

M n = xi M i = 33, 040 g/mol

b)

M w , the weight-average molecular weight

M w = wi M i = 36,240 g/mol

c) For polypropylene each repeat unit consists of three carbon atoms and 6 hydrogen atoms. Thus, the repeat unit molecular weight of polypropylene is given by: m = 3(atomic weight of carbon) + 6(atomic weight of hydrogen) = (3)(12.01 g/mol) + (6)(1.01 g/mol) = 42.09 g/mol

Hence DP will be equal to:

DP =

M n 33,040 g/mol = = 785 m 42.08 g/mol

Problem 14.13: Thermoplastic and thermosetting polymers:

(a) Thermoplastic polymers soften when heated and harden when cooled. On the molecular level, when the temperature is raised, secondary bonding forces are diminished so that the relative movement of adjacent chains is facilitated when a stress is applied. They can be heat-softened (melted) to process into a desired form, whereas thermosetting polymers harden upon heating, while further heating will not lead to softening. They cannot be heat-softened (melted). (b) Thermoplastic polymers have linear and branched structures, the polymer chains can be free to slide past one another. Thermosetting polymers; the structures will normally be network or cross linked. The polymer chains can be connected to each other with crosslinks.

Problem 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) No, phenol-formaldehyde is a network thermoset polymer which is not amenable to remolding. Thus, it is not possible to be grinded up and reused. They are formed into a permanent shape and are cured (set) by a chemical reaction that may require heat and pressure. Thermoset polymers are typically insoluble, and cannot be remelted or reformed into another shape after curing. Decompose when heated; thus, cannot be reformed or recycled. Presence of extensive crosslinks between long chains induces decomposition upon heating and renders thermosetting polymers brittle.

b) Yes, polypropylene since it is a thermoplastic polymer will soften when reheated, and, thus, may be remolded. Thermoplastic polymers that flow when heated; thus, easily reshaped and recycled. Thus it is possible to be grinded up and reused. This property is due to presence of long chains with limited or no crosslinks. In a thermoplastic material the very long chain-like molecules are held together by relatively weak Van der Waals forces. When the material is heated the intermolecular forces are weakened so that it becomes soft and flexible and eventually, at high temperatures, it is a viscous melt (it flows). When the material is allowed to cool it solidifies again.

Problem 15.8:
On the basis of the curves in Figure 15.5, sketch schematic straintime plots for the following polystyrene materials at the specified temperatures: (a) Amorphous at 120C (b) Crosslinked at 150C (c) Crystalline at 230C (d) Crosslinked at 50C

Solution
(a) Amorphous polystyrene at 120oC 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 oC behaves as a viscoelastic material (Figure 15.8, curve B). For the intermediate viscoelastic behavior, the imposition of a stress in the manner of Figure 15.5a results in an instantaneous elastic strain, which is followed by a viscous, time-dependent strain, a form of anelasticity. Therefore, the strain-time behavior will be as Figure 15.5c. (c) Crystalline polystyrene at 230 oC behaves as a viscous liquid (Figure 15.8, curve A). For totally viscous behavior, deformation or strain is not instantaneous; that is, in response to an applied stress, deformation is delayed or dependent on time. Also, this deformation is not reversible or completely recovered after the stress is released. Therefore, the strain-time behavior will be as Figure 15.5d. (c) Crosslinked polystyrene at 50 oC behaves in a glassy manner (Figure 15.8, curve B); Elastic deformation is instantaneous, which means that total deformation (or strain) occurs the instant the stress is applied or released (i.e., the strain is independent of time). In addition, upon release of the external stress, the deformation is totally recoveredthe specimen assumes its original dimensions. Therefore, the strain-time behavior will be as Figure 15.5b

Problem 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 chaininduced crystallinity, and a reduction in interchain bonding forces.

Problem 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 increase in its tensile strength. produces an