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West Virginia University Ceramics Mechanical & Aerospace Engineering West Virginia University Taxonomy of Ceramics Glasses Clay Refractories products Abrasives Cements Advanced ceramics -optical -whiteware -bricks for -sandpaper -composites engine high T -composite -bricks -cutting -structural -rotors (furnaces) -polishing reinforce -valves -containers/ -bearings Adapted from Fig. 13.1 and discussion in household Section 13.2-6, Callister 7e. -sensors • Properties: -- Tm for glass is moderate, but large for other ceramics. -- Small toughness, ductility; large moduli & creep resist. • Applications: -- High T, wear resistant, novel uses from charge neutrality. • Fabrication -- some glasses can be easily formed -- other ceramics can not be formed or cast. Mechanical & Aerospace Engineering 2 West Virginia University Application: Refractories • Need a material to use in high temperature furnaces. • Consider the Silica (SiO2) - Alumina (Al2O3) system. • Phase diagram shows: mullite, alumina, and crystobalite as candidate refractories. 2200 T(°C) 3Al2O3-2SiO2 2000 Liquid (L) 1800 mullite alumina + L mullite +L crystobalite +L 1600 1400 mullite + crystobalite 0 20 alumina + mullite Adapted from Fig. 12.27, Callister 7e. (Fig. 12.27 is adapted from F.J. Klug and R.H. Doremus, "Alumina Silica Phase Diagram in the Mullite Region", J. American Ceramic Society 70(10), p. 758, 1987.) 40 60 80 100 Composition (wt% alumina) Mechanical & Aerospace Engineering 3 West Virginia University Application: Die Blanks • Die blanks: die -- Need wear resistant properties! Ao die Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission. Ad tensile force Adapted from Fig. 11.8 (d), Callister 7e. • Die surface: -- 4 mm polycrystalline diamond particles that are sintered onto a cemented tungsten carbide substrate. -- polycrystalline diamond helps control fracture and gives uniform hardness in all directions. Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission. Mechanical & Aerospace Engineering 4 West Virginia University Application: Cutting Tools • Tools: -- for grinding glass, tungsten, carbide, ceramics -- for cutting Si wafers -- for oil drilling • Solutions: -- manufactured single crystal or polycrystalline diamonds in a metal or resin matrix. -- optional coatings (e.g., Ti to help diamonds bond to a Co matrix via alloying) -- polycrystalline diamonds resharpen by microfracturing along crystalline planes. oil drill bits blades coated single crystal diamonds polycrystalline diamonds in a resin matrix. Photos courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission. Mechanical & Aerospace Engineering 5 West Virginia University Application: Sensors • Example: Oxygen sensor ZrO2 • Principle: Make diffusion of ions Ca 2+ fast for rapid response. • Approach: Add Ca impurity to ZrO2: A Ca 2+ impurity removes a Zr 4+ and a O2- ion. -- increases O2- vacancies -- increases O2- diffusion rate • Operation: -- voltage difference produced when O2- ions diffuse from the external surface of the sensor to the reference gas. sensor gas with an unknown, higher oxygen content O2diffusion + reference gas at fixed oxygen content - voltage difference produced! Mechanical & Aerospace Engineering 6 West Virginia University Glass & Vitreous Ceramics Glass Vitreous Ceramics Mechanical & Aerospace Engineering West Virginia University High-performance Engineering Ceramics Diamond: used as cutting tools, rock drills, abrasive, etc. Generic High-performance Ceramics Mechanical & Aerospace Engineering West Virginia University Cement and Concrete Cement: Mixture of lime (CaO), silica (SiO2) and alumina (Al2O3), which sets when mixed with water Concrete: Sand and stones held together by cement. Mechanical & Aerospace Engineering West Virginia University Natural Ceramics Mechanical & Aerospace Engineering West Virginia University Structure of Ceramics - Ionic NaCl Structure MgO Structure: Can be thought of as an fcc packing with Mg ions in octahedral holes. Mechanical & Aerospace Engineering West Virginia University Structure of Ceramics - Ionic ZrO2: fcc packing of Zr with O in the tetrahedral holes Al2O3: c.p.h packing of O with Al in 2/3 of the octahedral holes Mechanical & Aerospace Engineering West Virginia University Structure of Ceramics – Simple Covalent Diamond: each atom has four neighbors. SiC: diamond structure with half the atoms replaced by Si. Mechanical & Aerospace Engineering West Virginia University Structure of Ceramics – Simple Covalent Cubic SiO4: diamond structure with an SiO4 tetrahedron on each atom site. Mechanical & Aerospace Engineering West Virginia University Structure of Ceramics Microstructure of Ceramics Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Elastic Moduli Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Strength, Hardness & Lattice Resistance Normalised Hardness of Pure Metals, Alloys and Ceramics Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Dislocation Movement Dislocation motion in covalent solids is intrinsically difficult because the interatomic bonds must be broken and reformed Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Dislocation Movement Dislocation motion in ionic solids is easy on some planes, but hard on others. The hard systems usually dominate. Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Fracture Strength of Ceramics The design strength of a ceramic is determined by fracture toughness and lengths of the microcracks it contains. Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Fracture Strength of Ceramics (a) Tensile test measures tensile strength, TS (b) Bend test measures modulus of rupture, r, typically 1.7 TS (c) Compression test measures crushing strength, c, typically 15TS Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics - Fracture Strength In compression, many flaws propagate stably to give general crashing In tension the largest flaw propagates unstably Mechanical & Aerospace Engineering West Virginia University Mechanical Properties of Ceramics Thermal Shock Resistance ET = TS Where E is the Young’s modulus, is the coefficient of expansion and TS is tensile strength. T represents the ceramic’s thermal shock resistance Mechanical & Aerospace Engineering West Virginia University Ceramic Fabrication Methods-I PARTICULATE FORMING GLASS FORMING CEMENTATION • Pressing: Gob Pressing operation plates, dishes, cheap glasses --mold is steel with graphite lining Parison mold • Fiber drawing: Compressed air • Blowing: suspended Parison Finishing mold Mechanical Adapted from Fig. 13.8, Callister, 7e. (Fig. 13.8 is adapted from C.J. Phillips, Glass: The Miracle Maker, Pittman Publishing Ltd., London.) wind up & Aerospace Engineering 24 West Virginia University Sheet Glass Forming • Sheet forming – continuous draw – originally sheet glass was made by “floating” glass on a pool of mercury Adapted from Fig. 13.9, Callister 7e. Mechanical & Aerospace Engineering 25 West Virginia University Glass Structure • Basic Unit: 4Si0 4 tetrahedron Si 4+ O2- • Quartz is crystalline SiO2: • Glass is amorphous • Amorphous structure occurs by adding impurities (Na+,Mg2+,Ca2+, Al3+) • Impurities: interfere with formation of crystalline structure. Na + Si 4+ O2- (soda glass) Adapted from Fig. 12.11, Callister, 7e. Mechanical & Aerospace Engineering 26 West Virginia University Glass Properties • Specific volume (1/r) vs Temperature (T): • Crystalline materials: Specific volume Liquid (disordered) Supercooled Liquid • Glasses: Glass (amorphous solid) Crystalline (i.e., ordered) Tg -- crystallize at melting temp, Tm -- have abrupt change in spec. vol. at Tm Tm solid T -- do not crystallize -- change in slope in spec. vol. curve at glass transition temperature, Tg -- transparent - no crystals to scatter light Adapted from Fig. 13.6, Callister, 7e. Mechanical & Aerospace Engineering 27 West Virginia University Glass Properties: Viscosity • Viscosity, h: -- relates shear stress and velocity gradient: dy glass dv dv dy dv h dy velocity gradient h has units of (Pa-s) Mechanical & Aerospace Engineering 28 West Virginia University Glass Viscosity vs. T and Impurities • Viscosity decreases with T • Impurities lower Tdeform • soda-lime glass: 70% SiO2 balance Na2O (soda) & CaO (lime) • borosilicate (Pyrex): 13% B2O3, 3.5% Na2O, 2.5% Al2O3 Viscosity [Pa s] • Vycor: 96% SiO2, 4% B2O3 • fused silica: > 99.5 wt% SiO2 10 14 10 10 10 6 10 2 1 200 strain point annealing range Tdeform : soft enough to deform or “work” Tmelt 600 1000 1400 1800 T(°C) Adapted from Fig. 13.7, Callister, 7e. (Fig. 13.7 is from E.B. Shand, Engineering Glass, Modern Materials, Vol. 6, Academic Press, New York, 1968, p. 262.) Mechanical & Aerospace Engineering 29 West Virginia University Heat Treating Glass • Annealing: --removes internal stress caused by uneven cooling. • Tempering: --puts surface of glass part into compression --suppresses growth of cracks from surface scratches. --sequence: before cooling hot surface cooling further cooled cooler hot cooler compression tension compression --Result: surface crack growth is suppressed. Mechanical & Aerospace Engineering 30 West Virginia University Ceramic Fabrication Methods-IIA GLASS FORMING PARTICULATE FORMING CEMENTATION • Milling and screening: desired particle size • Mixing particles & water: produces a "slip" Ao • Form a "green" component container --Hydroplastic forming: force extrude the slip (e.g., into a pipe) --Slip casting: pour slip into mold absorb water into mold “green ceramic” solid component pour slip into mold ram bille t container drain mold die holder extrusion Ad Adapted from Fig. 11.8 (c), Callister 7e. die “green ceramic” Adapted from Fig. 13.12, Callister 7e. (Fig. 13.12 is from W.D. Kingery, Introduction to Ceramics, John Wiley and Sons, Inc., 1960.) hollow component • Dry and fire the componentMechanical & Aerospace Engineering 31 West Virginia University Clay Composition A mixture of components used (50%) 1. Clay (25%) 2. Filler – e.g. quartz (finely ground) (25%) 3. Fluxing agent (Feldspar) binds it together aluminosilicates + K+, Na+, Ca+ Mechanical & Aerospace Engineering 32 West Virginia University Features of a Slip Shear • Clay is inexpensive • Adding water to clay -- allows material to shear easily along weak van der Waals bonds -- enables extrusion -- enables slip casting • Structure of Kaolinite Clay: Adapted from Fig. 12.14, Callister 7e. (Fig. 12.14 is adapted from W.E. Hauth, "Crystal Chemistry of Ceramics", American Ceramic Society Bulletin, Vol. 30 (4), 1951, p. 140.) charge neutral weak van der Waals bonding charge neutral 4+ Si 3+ Al OH 2O Mechanical & Aerospace Shear Engineering 33 West Virginia University Drying and Firing • Drying: layer size and spacing decrease. Adapted from Fig. 13.13, Callister 7e. (Fig. 13.13 is from W.D. Kingery, Introduction to Ceramics, John Wiley and Sons, Inc., 1960.) wet slip partially dry “green” ceramic Drying too fast causes sample to warp or crack due to non-uniform shrinkage • Firing: --T raised to (900-1400°C) --vitrification: liquid glass forms from clay and flows between SiO2 particles. Flux melts at lower T. Si02 particle (quartz) micrograph of porcelain glass formed around the particle 70mm Adapted from Fig. 13.14, Callister 7e. (Fig. 13.14 is courtesy H.G. Brinkies, Swinburne University of Technology, Hawthorn Campus, Hawthorn, Victoria, Australia.) Mechanical & Aerospace Engineering 34 West Virginia University Ceramic Fabrication Methods-IIB GLASS PARTICULATE CEMENTATION FORMING FORMING Sintering: useful for both clay and non-clay compositions. • Procedure: -- produce ceramic and/or glass particles by grinding -- place particles in mold -- press at elevated T to reduce pore size. • Aluminum oxide powder: -- sintered at 1700°C for 6 minutes. Adapted from Fig. 13.17, Callister 7e. (Fig. 13.17 is from W.D. Kingery, H.K. Bowen, and D.R. Uhlmann, Introduction to Ceramics, 2nd ed., John Wiley and Sons, Inc., 1976, p. 483.) 15Mechanical mm & Aerospace Engineering 35 West Virginia University Powder Pressing Sintering - powder touches - forms neck & gradually neck thickens – add processing aids to help form neck – little or no plastic deformation Uniaxial compression - compacted in single direction Isostatic (hydrostatic) compression - pressure applied by fluid - powder in rubber envelope Hot pressing - pressure + heat Adapted from Fig. 13.16, Callister 7e. Mechanical & Aerospace Engineering 36 West Virginia University Tape Casting • thin sheets of green ceramic cast as flexible tape • used for integrated circuits and capacitors • cast from liquid slip (ceramic + organic solvent) Adapted from Fig. 13.18, Callister 7e. Mechanical & Aerospace Engineering 37 West Virginia University Ceramic Fabrication Methods-III GLASS PARTICULATE CEMENTATION FORMING FORMING • Produced in extremely large quantities. • Portland cement: -- mix clay and lime bearing materials -- calcinate (heat to 1400°C) -- primary constituents: tri-calcium silicate di-calcium silicate • Adding water -- produces a paste which hardens -- hardening occurs due to hydration (chemical reactions with the water). • Forming: done usually minutes after hydration begins. Mechanical & Aerospace Engineering 38 West Virginia University Applications: Advanced Ceramics Heat Engines • Advantages: – Run at higher temperature – Excellent wear & corrosion resistance – Low frictional losses – Ability to operate without a cooling system – Low density • Disadvantages: – Brittle – Too easy to have voidsweaken the engine – Difficult to machine • Possible parts – engine block, piston coatings, jet engines Ex: Si3N4, SiC, & ZrO2 Mechanical & Aerospace Engineering 39 West Virginia University Applications: Advanced Ceramics • Ceramic Armor – Al2O3, B4C, SiC & TiB2 – Extremely hard materials » shatter the incoming projectile » energy absorbent material underneath Mechanical & Aerospace Engineering 40 West Virginia University Applications: Advanced Ceramics Electronic Packaging • Chosen to securely hold microelectronics & provide heat transfer • Must match the thermal expansion coefficient of the microelectronic chip & the electronic packaging material. Additional requirements include: – good heat transfer coefficient – poor electrical conductivity • Materials currently used include: » Boron nitride (BN) » Silicon Carbide (SiC) » Aluminum nitride (AlN) • thermal conductivity 10x that for Alumina • good expansion match with Si Mechanical & Aerospace Engineering 41