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Ceramics Thermal Coatings History and Background Applications date into antiquity - earthenware, pottery, clay product, bricks, etc More modern uses: Transparent glass, structural glass, refractories
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Ceramics Thermal Coatings
History and Background • Applications date into antiquity - earthenware, pottery, clay product, bricks, etc • More modern uses: Transparent glass, structural glass, refractories • Advanced uses: Thermal barrier coatings, structural ceramics, composite armor, electronics, glass-ceramics • Ceramics can be Amorphous or Crystalline • Atomic structure contains strong Ionic Bonds
What are they? • A compound of metallic and nonmetallic elements, for which the inter atomic bonding is predominantly ionic. • They tend to be oxides, carbides, etc of metallic elements. • The mechanical properties are usually good: high strength, especially at elevated temperature. • However, they exhibit low to nil-ductility, and have low fracture toughness.
Crystalline Ceramics • As with plastics, the amorphous ceramics tend to be transparent • The structural ceramics tend to be crystalline and show greater strength, as well as stability at high temperature
AX Structure - CsCl • Cl- Note: This is not a BCC structure. Cs+ Simple Cubic Crystal
AX Structure - NaCl 2- FCC interpenetrating lattices.
Try it! Compute the theoretical density of Rock Salt based on its crystal structure. For this NaCl structure, the crystal lattice parameter is a= 2 ( r Na+ + r Cl -), where r is ionic radius.
Silicate Ceramics • Silica, SiO2 • Many polymorphs:Quartz CrystobaliteTridymite • Low density: Quartz: 2.65g/cm3
Carbon • Pure carbon has many polymorphs with vastly varying properties. It also exists in the amorphous state. • Diamond: Is similar to ZnS in structure • Graphite is considered to be a crystalline ceramic • Fullerenes, C60, are a newly discovered polymorph - with interesting properties.
Diamond • AX type crystal structure similar to that of ZnS. • Each carbon atom is covalently bonded to four other C atoms in a diamond-cubic crystal structure. • The material is optically transparent and extremely hard (hardest natural material known) and durable. • In engineering applications, cruder or industrial forms of diamond, that are much less expensive than the gemstone forms, are used as abrasives, indentors, and coatings (especially thin films) for a variety of applications.
Graphite • Layers of hexagonally arranged and covalently bonded C atoms. • Between layers, weaker Van der Walls bonds are active, giving easy slip on the {0001} crystallographic planes. • Excellent as a dry lubricant, relatively high strength at elevated temperatures, high thermal and electrical conductivity, low thermal expansion, resistance to thermal shock, and good machinability. • Usage: electrodes, heating elements, crucibles, casting molds, rocket nozzles, and other applications.
Fullerenes, C60 • Molecular form of carbon with a hollow spherical structure resembling a geodesic dome (soccer ball.) • Called buckyballs after R. Buckminister Fuller, who pioneered the geodesic dome. Discovered in 1985 and have since been found to occur naturally in several sources. • In the solid crystalline state, C60 molecules pack together in a FCC unit cell arrangement with a lattice parameter a=1.41 nm. • The pure solid material density is about 1.65 g/cm3and it is relatively soft and is non-conducting since it has no free electrons.
Properties of Buckyballs • When alkali metal anions, most notably K+,are in the structure (usually 3 per C60 molecule), the resulting molecular material (K3C60) displays the characteristics of a metal. In fact, K3C60 is considered to be the first molecular metal ever encountered. • K3C60 buckyballs and similar molecular materials become super conducting (practically no electrical resistance) at about 18K (relatively high temperature for this phenomenon) • Applications in low-power consumption, low-pollution, magnetic-levitation and propulsion devices for mass transit systems. • Other synthetic ceramic materials have been developed that display superconductivity at even higher temperatures (up to 100K) above the temperature of liquid nitrogen, a relatively inexpensive and abundant coolant.
Try It! • Calcualte the theoretical density of pure C60 based on a FCC unit cell as shown: a=1.41 nm
Defects in Crystalline Ceramics • Vacancy • Interstitial • Dislocation • Grain Boundary Cation Interstitial Anion Vacancy Cation Vacancy Schotky Defect Frenkel Defect Electro- neutrality
Mechanical Properties • Brittle Materials, hard to perform a Tension Test. • Flexural Test (Bend) is often substituted. • Obtain Flexural Strength (Modulus of Rupture), Stiffness (Modulus of Elasticity), and Ductility. • Strength is often good, Stiffness my be high, but Ductility and affected properties are poor. • In crystalline ceramics, dislocation motion is difficult because of the need to maintain electro-neutrality. Consequently plastic deformation is restricted.
Flexural Test Configuration Rectangular: Circular:
Mechanical Properties of Various Ceramics a Sintered with about 5% porosity
Relative Hardness B4C, SiC WC, Al2O3 Glass
Effect of Porosity on Stiffness Where Eo is the theoretical modulus of elasticity with no porosity, and P is the volume fraction of porosity.
Effect of Porosity on Strength Where so is the theoretical modulus of rupture with no porosity, P is the volume fraction of porosity, and n is an empirical material constant
Fracture Toughness (MPam) Fracture Toughness
Amorphous Ceramics - Glasses (Na20, Ca0, K2O, etc) • The viscosity of the material at ambient temperature is relatively high, but as the temperature increases there is a continuous decrease in viscosity. • When the viscosity has decreased to the point that the ceramic is a fluid, it is considered to have melted. • At ambient temperature while it is still solid, it is said to be in the “glassy” condition. • There is no distinct melting temperature (Tm) for these materials as there is with the crystalline materials. • The glass transition temperature, Tg, is used to define the temperature below which the material is a “solid” and defines a practical upper limit on service temperature.
Viscous Behaviour in Amorphous Ceramics t = shear stress h = viscosity of material • Plastic deformation does not occur by dislocation motion in amorphous or non-crystalline ceramics, such as glass. • Deformation is by viscous flow: rate of deformation proportional to applied stress.
Ceramic Phase Diagrams • Note: They are similar to metal alloy systems - except the temperatures are generally higher.