EMSE 201 Introduction to Materials Science & Engineering Name:

4 May 2005

SOLUTION

Final Exam 180 minutes; 288 points; 11 questions; 11 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) (10 points) Austenite is slightly denser than martensite. Use this fact to explain why it is difficult to convert large or thick steel parts into martensite. For thick cross-sections of material, there will be temperature gradients (2 pts) during the quench. This means that the less rapidly quenched inner sections will transform to martensite later than the more rapidly quenched outer sections (2 pts). It also means that the degree of the martensite transformation (0% to 100%) will vary with time and with distance from the surface during the quenching (2 pts). Because the austenite-to-martensite transformation entails an increase in volume (2 pts), the regions that have transformed will be under compression, and the regions that are still austenite will be in tension (3 pts). These stresses may be enough to crack the brittle martensitic portions of the part (2 pts) or to plastically deform the ductile austenitic portions (2 pts). (Up to 5 pts extra credit as shown.)

2) Use the diagram at right to specify a heat treatment (temperature(s) and time(s)) that would impart the following microstructures to eutectoid steel: a) (4 points) 100% fine pearlite For each step: 2 pts time + 2 pts T. For a) and b): Start from 100% austenite above the eutectoid temperature (1 pt). For part a): Anything past the 100% curve in the lower part of the P field, e.g. 10 s at 560 C b) (10 points) 50% coarse pearlite, 25% bainite, 25% martensite 1st step: Hold at the 50% curve in the upper part of the P field, e.g. 100 s at 680 C 2nd step: Rapidly cool to, and hold at, a temperature at the 50% curve in the bainite field, e.g. 10 s at 450 C .
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3rd step: Quench to below 100 C.

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3) An electrochemical cell is set up at 25 C with one electrode of pure zinc immersed in a solution of Zn2+ ions, and the other electrode of pure chromium in a solution of Cr3+ ions. Data from the standard EMF series relevant to this problem are given below: Electrode reaction O2 + 2H 2O + 4e !! 4(OH ) " 3+ Cr + 3e !! Cr " 2+ Zn + 2e !! Zn " Standard electrode potential, V (Volts) +0.401 0.744 0.763

a) (4 points) If the two solutions are 1.0 M in their respective metals, compute the voltage that is generated. Which metal will corrode? More anodic species have lower (or more negative) V Zn will corrode (2 pts) Writing the Zn half-cell reaction in reverse and scaling it to balance electrons: 3 3 Cr 3+ + Zn !! Cr + Zn 2+ V = 0.744 (0.763) +0.019 V (2 pts) " 2 2

b) (10 points) Suppose that the two solutions have negligible concentrations of dissolved salts but different concentrations of dissolved oxygen. To cause the electrochemical reaction to run in the opposite direction from that of part a), which side of the cell must have a higher concentration of dissolved oxygen? Write the resulting half-cell reactions. Briefly justify your answer. In oxygen concentration cells, oxygen reduction (e.g. the first reaction listed in the table above) will proceed to a greater extent on the side of the cell with the higher concentration of dissolved oxygen (3 pts), driven by the tendency to equalize the oxygen concentrations on both sides of the cell. This makes that side of the cell the cathode (i.e., where electrons are consumed, per the oxygen reduction reaction as written in the table) (1 pt) and the other side of the cell the anode (i.e. where electrons are generated) (1 pt). In part a), Zn is the anode. To reverse the direction of the reaction in part a), the oxygen concentrations must be such as to make Zn the cathode and Cr the anode. Therefore, the concentration of dissolved oxygen would need to be higher on the Zn side of the cell (3 pts). In summary (1 pt for each reaction): cathode reaction: O2 + 2H 2O + 4e !! 4(OH ) +0.401 " 4 4 anode reaction: (0.744) Cr !! Cr 3+ + 4e " 3 3 " Note: the half-cell reaction Zn 2+ + 2e !! Zn can occur at the high-oxygen 2+ ions on that side of the cell. Here the electrode if there is a source of Zn conditions specified that the concentrations of dissolved salts on both sides of the cell were negligible.

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4) (24 points) Briefly describe the mechanisms underlying the following corrosion phenomena and identify which of the eight types of corrosion is chiefly responsible for each. a) A thin coating of zinc protects underlying plain carbon steel from corrosion. With no electrical barrier between the Zn and the steel, they form a galvanic couple (3 pts). Because zinc is below iron in the standard emf series (as discussed in lecture and the reading), zinc will be the anode (1 pt) and will therefore be oxidized, while steel will be the cathode and therefore will be kept in a reduced state (1 pt). This is a case of exploiting galvanic corrosion (3 pts) of the zinc to protect the steel. In fact, steel treated this way is said to be galvanized. Note that the zinc layer provides more than just a barrier to corrosion of the steel. Even where the steel might be exposed, for example at a scratch through the zinc coating, the corrosion of the zinc provides electrons to the steel to keep it reduced (i.e, in the metallic form rather than oxidized).

b) A metal bar, after being bent as shown at right and immersed in seawater, exhibits cracking preferentially at the bend. The bar is under stress, and the stress is highest at the bend (2 pts). The stored elastic (1 pt) and plastic (1 pt) energy will be highest there, as will the dislocation density (2 pts). This leads to enhanced corrosion at the bend (2 pts), with subsequent weakening and cracking. This is a case of stress corrosion (3 pts; 8 pts max).

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4) c) Pipes carrying turbulent flows exhibit greater corrosion than those carrying non-turbulent flows. This is an example of erosion-corrosion (3 pts). Turbulent flows carry greater mechanical energy than laminar (non-turbulent) flows (2 pts). Some of this mechanical energy is transferred to the pipe, which can break down and continuously remove protective oxide that might be forming on the metal (3 pts).

5) (20 points) The Rockwell family of tests comprises the most common type of indentation hardness tests for metallic engineering materials. Briefly describe the most important characteristics of Rockwell hardness tests. State three advantages of this family of tests that contribute to their widespread use in industry. (The following is a more thorough answer than was expected, so extra credit was possible as indicated.) In Rockwell hardness tests, an indenter is seated with a low specified load (the minor load) (1 pt) and then vertically impressed under a larger specified load (the major load) (2 pts) into the specimen. The greater the depth of the indentation, the lower the hardness reading (2 pts). The 30 different tests (2 pts) in the Rockwell family differ in the type of indenter (a hardened ball of one of four possible sizes for the so-called standard tests (2 pts), or a diamond cone (2 pts) for the so-called superficial tests ) and in the size of the major load (three different possible values using ball indenters (1 pt) and three using the diamond cone (1 pt)). The scales for all of the tests are dimensionless (1 pt) and range from zero to 130 (1 pt), but are most accurate from about 20 to about 100 (2 pts). The advantages of Rockwell tests are: the versatility of the instrument (2 pts) (a single machine can perform all 15 standard tests, and another machine can perform all 15 superficial tests); the sensitivity of each scale to a particular range of hardness (2 pts); the speed with which multiple measurements can be made (2 pts); the objectivity and ease of the reading (1 pt) (read directly off a dial or display, with no calculations and little room for user error); and the ease with which the testing can be automated (1 pt).

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EMSE 201 Introduction to Materials Science & Engineering

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6) (36 points) Polymers have very low thermal conductivities: typically 0.2-0.5 W m1 K1, compared to 10-50 W m1 K1 for most ceramics and 20-400 W m1 K1 for metals. Check () which of the following statements (all of which are true) contribute to the low thermal conductivity of polymers. Justify each answer with one sentence. 3 pts correctly checked or unchecked; 3 pts explanation. a) The bonds along the macromolecular backbone are strong, usually saturated, and covalent. Normally, strong covalent bonding contributes to high thermal conductivity, as in diamond. In polymers, this effect is thwarted by the weak bonding between the macromolecules (see b) and, in network polymers, by non-crystallinity of the network, giving low mean free path (see e).

b)

The bonding between the macromolecules is usually of the van der Waals type.

Van der Waals bonds are relatively weak, which leads to weak coupling of phonons between the molecules and a low overall phonon velocity v. (Recall that for each mode of thermal conduction, the thermal conductivity can be expressed as 1 ! = cV v" (the other terms are defined below). 3

c)

The heat capacities per unit volume of polymers are relatively low.

Phonon thermal conductivity is proportional to the heat capacities per unit volume, cv (equal to the specific heat times the density). (You can check these number in Callisters Appendices B1 and B8. The specific heats of polymers are high compared to metals, but their densities are much lower, giving them low cv.)

d)

Most polymers are electrically insulating.

= el + phon (+ phot if the material is transparent). The dearth of conduction electrons in electrically insulating polymers means that electronic heat conduction is negligible, which will contribute to low thermal conductivity overall.

e)

In non-crystalline regions of polymers, the mean free path for thermal carriers will be very low, on the order of an atomic distance.

Phonon thermal conductivity is proportional to the phonon mean free path . The more non-crystalline the polymer, the lower its thermal conductivity.

f)

The elastic moduli of polymers are relatively low.

Phonon velocity v is proportional to (E/)1/2, where E is the elastic modulus and is the density. Because phonon thermal conductivity is proportional to phonon velocity, low modulus contributes to low phonon thermal conductivity.

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7) Sketch typical engineering stress-strain curves for the following materials: a) (5 points) a ductile metal such as brass b) (5 points) a semicrystalline polymer above its glass transition temperature

Contrast these two categories of materials with respect to: c) (12 points) typical values (one significant digit and order of magnitude, plus units) of elastic modulus, yield strength, and strain to failure at room temperature Answers in the following ranges were acceptable. Value: 1.5 pts per answer; units (either SI or English): 0.5 pt per answer Property Metals Semicrystalline polymers Elastic modulus 100-200 GPa 10,0000.2-4 GPa 25-600 ksi 30,000 ksi Yield strength 100-1000 MPa 15-150 ksi 20-50 MPa 3-7 ksi Strain to failure 5-60% 5-1000% d) (10 points) change in shape of a specimen at the early, middle, and late stages of a tensile test See the insets in the figures above. The key features are: in both, initially uniform elongation and diameter reduction in the elastic region (2 pts); in metals, uniform elongation and diameter reduction also in the early stages of plastic deformation (1 pt), with the onset of necking coinciding with reaching the ultimate tensile strength (2 pts), followed by failure at the neck (1 pt); whereas in polymers, the onset of localized area reduction corresponds to a yield point (local maximum in the engineering stress-strain curve) (2 pts), followed by growth of the region of reduced cross-section until it consumes the whole gage length (2 pts), sometimes coinciding with a strengthening of the polymer (upward slope of the stress-strain curve) (1 pt).

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EMSE 201 Introduction to Materials Science & Engineering

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7) e) (20 points) mechanism of plastic deformation on an atomic or molecular level The mechanism of plastic deformation in metals is slip (3 pts), i.e. the movement of dislocations in response to applied stresses (3 pts). Slip usually occurs most readily along particular directions and on particular planes in a material, based on a property called the critical resolved shear stress (2 pts) for each combination of direction and plane (known as a slip system) (2 pts). The mechanisms of plastic deformation in semicrystalline polymers consist of tilting of the crystalline lamellae (3 pts), separation of crystalline block segments from the lamellae (3 pts), and reorientation of the blocks (2 pts) and the tie molecules (2 pts) along the tensile axis (see Figure 15.12 in Callister).

8) (22 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, structureperformance, or properties-performance.

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EMSE 201 Introduction to Materials Science & Engineering

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9) The mineral spinel has the nominal composition MgAl2O4. The crystal structure consists of O2 anions in an FCC arrangement, with cations occupying tetrahedral and octahedral interstices. a) (8 points) For the composition MgAl2O4, assuming all Mg2+ cations in tetrahedral interstices and all Al3+ cations in octahedral interstices, what fractions of the tetrahedral and octahedral interstices are occupied? 2 tetrahedral sites per oxygen anion (2 pts) 8 tetrahedral sites per spinel formula unit. 1 Mg ion per formula unit to occupy the tetrahedral sites 1/8 of the tetrahedral sites are occupied (2 pts). 1 octahedral site per oxygen anion (2 pts) 4 tetrahedral sites per spinel formula unit. 2 Al ions per formula unit to occupy the octahedral sites 1/2 of the tetrahedral sites are occupied (2 pts). b) (8 points) Given the values of the cationic radii (rMg2+ = 0.057 nm; rAl3+ = 0.0535 nm), would you expect Mg2+ to be in tetrahedral sites and Al3+ to be in octahedral sites? Explain. (The radius of the oxygen ion in this structure is 0.138 nm. (The CN of O in spinel is non-tetrl 4.) Octahedral sites are larger than tetrahedral (2 pts). Size alone would indicate a higher or the same coordination number for the larger Mg cation, not smaller as is observed (4 pts). Considering the radius ratio concept more critically (see p. 6.8 in the Polyatomic Structures overheads), we recall that in the upper end of each of the ranges of radius ratio, the next higher coordination number is favored (2 pts). (In this case, both Mg and Al are just below the borderline between four-fold and six-fold coordination, so six-fold in fact favored by these geometric-electrostatic considerations.) Partial covalency of the bonds (as virtually always occurs) may further weigh against the simple radius-ratio prediction (2 pts; 8 pts max). Spinel exhibits significant solid solubility for both MgO and Al2O3, as shown in the phase diagram below. (The composition MgAl2O4 corresponds to 50.0 mol% Al2O3 and 71.7 wt% Al2O3.) In these solid solutions, point defects such as magnesium cations on aluminum sites and aluminum cations on magnesium sites occur to accommodate the deviation in composition from MgAl2O4. c) (10 points) For spinel with greater than 50.0 mol% Al2O3, what type(s) of point defects will accommodate this nonstoichiometry? How many such defects will occur per excess formula unit of Al2O3? Assume that all oxygen ions occupy oxygen sites. Consider 4 excess Al2O3 formula units 12 new O sites filled 3 new spinel f. u. worth of sites added. This includes 6 new Al sites and 3 new Mg sites. Were adding 8 aluminum ions. 6 can go on the new Al sites, 2 can go on the new Mg sites (2 AlMg per 4 Al2O3 f.u.), leaving one of those sites empty i.e., 1 VMg for every 4 Al2O3 f. u.
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Another possibility, though less likely because it generates so many more point defects, is for the two remaining new Al ions to go into interstitial positions (e.g. some of the unoccupied octahedral sites), leaving three Mg vacancies.

9) d) (10 points) For spinel with greater than 50.0 mol% MgO, what type(s) of point defects will accommodate this nonstoichiometry? How many such defects will occur per excess formula unit of MgO? Again, assume that all oxygen ions occupy oxygen sites. Consider 3 MgO f.u. 1 Mg on a new Mg site, 2 Mg on new Al sites, 3 O on 3 of the 4 new O sites, leaving 1 oxygen vacancy, i.e. 2 MgAl and 1 VO per 3 MgO f.u. Another possibility, this one quite likely: 4 MgO f.u. 4 O sites filled, 1 Mg on a Mg site, 2 Mg on Al sites, and one Mg interstitial (e.g. some of those unfilled tetrahedral sites), i.e. 2 MgAl and 1 Mgi per 4 MgO f.u. (Full credit was given for either approach.) e) For MgO-Al2O3 ceramic with overall composition 38.8 wt% Al2O3 (20.0 mol% Al2O3), sketch the microstructures that would occur at the following temperatures during equilibrium solidification from above the liquidus temperature. Identify all phases in your sketch and give their compositions in wt% Al2O3. Set up the computations for the fractions of each phase (in wt%). i) (10 points) Just above 2000 C This is just above the eutectic temperature. The microstructure will consist of primary MgO dendrites (2 pts) in liquid (2 pts); see Callister Fig. 9.14, sketch l. MgO solid solution: 211 wt% Al2O3, 791 wt% MgO (1 pt) Liquid: 531 wt% Al2O3, 471 wt% MgO (1 pt) ii) (10 points) Just below 2000 C This is just below the eutectic temperature. The microstructure will consist of primary MgO dendrites (1 pt) in eutectic MgO + spinel (3 pts); see Callister Fig. 9.14, sketch m. MgO solid solution: 211 wt% Al2O3, 791 wt% MgO (1 pt) spinel: 621 wt% Al2O3, 381 wt% MgO (1 pt) 9 of 11 Wt% MgO ss: (6238.8)/(62-21) (2 pts) Wt% spinel: (38.821)/(6221) (2 pts) Wt% solid: (5338.8)/(53-21) (2 pts) Wt% liquid: (38.821)/(5321) (2 pts)

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EMSE 201 Introduction to Materials Science & Engineering

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10) (20 points) The electron configuration of Cu is (Ar)3d104s1 and that of Zn is (Ar)3d104s2. What does this suggest about the degree of occupancy of the bands in copper metal and in zinc metal? Account for the metallic electrical conductivity of copper and zinc in terms of probable features of their band structures. Atomic copper has filled shells up to and including 3d (1 pt), with a half-filled 4s valence shell (1 pt). This suggests that, in the absence of hybridization, bands up to and including 3d are filled (2 pts), and the valence band is the half-filled 4s band (2 pts). Half-filled valence bands impart metallic conductivity because the empty states in the upper portion of the band are readily accessible to the electrons near the Fermi level, without their having to cross a gap (4 pts). Atomic zinc has filled shells up to and including 4s (2 pts). In the absence of hybridization, bands up to and including the 4s valence band will be filled (3 pts). The empty 4p level in the free atom broadens out into a band in the solid (1 pt). The 3s and 4p states in the free atom are close enough in energy that the corresponding bands in the solid overlap (3 pts). This makes empty states accessible to electrons in the filled 3s band, again without their having to cross a gap (1 pt).

11) Callister, 18.D5 An integrated circuit design calls for diffusing boron from the surroundings into very high purity silicon at a constant elevated temperature. During the diffusion treatment, the concentration of B at the surface of the Si will be maintained at a constant level of 1.01025 m3. a) (3 points) Check () all of the following statements that apply to this diffusion treatment: i) The diffusion will be steady-state. ii) The thin-film solution to Ficks laws will apply.

iii)

The error-function solution to Ficks laws will apply. 1 pt per correctly checked or unchecked item

b) (17 points) According to the design requirements, at a distance 0.2 m from the surface of the silicon wafer, the room-temperature electrical conductivity must be 1000 1 m1. The diffusion treatment is to last 1.0 h. Given the data below and on the next page, describe how to determine the temperature of the heat treatment that would be necessary to achieve the design goals.

" 347kJ / mol % diffusion coefficient for B in Si (in m2 s1): D = 2.4 !10 4 exp $ ' # & RT
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EMSE 201 Introduction to Materials Science & Engineering Name:

4 May 2005

SOLUTION

Boron is an acceptor dopant (1 pt). Assuming that the carrier concentration will equal the dopant concentration (1 pt) and that the hole concentration p will be much greater than the electron concentration n (1 pt) (good assumptions, by the way) allows us to set the required conductivity = qph where h is the hole mobility and q is the charge on an electron, i.e. /q = n, where (4 pts). Given the required value of ph, go to the graphs for hole mobilities (1 pt) and find a suitable hole concentration that meets the requirement at 300 K (3 pts). This hole concentration then becomes the required C(x) in the erf solution: " x % " % C(x) Co C(x) 0 0.2m = = 1 erf $ ' = 1 erf $ ' C s Co 1.0 !10 25 m 3 0 # 2 Dt & # 2 D ! 3600s & (Knowing the form of this expression was given 3 pts extra credit.) This enables us (with the help of an erf table) to solve for the diffusion coefficient D that will give the required concentration at a depth of 0.2 m in 1 h (4 pts). Finally, knowing the required D lets us solve for the required temperature, using the expression given on the preceding page (4 pts).

1 8

/10 2 /22 9

/14 3 /56 10

/14 4 /20 11

/24 5 /20 11 of 11

/20 6
TOTAL:

/36 7

/52 /288

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