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Solid State Chemistryvia Glass and Ceramics
John Tanaka and Edward J. NethChemistry DepartmentUniversity of Connecticut Storrs, Connecticut 06269
• Glass, Ceramics and Mankind
• History– Discovered in prehistory by unknown
inventor – Reconstructions of old civilizations– Food and beverage storage
Current technology
• Fiber Optics• LC, electroluminescent, and plasma
displays• Chemistry• Electric insulators • Superconductors • Electronic components• Household goods
Glass• GLASS• Quartz• Coefficient of expansion 8 x 10−7 cm/cm/oC• Softening point 1500oC
• 7740 Pyrex• 80.5% SiO2
• 12.9% B2O3
• 3.8% Na2O• 0.4% K2O• 2.2% Al2O3
• Coefficient of expansion 33 x 10−7 cm/cm/oC• Softening point 820oC• Working point 1200oC
• Container Glass• 74.1% SiO2
• 1.8% Al2O3
• 8.8% CaO• 1.4% MgO• 13.0% Na2O• 0.4% K2O• Coefficient of expansion 92 x 10−7 cm/cm/oC• Softening point 696 oC• Working point 1000 oC
Quartz
• STRUCTURES OF SiO2
• Quartz, α and β (to 870oC)
• Tridymite ( 870oC to 1470oC)
• Cristobalite (1470oC to 1710oC)
Beta quartz
Tridymite, cristobalite
Silicates• SILICATE “ISLAND” STRUCTURES• Orthosilicates
– Be2SiO4 phenacite – (Mg, Fe)2SiO4 olivine – ZrSiO4 zircon– R3IIR2III(SiO4)3 garnet
• Pyrosilicates– Sc2Si2O7 Si-O-Si = 180o
– Gd2Si2O7 Si-O-Si = 159o
– Nd2Si2O7 Si-O-Si = 133o
• Nets– 1 connection dimer as above – 2 connection chain or ring– 3-connection 2 dimensional “infinite” structure or 3
dimensional “infinite” structure– 4-connection 2 dimensional “infinite” structure or
3-dimensional “infinite” structure
Representations
• To understand the structure of a three dimensional solid, more than one representation is needed
• It is not possible to display all structural elements using a single model
Three Views
• 1. Classical Molecular view of P4O10
P OO
O
O
P O P O
OO
OP
O
Ball and stick
2. Polyhedral View
3. Sphere Packing View
More Examples
• REPRESENTATIONS OF SOLID STATE STRUCTURES• Ball and Stick• P4O10 Picture• NaCl Picture• Zinc Blende Picture• Polyhedral• P4O10 Picture• NaCl Picture• Zinc Blende Picture• Close Packed • P4O10 Picture• NaCl Picture• Zinc Blende Picture
Diamond (Zincblende)
ZnS, polyhedral
ZnS, close packed
NaCl, ball and stick
NaCl, polyhedral
Ceramics
• Quartz– Shown earlier
• Feldspar
• Kaolin
Ceramics
• FELDSPAR
• Plagioclase feldspars– NaAlSi3O8 albite
– CaAl2Si2O8 anorthite
• Paracelsian– Ba(Al2Si2O8)
Feldspars
Kaolin and asbestos
Kaolin, 2D view
2-connected
3-connected
4-connected
Nets
• 4-connected, two dimensional net– HgI
• 4-connected, three dimensional net– Diamond, zincblende shown earlier
HgI
Li2Si2O5
Thorium disilicide