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KJM3100 V2006
Minerals; The background of materials science
Formation, structure, properties and applications of minerals are in many ways the starting points of materials science.
Learning from Nature (stealing “ideas” matured over millions of years) is a good way to make some progress.
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Minerals
•naturally occurring
•inorganic
•solid
•fixed composition or within fixed range
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Hardness scale (Mohs)
1 Talc (Mg3Si4O10(OH)2)
2 Gypsum (CaSO4·2H2O)
3 Calcite (CaCO3)
4 Fluorite (CaF2)
5 Apatite (Ca5(PO4)3(OH-,Cl-,F-))
6 Orthoclase Feldspar (KAlSi3O8)
7 Quartz (SiO2)
8 Topaz (Al2SiO4(OH-,F-)2)
9 Corundum (Al2O3)
10 Diamond (C) 1500
Hardness Substance or Mineral1 Liquid2 Gypsum2.5 to 3 Gold, Silver3 Calcite, Copper penny4 Fluorite4 to 4.5 Platinum4 to 5 Iron5 Apatite6 Orthoclase6.5 Iron pyrite6 to 7 Glass, Vitreous pure silica7 Quartz7 and up Hardened steel8 Topaz9 Corundum10 Garnet 11 Fused zirconia12 Fused alumina 13 Silicon carbide 14 Boron carbide 15 Diamond
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Formation of minerals
•Formation from melts•Solid state reactions•Hydrothermal conditions•Sedimentation/precipitation•Vapor phase deposition•Exsolution
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A few important mineral types/structures
Perovskite CaTiO3Spinel MgAl2O4Rutile TiO2Rock Salt NaCl, MgOCorundum Al2O3
GarnetOlivine……
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Class Arrangement oftetrahredra
Shared corners Repeat unit Si:O Example
Nesosilicates Independenttetrahedra
0 SiO44- 1:4 Olivine
Sorosilicates Pair oftetrahedrasharing corner
1 Si2O76- 1:3.5 Hemimorphite
Cyclosilicates Closed rings oftetrahedra
2 SiO32- 1:3 Tourmaline
Inosilicates Infinite singlechain oftetrahedra
2 SiO32- 1:3 Pyroxenes
Infinite doublechains oftetrahedra
2.5 Si4O116- 1:2.75 Amphiboles
Phyllosilicates Infinite sheetsof tetrahedra
3 Si2O52- 1:2.5 Micas
Tektosilicates Unboundedframework oftetrahedra
4 SiO2 1:2 Quartz,feldspars
SILICATE CLASSIFICATION
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Isomorphous replacement in silicates
Some cations and anions are readily replacable:(Not always carrying the same charge!)
Na+, Mg2+, Ca2+, Mn2+, Fe3+
O2-, F-, OH-
And typically:
Si4+, Al3+
E.g. Hornblende,
(Ca, Na)(Ca, Na)22--3 3 (Mg, Fe, Al)(Mg, Fe, Al)55 [(Si,Al)[(Si,Al)88OO2222] (OH)] (OH)22
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Mineral Structures
Silicates are classified on the basis of Si-O polymerismThe building unit: [SiO4]4- tetrahedron
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Mineral Structures
Silicates are classified on the basis of Si-O polymerism[SiO4]4- Independent tetrahedra Nesosilicates
Examples: olivine garnet
[Si2O7]6- Double tetrahedra Sorosilicates
Examples: lawsonite
n[SiO3]2- n = 3, 4, 6 Cyclosilicates
Examples: benitoite BaTi[Si3O9]axinite Ca3Al2BO3[Si4O12]OHberyl Be3Al2[Si6O18] (aquamarine, emerald)
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Mineral Structures
Silicates are classified on the basis of Si-O polymerism
[SiO3]2- single chains Inosilicates [Si4O11]4- Double tetrahedrapryoxenes pyroxenoids amphiboles
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Mineral Structures
Silicates are classified on the basis of Si-O polymerism
[Si2O5]2- Sheets of tetrahedra Phyllosilicatesmicas talc clay minerals serpentine
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Mineral Structures
Silicates are classified on the basis of Si-O polymerism
[SiO2] 3-D frameworks of tetrahedra: fully polymerized Tectosilicatesquartz and the silica minerals feldspars feldspathoids zeolites
lowlow--quartzquartz
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Mineral Structures
Nesosilicates: independent SiO4 tetrahedra
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Examples:
Forsterite Mg2SiO4Fayalite Fe(II)2SiO4Tephroite Mn(II)2SiO4 Liebenbergite (Ni,Mg)2SiO4Monticellite CaMgSiO4Kirschsteinite CaFe(II)SiO4Glaucochroite CaMnSiO4
Olivine group
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Nesosilicates: independent SiO4 tetrahedra
Olivine (100) view blue = M1 yellow = M2Olivine (100) view blue = M1 yellow = M2
bb
cc
projectionprojection
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KJM3100 V2006Olivine (100) view blue = M1 yellow = M2Olivine (100) view blue = M1 yellow = M2
bb
cc
perspectiveperspective
Nesosilicates: independent SiO4 tetrahedra
KJM3100 V2006Olivine (001) view blue = M1 yellow = M2Olivine (001) view blue = M1 yellow = M2
M1 in rows M1 in rows and share and share edgesedges
M2 form M2 form layers in alayers in a--c c that share that share corners corners
Some M2 Some M2 and M1 share and M1 share edgesedges
bb
aa
Nesosilicates: independent SiO4 tetrahedra
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Nesosilicates: independent SiO4 tetrahedra
Olivine (100) view blue = M1 yellow = M2Olivine (100) view blue = M1 yellow = M2
bb
cc
M1 and M2 as polyhedraM1 and M2 as polyhedra
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Green sand beach, Papakolea, Hawaii
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Nesosilicates: independent SiO4 tetrahedra
Garnet (001) view blue = Si purple = B turquoise = AGarnet (001) view blue = Si purple = B turquoise = A
Garnet: AGarnet: A2+2+33 BB3+3+
22 [SiO[SiO44]]3 3
““PyralspitesPyralspites”” -- B = AlB = AlPyPyrope: Mgrope: Mg33 AlAl22 [SiO[SiO44]]3 3 AlAlmandine: Femandine: Fe33 AlAl22 [SiO[SiO44]]33SpSpessartine: Mnessartine: Mn33 AlAl22 [SiO[SiO44]]33
““UgranditesUgrandites”” -- A = CaA = CaUUvarovitevarovite: Ca: Ca33 CrCr22 [SiO[SiO44]]33GrGrossularite: ossularite: CaCa33 AlAl22 [SiO[SiO44]]33AndAndradite: Caradite: Ca33 FeFe22 [SiO[SiO44]]33
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Nesosilicates: independent SiO4 tetrahedra
Garnet (111) view blue = Si purple = B turquoise = AGarnet (111) view blue = Si purple = B turquoise = A
Garnet: AGarnet: A2+2+33 BB3+3+
22 [SiO[SiO44]]3 3
““PyralspitesPyralspites”” -- B = AlB = AlPyPyrope: Mgrope: Mg33 AlAl22 [SiO[SiO44]]3 3 AlAlmandine: Femandine: Fe33 AlAl22 [SiO[SiO44]]33SpSpessartine: Mnessartine: Mn33 AlAl22 [SiO[SiO44]]33
““UgranditesUgrandites”” -- A = CaA = CaUUvarovitevarovite: Ca: Ca33 CrCr22 [SiO[SiO44]]33GrGrossularite: ossularite: CaCa33 AlAl22 [SiO[SiO44]]33AndAndradite: Caradite: Ca33 FeFe22 [SiO[SiO44]]33
aa11
aa22
aa33
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LED White light is currently achieved by using two different methods. One is by combining a blue 450nm – 470nm GaN (gallium nitride) LED with YAG (Yttrium Aluminum Garnet) phosphor. The blue wavelength excites the phosphor causing it to glow white.
YIG-YAGY3Fe5O12 , Y3Al5O12
YIG: Magnetic domains
Garnet: A(II)Garnet: A(II)33B(III)B(III)22 [SiO[SiO44]]33
YIG: YYIG: Y33Fe(III)Fe(III)22 [Fe(III)O[Fe(III)O44]]33YAG: YYAG: Y33AlAl22 [AlO[AlO44]]33
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
Diopside: Diopside: CaMgCaMg [Si[Si22OO66]]bb
a si
na
sin ββ
Where are the SiWhere are the Si--OO--SiSi--O chains??O chains??
Ruby w. diopside
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
bb
a si
na
sin ββ
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
bb
a si
na
sin ββ
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
bb
a si
na
sin ββ
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
bb
a si
na
sin ββ
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
bb
a si
na
sin ββ
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
Perspective viewPerspective view
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Inosilicates: single chains- pyroxenes
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)(Ca)
IV slabIV slab
IV slabIV slab
IV slabIV slab
IV slabIV slab
VI slabVI slab
VI slabVI slab
VI slabVI slab
bb
a si
na
sin ββ
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Pyroxene Chemistry
The general pyroxene formula: W1-P (X,Y)1+P Z2O6
Where– W = Ca Na– X = Mg Fe2+ Mn Ni Li– Y = Al Fe3+ Cr Ti– Z = Si Al
Anhydrous so high-temperature or dry conditions favor pyroxenes over amphiboles
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Pyroxenoids“Ideal” pyroxene chains with
5.2 A repeat (2 tetrahedra) become distorted as other cations occupy VI sites
WollastoniteWollastonite(Ca (Ca →→ M1) M1)
→→ 33--tet repeattet repeat
RhodoniteRhodoniteMnSiOMnSiO33
→→ 55--tet repeattet repeat
PyroxmangitePyroxmangite(Mn, Fe)SiO(Mn, Fe)SiO33→→ 77--tet repeattet repeat
PyroxenePyroxene22--tet repeattet repeat
7.1 A12.5 A
17.4 A
5.2 A
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Inosilicates: double chains- amphiboles
Hornblende:Hornblende:(Ca, Na)(Ca, Na)22--3 3 (Mg, Fe, Al)(Mg, Fe, Al)55
[(Si,Al)[(Si,Al)88OO2222] (OH)] (OH)22
bb
a si
na
sin ββ
Hornblende (001) view dark blue = Si, Al purple = M1 rose = Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2 M2 light blue = M3 (all Mg, Fe) yellow ball = M4 (Ca) purpllight blue = M3 (all Mg, Fe) yellow ball = M4 (Ca) purple ball = A (Na)e ball = A (Na)
little turquoise ball = Hlittle turquoise ball = H
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SiO4 tetrahedra polymerized into 2-D sheets: [Si2O5]Apical O’s are unpolymerized and are bonded to other constituents
Phyllosilicates
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Tetrahedral layers are bonded to octahedral layers (OH) pairs are located in center of T rings where no apical O
Phyllosilicates
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Octahedral layers can be understood by analogy with hydroxides
Phyllosilicates
Brucite: Mg(OH)Brucite: Mg(OH)22
Layers of octahedral Mg in Layers of octahedral Mg in coordination with (OH)coordination with (OH)
Large spacing along Large spacing along cc due due to weak van to weak van derder WaalsWaalsbondsbonds
cc
Hydrotalcite
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Phyllosilicates
Gibbsite: Al(OH)Gibbsite: Al(OH)33
Layers of octahedral Al in coordination with (OH)Layers of octahedral Al in coordination with (OH)
AlAl3+3+ means that means that only 2/3 of the VI sites may be occupiedonly 2/3 of the VI sites may be occupied for chargefor charge--balance reasonsbalance reasons
BruciteBrucite--type layers may be called type layers may be called trioctahedraltrioctahedral and gibbsiteand gibbsite--type type dioctahedraldioctahedral
aa11
aa22
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Phyllosilicates
Kaolinite:Kaolinite: AlAl22 [Si[Si22OO55] (OH)] (OH)44
TT--layers and layers and didiocathedralocathedral (Al(Al3+3+) layers ) layers
(OH) at center of T(OH) at center of T--rings and fill base of VI layer rings and fill base of VI layer →→
Yellow = (OH)Yellow = (OH)T T O O --T T O O --T T OO
vdwvdw
vdwvdw
weak van weak van derder WaalsWaals bonds between Tbonds between T--O groups O groups
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Phyllosilicates
Serpentine:Serpentine: MgMg33 [Si[Si22OO55] (OH)] (OH)44
TT--layers and layers and tritriocathedralocathedral (Mg(Mg2+2+) layers ) layers
(OH) at center of T(OH) at center of T--rings and fill base of VI layer rings and fill base of VI layer →→
Yellow = (OH)Yellow = (OH)T T O O --T T O O --T T OO
vdwvdw
vdwvdw
weak van weak van derder WaalsWaals bonds between Tbonds between T--O groups O groups
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Serpentine
Octahedra are a bit larger than tetrahedral Octahedra are a bit larger than tetrahedral match, so they cause bending of the Tmatch, so they cause bending of the T--O O layers (after Klein and layers (after Klein and HurlbutHurlbut, 1999)., 1999).
Antigorite maintains a Antigorite maintains a sheetsheet--like form by like form by
alternating segments of alternating segments of opposite curvatureopposite curvature
Chrysotile does not do this Chrysotile does not do this and tends to roll into tubesand tends to roll into tubes
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ChrysotileChrysotile, asbestos, asbestos
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Serpentine
The rolled tubes in chrysotile resolves the apparent The rolled tubes in chrysotile resolves the apparent paradox of paradox of asbestosformasbestosform sheet silicatessheet silicates
S = serpentine T = talcS = serpentine T = talcNagby and Faust (1956) Am. Mineralogist 41, 817-836.
Veblen and Busek, 1979, Science 206, 1398-1400.
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Phyllosilicates
Pyrophyllite:Pyrophyllite: AlAl22 [Si[Si44OO1010] (OH)] (OH)22
TT--layer layer -- didiocathedralocathedral (Al(Al3+3+) layer ) layer -- TT--layer layer
T T O O T T --T T O O T T --T T O O TT
vdwvdw
vdwvdw
weak van weak van derder WaalsWaals bonds between T bonds between T -- O O -- T groups T groups
Yellow = (OH)Yellow = (OH)
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Phyllosilicates
Talc:Talc: MgMg33 [Si[Si44OO1010] (OH)] (OH)22
TT--layer layer -- tritriocathedralocathedral (Mg(Mg2+2+) layer ) layer -- TT--layer layer
T T O O T T --T T O O T T --T T O O TT
vdwvdw
vdwvdw
weak van weak van derder WaalsWaals bonds between T bonds between T -- O O -- T groups T groups
Yellow = (OH)Yellow = (OH)
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Phyllosilicates
Muscovite:Muscovite: KK AlAl22 [Si[Si33AlAlOO1010] (OH)] (OH)2 2 (coupled K (coupled K -- AlAlIVIV))
TT--layer layer -- didiocathedralocathedral (Al(Al3+3+) layer ) layer -- TT--layer layer -- KK
T T O O T T KKT T O O T T KKT T O O TT
K between T K between T -- O O -- T groups is stronger than T groups is stronger than vdwvdw
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Phyllosilicates
Phlogopite:Phlogopite: K MgK Mg33 [Si[Si33AlOAlO1010] (OH)] (OH)22
TT--layer layer -- tritriocathedralocathedral (Mg(Mg2+2+) layer ) layer -- TT--layer layer -- KK
T T O O T T KKT T O O T T KKT T O O TT
K between T K between T -- O O -- T groups is stronger than T groups is stronger than vdwvdw
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SOLID SOLUTION
• Occurs when, in a crystalline solid, one element substitutes for another.
• For example, a garnet may have the composition: (Mg1.7Fe0.9Mn0.2Ca0.2)Al2Si3O12.
• The garnet is a solid solution of the following end member components:
Pyrope - Mg3Al2Si3O12; Spessartine - Mn3Al2Si3O12;Almandine - Fe3Al2Si3O12; and Grossular -
Ca3Al2Si3O12.
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GOLDSCHMIDT’S RULES
1. The ions of one element can extensively replace those of another in ionic crystals if their radii differ by less than approximately 15%.
2. Ions whose charges differ by one unit substitute readily for one another provided electrical neutrality of the crystal is maintained. If the charges differ by more than one unit, substitution is generally slight.
3. When two different ions can occupy a particular position in a crystal lattice, the ion with the higher ionic potential forms a stronger bond with the anions surrounding the site.
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RINGWOOD’S MODIFICATION OFGOLDSCHMIDT’S RULES
4. Substitutions may be limited, even when the size and charge criteria are satisfied, when the competing ions have different electronegativities and form bonds of different ionic character.
This rule was proposed in 1955 to explain discrepancies with respect to the first three Goldschmidt rules.
For example, Na+ and Cu+ have the same radius and charge, but do not substitute for one another.
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COUPLED SUBSTITUTIONS
Can Th4+ substitute for Ce3+ in monazite (CePO4)? Rule 1: When CN = 9, rTh4+ = 1.17 Å, rCe3+ = 1.23Å. OKRule 2: Only 1 charge unit difference. OKRule 3: Ionic potential (Th4+) = 4/1.17 = 3.42; ionic
potential (Ce3+) = 3/1.23 = 2.44, so Th4+ is preferred!Rule 4: χTh = 1.3; χCe = 1.1. OK
But we must have a coupled substitution to maintain neutrality:
Th4+ + Si4+ ↔ Ce3+ + P5+
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But can Si4+ substitute for P5+ according to Goldschmidt’s rules?
Rule 1: When CN = 4, rSi4+ = 0.34 Å, rP5+ = 0.25 Å. OK
Rule 2: Only 1 charge unit difference. OKRule 3: Ionic potential (Si4+) = 4/0.34 = 11.76; ionic
potential (P5+) = 5/0.25 = 20, so P5+ is preferred.Rule 4: χSi = 1.8; χP = 2.1. OK
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OTHER EXAMPLES OF COUPLED SUBSTITUTION
Plagioclase: NaAlSi3O8 - CaAl2Si2O8
Na+ + Si4+ ↔ Ca2+ + Al3+
Gold and arsenic in pyrite (FeS2):Au+ + As3+ ↔ 2Fe2+
REE and Na in apatite (Ca5(PO4)3F):REE3+ + Na+ ↔ 2Ca2+
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INCOMPATIBLE VS. COMPATIBLE TRACE ELEMENTS
Incompatible elements: Elements that are too large and/or too highly charged to fit easily into common rock-forming minerals that crystallize from melts. These elements become concentrated in melts.
Large-ion lithophile elements (LIL’s): Incompatible owing to large size, e.g., Rb+, Cs+, Sr2+, Ba2+, (K+).
High-field strength elements (HFSE’s): Incompatible owing to high charge, e.g., Zr4+, Hf 4+, Ta4+, Nb5+, Th4+, U4+, Mo6+, W6+, etc.
Compatible elements: Elements that fit easily into rock-forming minerals, and may in fact be preferred, e.g., Cr, V, Ni, Co, Ti, etc.