saser_ei12_414-459 12/6/05 20:13 Page 455 Green, D. J, An Introduction 10 the Mechanical Properties of Ceramics, Cambridge University Press, Cambridge, 1998, Hauth, W. E., “Crystal Chemistry in Ceramics,” American Ceramic Society Bulletin, Vol. 30, 1951: No. 1, pp. 3=1; No. 2, pp. 47-44; No. 3, p.76-77;No.4, pp. 137-142; No.5, pp. 165-167: No.6, pp. 203-205. good overview of silicate structures. Kingery, WD. HK Rowen DR Uhlmann, Introduction 10 Ceramics, 2nd edi- tion, Wiley, New York, 1976. Chapters 1-4, 14, sand 15. QUESTIONS AND PROBLEMS D REVISED PAGES. Questions and Problems + 455 Norton, FH. Elements of Ceramics, Addison- Wesley, 1974. Reprinted by TechBooks, Marietta, OH, 1991. Chapters 2 and 23. Phase Equilibria Diagrams (tor Ceramists), Ameri- ‘can Ceramie Society, Westerville, OH. In four- teen volumes, published between 1964 and 2009, Also on CD-ROM. Richerson, D.W., The Magic of Ceramies, Ameti- can Ceramic Society, Westerville, OH, 2000. Richerson. TW. Modern Coramic Engineering, 2nd edition, Marcel Dekker, New York, 1992. Wachtman, J. B., Mechanical Properties of Ceram- “cs, Wiley, New York, 1996, Crystal Structures 12.1 For a ceramic compound, what are the two characteristics of the component ions that determine the crystal structure? 12.2 Show that the minimum cation-to-anion radius ratio for a coordination number of 4 is 0.225. 12.3 Show that the minimum cation-to-anion ra- dive ratio for a coordination number of 6 ic (O14, [Hint: Use the NaCl erystal structure (Figure 12.2), and assume that anions and cations are just touching along cube edges and across face diagonals.) 124 Demonstrate that the minimum cation-to- anion radius ratio for a coordination num- ber of 8 is 0.732 125 On the basis of ionic charge and ionic radii given in lable 12.5, predict crystal structures for the following materials: (a) CaO, (b) ‘MaS. (e) KBr, and (d) CsBr. Justify your selections. 126 Which of the cations in Table 123 would you predict to form fluorides having the cesium chloride crystal structure’ Justify your choices. 12.7 Compute the atomic packing factor for the rock salt crystal structure in which relty = 0414. 128 The zine blende crystal structure is one that may be generated from close-packed planes of anions. (a) Will the stacking sequence for this struc- ture be FCC or HCP? Why? D () Will cations fill tetrahedral oF octabe- dral positions? Why? (©) What fraction of the p cccupied? 129 The corundum erystal structure, found for AOS, consists of an HCP arrangement of © ions; the AP" ions occupy octahedral positions, (a) What fraction of the available oetahe- drat positions are hile with AV" 1ons? (b) Sketch two close-packed O*~ planes Stacked in an AB sequence, and note octa- hedral positions that will be filled with the AB * ions. 12.10 Beryllium oxide (BeO) may form a crystal structure that consists of an HCP arrange- ment of O° ions If the ionic radius of Be" js 0035 nm, then (a) Which type of interst Be** ions occupy? () What fraction of these available inter stitial sites will be occupied by Be" ions? 1241 Iron titanate, FeTiO,, forms in the ilmenite crystal structure that consists of an HCP arrangement of O?~ ions, (a) Which type of interstitial site will the Fe?" ions occupy? Why? (©) Which type of interstitial site will the ‘Ti** ions occupy? Why? (©) What fraction of the total tetrahedral sites will be occupied? (@) What fraction of the total octahedral sites will be occupied? tions will be site will the EQAsaser_ei2 414-459 12/6/05 20:19 Page 456 D REVISED PAGES. 456 + Chapter 12 | Structures and Properties of Ceramics 12.12 Using the Molecule Definition Utility found inboth "Metalic Crystal Sructures and Crys OD itowaphy" and “ceramic Crystal Sve. BAB tures" modules of VME, located on the book's web site [wor wle.comicollegecal ister (Student Companion Sit)} generate (and print out) a threedimensionl unt ell {or lead oxide, PbO, given the following: (1) ‘The unit cel is tetragonal with a = 0.397 nm and ¢= 0507 am. O) oxygen atoms ate located at the following point coordinates: 000 oot 100 101 010 oll 110 eet 14 22! and (3) Pb atoms are located at the follow- ing point coordinates o 2 300763 050237 trams i taan 1243 Calculaw the teoredeal density of NO, given that it has the rock salt crystal structure 12.14 Iron oxide (FeO) has the rock salt crystal structure and a density of $.70 glem’, (a) Determine the unit coll edge length, (b) How does this result compare with the edge length as determined from the radii in Table 12.3, assuming that the Fe’* and ions just touch each other along the edges? 12.15 Compute the theoretical density of diamond given that the C—C distance and bond an- gle are 0.154 nm and 109.5°, respectively. How does this value compare with the mea- sured density? 12.16 Compute the theoretical density of ZnS given that the Zn—S distance and bond an- gle are 0.234 nm and 109.5%, respectively. How does this value compare with the mea sured density? 12.17 One crystalline form of silica (SiOx) has a cubic unit cell, and from X-ray diffraction data it is known that the cell edge length D is 0.700 nm. If the measured density is 232 glem', how many Si” and O° ions are there per unit cell? 12.18 (a) Using the ionic rai in Table 12.3com- pute the theoretical density of CsCl, (Hint: Use a modification of the result of Prob- lem 33,) (b) The measured density is 399 glem’. How do you explain the slight discrepancy be- tween your calculated value and the mea: sured one? 1219 From the data in Table 12.3, compute the theoretical density of CaF;, which has the fluorite structure. A hypothetical AX type of ceramic material isknown to have a density of2.10 gem’ and ‘unit cell of cubie symmetry with a cell edge length of 0.57 nm. The atomic weights of the ‘A and X elements are 28.5 and 300 ghmol, respectvely.On the basso this information, ‘which of the following erystal structures is (ate) possible for this material: sodium chlo- ride, cesium chloride, or zine blende? Justify your choice(s) 12.21 The unit cell for Fe,O, (FeO-FesO,) has cu- bic symmetry with a unit cell edge length of ‘04839 nm. If the density of this material is 524 lem, compute its atomic packing fac- tor. For this computation, you will need to use ionic radi listed in Table 12.3. 12.22 The unit cell for ALLOs has hexagonal sym- retry with lattice parameters, and ¢ = 1.2989 nm. I the density of terial ¢ 109 ple. caleutate ite atomic pack ing factor. For this computation use ionic rai listed in Table 123. 12.23 Compute the atomic packing factor for the diamond cubic crystal structure (Figure 12.15). Assume that bonding atoms touch cone another, that the angle between adjacent trond is 100 Sand that each atom internal to the unit cell is positioned «/4 of the dis- tance away from the two nearest cell faces (ais the unit coll edge length). 12.24 Compute the atomic packing factor for ce- sium chloride using the ionie radi in Table 123 and assuming that the ions touch along the cube diagonals. 1220 EQAsaser_e12_414-459 12/6/05 20:13 Page 457 12.25 For each of the following erystal structures, represent the indicated plane in the manner of Figures 3.10 and 3.11, showing both an- ions and cations: (a) (100) plane for the ce- sium chloride crystal structure, (b) (200) plane for the cesium chloride crystal struc- ture, (e) (111) plane for the diamond cubic crystal structure, and (a) (110) plane for the luorite crystal structure. aye 12.26 In terms of bonding, explain why silicate ma- terials have relatively low densities. 12.27 Determine the angle between covalent bonds in an SiO{- tetrahedron. Impertections in Ceramics 12.28 Would you expect Frenkel defects for anions to exist in ionic ceramics in relatively large concentrations? Why or why not? 12.29 Calculate the fraction of lattice sites that are Schottky defects for cesium chloride at its ‘melting temperature (645°C). Assume an cenergy for defect formation of 1.86 eV. 12.30 Calculate the number of Frenkel defects per cubic meter in silver chloride at 350°C. The energy for defect formation is 1.1 eV, while the density for AgClis 550 gicm’ at (350°C). 12.31 Using the data given below that relate to the formation of Schottky defects in some oxide ceramic (having the chemical formula MO), determine the following (a) The energy for defect formation (in eV), (b) the cquilibrium number of Schottky defects per cubic meter at 1000°C, and (©) the identity of the vaide (ie. what is the ‘metal M2) TCC) piglem) Ny) 750 350 s7 x19 1000 Bas 2 1300 340 58x10" 12.32 In your own words, briefly define the term “stoichiometric.” 12.33 If cupric oxide (CuO) is exposed to redue~ ing atmospheres at clevated temperatures, some of the Cu” ions will become Cu D D REVISED PAGES. Questions and Problems + 457 (a) Under these conditions, name one erys- talline defect that you would expect to form in order to maintain charge neutrality. (b) How many Cu" ions are required for the creation of each defect? (€) How would you express the chemical formula for this nonstoichiometrie material? 1234 (a) Suppose that CaO is added as an impu- iO. If the Ca°” substitutes for Li”, of vacancies would you expect t6 form? How many of these vacancies are cre ated for every Ca* adatest?” (b) Suppose that CaO is added as an impu- rity to CaCh Ifthe OF” substitutes for CI”, what kind of vacancies would you expect to form? How many of these vacancies are created for every O° added? Ceramic Phase Diagrams 1235 For the ZrO-CaO system (Figure 12.26), write all eutectic und cutectoid reactions for cooling. 12.36 From Figure 12.25, the phase diagram for the MgO-AI.0; system, it may be noted that the spinel solid solution exists over a range of compositions, which means that it is non- stoichiometric at compositions other than 50 mol% MgO-S0 mol% ALOy. (a) The maximum nonstoichiometry on the ‘AlOsrich side ofthe spine phase field ex- tS at about 2000°C (3630°F) corresponding to approximately 82 mol% (92 wt%) ALOs. Determine the type of vacaney defect that is, provdiced and the percentage of vacancies that exist at this composition. (b) The maximum nonstoichiometry on the ‘MgO-nech side of the spinel phase field ex- ists at about 2000°C (3630°F) corresponding {0 approximately 39 mol% (62 wt%) ALOs, Determine the type of vacaney defect that is, produced and the percentage of vacancies that exist at this composition. 1237 When kaolinite clay [Al,(Si,0,)(OH),) is heated to a sufficiently high temperature, chemical water is driven off (a) Under these circumstances, what is the composition of the remaining product (in weight percent ALO)? EQA