# EMSE 201 — Introduction to Materials Science & Engineering Name

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5 May 2004

Final Exam — 180 minutes; 250 points; 6 questions; 12 pages; 25% of course grade
No calculators or formula sheets are allowed. Where numerical answers are requested, full credit will be given for correctly setting up the calculation and for specifying the correct units. 1) The unit cell of a compound of molybdenum (Mo) and silicon (Si) has the following characteristics: Mo: 0, 0, 0 1 1 1 , , 2 2 2 Si: 0, 0, 1 3 0, 0, 2 3 1 1 1 , , 2 2 6 1 1 5 , , 2 2 6

a = b = 0.3202 nm α = β = γ = 90°

c = 0.7851 nm
Si Mo

a) (6 points) In the space at right, sketch the unit cell. Clearly identify the atoms.

b) (4 points) How many atoms of each type are in the unit cell? Mo:

2

Si:

4 body-centered tetragonal

c) (4 points) What is the Bravais lattice of this structure?

d) (2 points) How many nearest-neighbor Si atoms does each Mo atom have? 10 1 1 1 1 1 1 1 (Hint: the Si atoms at 0, 0, and , , are almost exactly equidistant from the Mo atom at , , .) 3 2 2 6 2 2 2 e) (2 points) How many nearest-neighbor Mo atoms does each Si atom have? 5 Sketch the arrangement of atoms on the specified planes in this structure. Label the atoms in your sketches. f) (5 points) (100) g) (7 points) (110)

Si Mo

Si Mo

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h) (8 points) Set up the calculation of the density of this material. The atomic weights of Mo and Si are 95.94 and 28.09 g mol–1, respectively. Avogadro’s number is 6.023×1023 mol–1. density = (mass of atoms per cell)/(volume of cell) (2 pts) = (2AWMo + 4AWSi)/(ca2×N A) (4 pts) = (2×95.94 + 4×28.09)[g mol–1]/{(0.7851×.32022)[10–21cm3]×6.023×1023[mol–1]} (1 pt for inserting values; 1 pt for units) (This comes out to 6.275 g cm–3.)

i) (10 points) A compound of tungsten (W) and silicon forms with the same stoichiometry and structure as the compound discussed above. Would you expect these two compounds to form a continuous solid solution with each other? Evaluate each of the Hume-Rothery rules to justify your answer. atomic radius, nm 0.136 0.137 electronegativity 2.16 2.36 allowed valences 6, 5, 4, 3, 2 6, 5, 4, 3, 2

Mo W

Same structure (given): √ (1+1 pts) ∆r/r < 15%: √ (1+1 pts) ∆EN < 0.4: √ (1+1 pts) similar valences: √ (1+1 pts) Yes, we expect MoSi2 and WSi2 to form a continuous solid solution (2 pts) (and they do). Various properties of the Mo-Si compound are listed at right. j) (8 points) In what respect(s) does this compound behave like a ceramic? What aspects of the crystal structure might contribute to this behavior? Answer on next page. Melting point: 2230 °C Young’s modulus (25 °C): 430 GPa Ductility (25 °C): 0.0% Ductility rises rapidly with temperature above 1200°C Electrical conductivity (25 °C): 2.8×106 Ω–1 m–1 Electrical conductivity (1700 °C): 2.5×105 Ω–1 m–1

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The very high Young’s modulus (over twice that of steel, whose modulus is among the highest for metals) is typical of a ceramic (3 pts). The brittleness (zero ductility) at room temperature is also typical of a ceramic (3 pts). The alternating arrangement of Mo and Si atoms is ceramic-like (1 pt). The somewhat long c axis suggest that this material would have longer Burger’s vectors than simple metals (1 pt), which would lead to brittle behavior at room temperature (1 pt; 8 pts max). j) (8 points) In what respect(s) does this compound behave like a metal? What does this suggest about the bonding in this material? (The electronegativity of Si is 1.9 on Pauling’s scale, which ranges from 0.7 to 4.0 among all of the elements.) The high electrical conductivity is typical of a metal (2 pts), as is the slight decrease in this property with increasing temperature (2 pts). The appearance of ductility at high temperature is reminiscent of the brittle-toductile transition of body-centered metals, but occurring here at much higher temperatures (1200 °C vs. 0-100 °C for plain steels) (2 pts). The electrons are apparently delocalized as in metallic bonding of (1 pt), and the decrease of conductivity with increasing temperature suggests that the material does not have a band gap (1 pt). The low electronegativities of the elements (1 pt) and the low difference in electronegativities (1 pt; 8 pts max)) further suggest metallic bonding.

k) (6 points) Would you expect this material to have a thermal expansion coefficient closer to those of metals or to those of ceramics? Justify your answer. The high modulus (1 pt) and the high melting point (1 pt) suggest that this compound has a deep, narrow interatomic potential (2 pts), which would give it a low thermal expansion coefficient (2 pts), i.e. more like that of ceramics (2 pts) than metals (6 pts max).

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2) The hardness of a cylindrical rod of plain carbon steel (0.3 wt% C; 1.4" dia.) is plotted below as a function of radial distance from the perimeter. Given only this information, comment on the plausibility of the following possible explanations (PE1, PE2, PE3) for how this hardness profile was achieved. Justify your answer. You may find the charts on page 6 useful. a) (10 points) PE1: The rod had been carburized. This would lead to a higher concentration of carbon on the surface than in the interior (3 pts) (see Ch. 5 in Callister), which would raise the hardness of the surface relative to that of the interior (3 pts), as seen in the graph on the upper left of p. 6. So qualitatively PE1 moves in the right direction. (Callister, Fig. 8.38) However, according to the graph on the upper left of p. 6, simply raising the carbon content on the surface of this plain carbon steel without changing what phases are present would bring the Brinell hardness values up only to around 300 (2 pts), which according to the graphs on the right of p. 6 correspond to Rockwell C values of around 33 (2 pts). Also, it would take a very long time to diffuse carbon into steel to depths of 0.2” (2 pts), and the erf concentration profile wouldn’t level off near the surface as the hardness data do (2 pts). So quantitatively, PE1 is probably not the correct explanation (10 pts max).

b) (10 points) PE2: The surface of the rod had been cold worked (e.g. by surface machining). Cold-working the surface would lead to a higher concentration of dislocations on the surface (3 pts), which would raise the hardness of the surface relative to that of the interior (3 pts). So qualitatively PE2 also moves in the right direction. However, according to the graphs on the bottom of p. 6 (assuming the curve for 1040 steel is similar to that of this steel, which is probably an xx30 — 2 pts), cold work alone would raise the strength to around 130 ksi (2 pts), corresponding to RC hardness around 30 (2 pts), lower than those observed on the surface of the rod. Also, it is questionable that the hardening effect of surface machining (such as cutting of threads) would penetrate to 0.2” (2 pts). So quantitatively, PE2 is probably not the correct explanation (10 pts max).

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c) (10 points) PE3: The surface of the rod had been heated, then rapidly quenched. If the quenching is fast enough, martensite will form (3 pts), more likely on the surface, which will be cooled more rapidly than the interior (2 pts). Martensite can exhibit RC values between 50 and 60 for a steel of 0.3 wt% C (3 pts), matching the surface hardness here. In contrast, the interior region, which would have been quenched more slowly and therefore could have formed microconstituents like bainite or fine pearlite, would have RC values of 20 or below (2 pts), again consistent with the observed hardness profile. Heat transfer is faster than mass transfer in a metal, so it is more likely that the hardening effect of this treatment could penetrate to 0.2” than could a carburizing treatment (2 pts). PE3 is probably the correct explanation (10 pts max).

d) (10 points) Subsequent examination under the optical microscope shows that the rod’s surface consists of martensite, whereas the rod’s interior consists of ferrite, pearlite, and possibly bainite. Which of the three possible explanations now seems most plausible? Justify your answer. Martensite in steels is typically obtained only by quenching (2 pts), and bainite by fairly rapid cooling (2 pts) (or heating at temperatures below the nose of the TTT curve — an observation worth 1 pt, though it’s not directly relevant here). Where martensite and bainite did not form, the microstructure of a steel like this one containing 0.3 wt% C would consist of (proeutectoid) ferrite (2 pts) and pearlite (2 pts). The microstructure therefore supports PE3 (4 pts) as the most likely explanation for the hardness profile (10 pts max).

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3) A recent article in the Observer noted that the glaze on an ancient Chinese statue is cracked. A glaze is a thin layer of glass on the surface of a thicker polycrystalline ceramic piece. During firing, the glaze melts and flows, coating the ceramic evenly. a) (16 points) Explain how thermal stresses that arise during heat treatment of the glazed piece could have caused the cracks. Give the relevant equation for thermal stress in the glaze; define all terms and give units. If the thermal expansion coefficients of the glaze ( g) and the ceramic ( c) are different, they will contract at different rates during cooling (1 pt). Because the glaze is much thinner than the ceramic but bonded to it, the ceramic will impose that part of its dimensional change that is parallel to the glaze-ceramic interface on the glaze (1 pt). As long as the glaze is fluid, it will flow to accommodate the dimensional change (1 pt), but as it becomes rigid during cooling, the imposed strain will lead to stress in the glaze (1 pt). If ag<ac, the stress in the glaze will be compressive (1 pt); if g> c, the stress in the glaze will be tensile (1 pt). If the stress exceeds the glaze’s fracture strength (either in compression or in tension), the glaze will crack (1 pt). (The glaze’s fracture strength is probably lower than the shear strength of the glaze-ceramic interface, or else the glaze would debond from the ceramic rather than crack internally (1 pt).) (5 pts max.) The relevant equation is: σg = Eg(α c–α g)∆T (3 pts), where: σg is the stress in the glaze (Pa); Eg is the Young’s modulus of the glaze (Pa); α g and α c are the linear thermal expansion coefficients of the glaze and the ceramic (m m–1 K–1), respectively; and ∆T = T f – Ti is the difference between the final and initial temperatures (in K) over which stress is generated (1 pt each definition, 1 pt each units, 8 pts total).

b) (5 points) When will most of the stress develop: when the glaze is above its glass transition temperature Tg, or below Tg? Explain. Because the glaze can still flow above Tg (2 pts), little stress will develop until the glaze it is cooled below Tg, (2 pts) i.e. when it becomes rigid (2 pts; 5 pts max).

c) (12 points) Which of the following options (keeping everything else constant) would have reduced the probability that the glaze would crack? (Check all that apply.) (3 pts per correct check/uncheck)

√ √

Choosing a glaze with a thermal expansion coefficient closer to that of the ceramic. Choosing a glaze with a lower Tg. 7 of 12

Choosing a glaze with a higher Young’s modulus. Lower glaze modulus would decrease the likelihood of cracks. Choosing a ceramic with a higher Young’s modulus. No effect.
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EMSE 201 — Introduction to Materials Science & Engineering

5 May 2004

4) (40 points) The eight types of corrosion are: uniform attack, intergranular corrosion, galvanic corrosion, selective leaching, crevice corrosion, erosion-corrosion, pitting, and stress corrosion. Briefly explain the reasons for the following corrosion phenomena and identify which of the eight types of corrosion is chiefly responsible for each. a) A piece of magnesium, in electrical contact with steel pipe and buried underground with it, inhibits the corrosion of the pipe. When connected in this way, magnesium and steel form a galvanic couple (3 pts). Because magnesium is below iron in the standard emf series, magnesium will be the anode (3 pts). This is a case of exploiting galvanic corrosion (3 pts; 8 pts max) of the magnesium to protect the steel.

b) The steel in a heavily traveled bridge corrodes faster than that in a lightly traveled one. The bridge will be repeatedly loaded and unloaded as traffic moves over it. Any corrosion being experienced by the steel will be exacerbated by the stress (2 pts), because of the increased energy stored in elastic deformation (2 pts) and in dislocations during plastic deformation (2 pts). This is a case of stress corrosion (3 pts; 8 pts max).

c) Corrosion is observed to occur preferentially under steel washers on steel that has experienced prolonged exposure to water vapor. The moisture under the washers will become stagnant and depleted in oxygen (2 pts) because of its limited exposure to the surrounding atmosphere (1 pt). This sets up an oxygen concentration cell with the metal under the oxygen-depleted liquid being the anode (3 pts). This is a case of crevice corrosion (3 pts; 8 pts max).
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d) Exhaust gases that carry soot cause corrosion faster than soot-free exhaust gases. Corrosion by gases is worsened by the additional kinetic energy of the gas if it is flowing (2 pts). If the gas carries solid particles like soot, there is additional mechanical attack from the solid particles (2 pts), including the potential to wear away any protective oxide that may be present (2 pts). This is a case of erosion corrosion (3 pts; 8 pts max). There could also be erosion at work here, if we consider abrasion of the exposed surfaces by the passing traffic (2-4 pts).

e) Copper gutters on old buildings are covered with green copper salts. This is a case of continuous deposits (2 pts) forming over surfaces that are exposed to unchanging, uniform environments such as acid rain and polluted air (2 pts each). This is a case of uniform attack (3 pts; 8 pts max).

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5) a) (12 points) Sketch the mer structures for the following polymers: i) polyethylene ii) polypropylene iii) polyvinyl chloride iv) polystyrene

H H –C–C– H H

H CH3 –C–C– H H

H Cl –C–C– H H

H H –C–C– H

Mechanical properties for these four polymers at room temperature are listed below. tensile modulus, GPa polyethylene, high-density 1.1 polypropylene 1.1-1.6 polyvinyl chloride 2.4-4.1 polystyrene 2.3-3.3 tensile strength, MPa 22-31 31-41 41-52 36-52 yield strength, MPa 26-33 31-38 41-45 — elongation at break, % 10-1200 100-600 40-80 1.2-2.5

b) (12 points) The glass transition temperatures Tg for these polymers (in no particular order) are 100, –90, 87, and –18 °C. Considering the values of modulus, strength, and elongation, match each polymer with its Tg . Justify your answers. The farther a polymer is above its Tg, the lower its strength and the higher its elongation; vice versa for a polymer below its Tg. HDPE: –90 °C (highest elongation, lowest strength and modulus) (3 pts) PP: –18 °C (high elongation, low strength and modulus) (3 pts) PVC: 87 °C (low elongation, high strength and modulus) (3 pts) PS: 100 °C (lowest elongation, high strength and modulus) (3 pts)

c) (12 points) Further support your assignment of Tg for these polymers on the basis of their structures. Given the same degree of linearity/crosslinking (all of these are linear polymers — 2 pts) and the same type of chain (here, straight -C-C-C-; 2 pts), simple mer structures usually lead to low Tg (2 pts) and bulkier side groups tend to raise Tg (2 pts). All of this indicates that Tg should increases from HDPE to PP to PVC to PS (4 pts).

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d) (10 points) Many consumer products (shampoos, lotions, medicines) come in containers of highdensity polyethylene with caps of polypropylene. Justify these material selections on the basis of the mechanical properties of these two polymers. PP is more rigid (1 pt) and strong (1 pt) — appropriate for the part of the package that must grip the opening (1 pt) and seal tightly (1 pt). HDPE is more flexible (1 pt) and ductile (1 pt), making it easy both to squeeze (1 pt) and to fabricate into complex shapes (1 pt). With the Tg of both polymers below room temperature (1 pt), they will be ductile enough to be tough (1 pt) and not brittle (1 pt).

6) (21 points) Pick one of the Materials in the News topics that was presented in class or posted to the web site this semester or previously (not one that you handed in). Discuss how that topic illustrates one or more of the legs of the “Materials Tetrahedron”: processing-performance, structure-performance, or properties-performance.

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EMSE 201 — Introduction to Materials Science & Engineering Name:

5 May 2004

SOLUTION

TOTAL:

1

/70 2

/40 3

/33 4

/40

5

/46 6

/21

/250

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