1. ISSUES TO ADDRESS... Structures of ceramic materials: How do they differ from those of metals? Point defects: How are they different from those in metals? Impurities: How are they accommodated in the lattice and how do they affect properties? Mechanical Properties: What special provisions/tests are made for ceramic materials? Chapter 12: Ceramics Materials - Structures and Properties

2. Bonding: -- Mostly ionic, some covalent. -- % ionic character increases with difference in electronegativity. Large vs small ionic bond character: Ceramic Bonding SiC: small CaF 2 : large

3. Ionic Bonding & Structure 1. Size - Stable structures: --maximize the # of nearest oppositely charged neighbors. - - -- + unstable Charge Neutrality: --Net charge in the structure should be zero. SiO 2, MgO, SiC, Al 2 O 3 - - - - + stable - - - - + CaF 2 : Ca 2+ cation F - F - anions +

4. Coordination # increases with Coordination # and Ionic Radii 2 r cation r anion Coord # < 0.155 0.155 - 0.225 0.225 - 0.414 0.414 - 0.732 0.732 - 1.0 3 4 6 8 linear triangular TDTD OHOH cubic ZnS (zincblende) NaCl (sodium chloride) CsCl (cesium chloride) r cation r anion Issue: How many anions can you arrange around a cation?

5. Site Selection II 2.Stoichiometry –If all of one type of site is full the remainder have to go into other types of sites. Ex: FCC unit cell has 4 O H and 8 T D sites. If for a specific ceramic each unit cell has 6 cations and the cations prefer O H sites 4 in O H 2 in T D

6. Site Selection III 3.Bond Hybridization – significant covalent bonding –the hybrid orbitals can have impact if significant covalent bond character present –For example in SiC X Si = 1.8 and X C = 2.5 ca. 89% covalent bonding both Si and C prefer sp 3 hybridization Therefore in SiC get T D sites

7. On the basis of ionic radii, what crystal structure would you predict for FeO? Answer: based on this ratio, --coord # = 6 --structure = NaCl Example: Predicting Structure of FeO Ionic radius (nm) 0.053 0.077 0.069 0.100 0.140 0.181 0.133 Cation Anion Al 3+ Fe 2+ 3+ Ca 2+ O 2- Cl - F -

8. Rock Salt Structure Same concepts can be applied to ionic solids in general. Example: NaCl (rock salt) structure r Na = 0.102 nm r Na /r Cl = 0.564  cations prefer O H sites r Cl = 0.181 nm

9. MgO and FeO MgO and FeO also have the NaCl structure O 2- r O = 0.140 nm Mg 2+ r Mg = 0.072 nm r Mg /r O = 0.514  cations prefer O H sites So each oxygen has 6 neighboring Mg 2+

10. AX Crystal Structures AX–Type Crystal Structures include NaCl, CsCl, and zinc blende Cesium Chloride structure:  cubic sites preferred So each Cs + has 8 neighboring Cl -

11. AX Crystal Structures So each Zn 2+ has 4 neighboring S 2- Zinc Blende structure Size arguments predict Zn 2+ in O H sites, In observed structure Zn 2+ in T D sites Why is Zn 2+ in T D sites? –%ionic approx. 18% –bonding hybridization of zinc favors T D sites Ex: ZnO, ZnS, SiC

12. AX 2 Crystal Structures Fluorite structure Calcium Fluorite (CaF 2 ) cations in cubic sites UO 2, ThO 2, ZrO 2, CeO 2 antifluorite structure – cations and anions reversed

13. ABX 3 Crystal Structures Perovskite Ex: complex oxide BaTiO 3

14. Silicate Ceramics Most common elements on earth are Si & O SiO 2 (silica) structures are quartz, crystobalite, & tridymite The strong Si-O bond leads to a strong, high melting material (1710ºC) Si 4+ O 2- crystobalite

15. Amorphous Silica Silica gels - amorphous SiO 2 –Si 4+ and O 2- not in well- ordered lattice –Charge balanced by H + (to form OH - ) at “dangling” bonds –SiO 2 is quite stable, therefore un-reactive to makes good catalyst support

16. Silica Glass Dense form of amorphous silica –Charge imbalance corrected with “counter cations” such as Na + –Borosilicate glass is the pyrex glass used in labs better temperature stability & less brittle than sodium glass Si, B - Network former Other Cations - Network modifier

17. –Combine SiO 4 4- tetrahedra by having them share corners, edges, or faces –Cations such as Ca 2+, Mg 2+, & Al 3+ act to neutralize & provide ionic bonding Silicate elements Mg 2 SiO 4 Ca 2 MgSi 2 O 7

18. Layered Silicates Layered silicates (clay silicates) –SiO 4 tetrahedra connected together to form 2-D plane (Si 2 O 5 ) 2- So need cations to balance charge =

19. Kaolinite clay alternates (Si 2 O 5 ) 2- layer with Al 2 (OH) 4 2+ layer Layered Silicates Note: these sheets loosely bound by van der Waal’s forces

20. Carbon Forms Carbon black Diamond –tetrahedral carbon hard – no good slip planes brittle – can cut it –large diamonds – jewelry –small diamonds often man made - used for cutting tools and polishing –diamond films hard surface coat – tools, medical devices, etc.

21. Carbon Forms - Graphite layer structure – aromatic layers –weak van der Waal’s forces between layers –planes slide easily, good lubricant

22. Carbon Forms – Fullerenes and Nanotubes Fullerenes or carbon nanotubes –wrap the graphite sheet by curving into ball or tube –Buckminister fullerenes Like a soccer ball C 60 - also C 70 + others

23. Frenkel Defect -- a cation is out of place. Shottky Defect -- a paired set of cation and anion vacancies. Defects in Ceramic Structures Shottky Defect: Frenkel Defect

24. Impurities must also satisfy charge balance = Electroneutrality Ex: NaCl Substitutional cation impurity Impurities Na + Cl - initial geometryCa 2+ impurityresulting geometry Ca 2+ Na + + Ca 2+ cation vacancy Substitutional anion impurity initial geometry O 2- impurity O 2- Cl - anion vacancy Cl - resulting geometry

25. Ceramic Phase Diagrams

26. 

29. Ternary phase diagram 45% SiO2 34% Al2O3

30. General properties of ceramics Brittle (very low fracture toughness) Better strength under compressive Flexural strength is the rupture strength achieved from bending test Creep occurs at higher temperature than metal (compressive) Almost good hardness (used as abrasive materials) A little plastic deformation may be observed in crystalline ceramics; slip plane Non-crystalline ceramics; viscous flow Porosity in ceramics decreases the modulus of elasticity and strength High chemical durability

31. Mechanical Properties We know that ceramics are more brittle than metals. Why? Consider method of deformation –slippage along slip planes in ionic solids this slippage is very difficult too much energy needed to move one anion past another anion Higher strength under compressive stress –Generally utilized when load conditions are compressive

32. Load and crack origin

33. Room T behavior is usually elastic, with brittle failure. 3-Point Bend Testing often used. --tensile tests are difficult for brittle materials. Measuring Elastic Modulus F L/2 δ = midpoint deflection cross section R b d rect.circ. Determine elastic modulus according to: F x linear-elastic behavior  F  slope = E = F  L 3 4bd 3 = F  L 3 12  R 4 rect. cross section circ. cross section

34. 3-point bend test to measure room T strength. Measuring Strength F L/2 δ = midpoint deflection cross section R b d rect.circ. location of max tension Flexural strength: Typ. values: Rect.  fs  3F f L 2bd 2  F f L R3R3 Si nitride Si carbide Al oxide glass (soda) 250-1000 100-820 275-700 69 304 345 393 69 Material  fs (MPa) E(GPa) x F FfFf  fs  Cir.

35. Flexural strength and Modulus of elasticity of Ceramics

36. Stress-strain behavior / Porosity

37. Viscosity

38. Measuring Elevated T Response  time Elevated Temperature Tensile Test (T > 0.4 T m ). creep test   slope =  ss = steady-state creep rate. x

39. Ceramic materials have covalent & ionic bonding. Structures are based on: -- charge neutrality -- maximizing # of nearest oppositely charged neighbors. Structures may be predicted based on: -- ratio of the cation and anion radii. Defects -- must preserve charge neutrality -- have a concentration that varies exponentially w/T. Room T mechanical response is elastic, but fracture is brittle, with negligible deformation. Elevated T creep properties are generally superior to those of metals (and polymers). Summary