Crystallography and

Crystal Structures

Guna Selvaduray
MatE 115 – Fall 2006
 Concepts of Crystallinity
¾ Crystalline solids
G. Selvaduray – SJSU – Fall 2006

¾ Features:

¾ Amorphous solids

¾ Features:

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 Symmetry Operations
¾ Mirror planes
¾ Rotational symmetry,
e.g., 90o, 180o
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¾ Translational
symmetry
¾ e.g., chess board with
identical chess pieces
¾ 1-D or 2-D
symmetry?
¾ Translation vector
¾ Length, direction b a
¾ Straight-line path

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 Arrays
¾ 1-D arrays Æ line lattice
¾ 2-D arrays Æ plane lattice
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¾ 3-D arrays Æ space lattice

¾ Repetition of identical points
¾ Lattice: Set of points in space such that
the surroundings of one point are identical
with those of all others

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 Lattice Points
¾ Points arranged periodically in 3-D space
¾ Points with identical surroundings
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 Unit Cell
¾ Smallest possible “structural” unit that is
repeated, 3 dimensionally
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¾ Contains a full description of the structure

as a whole
¾ Complete structure can be generated by
the repeated stacking of adjacent unit
cells, face to face, throughout three-
dimensional space
¾ Crystallographic analog of “atom”

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 Crystal Systems
¾ Seven unique unit cell shapes that can be
stacked together to fill three-dimensional
space
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 Bravais Lattices
¾ Crystal systems, combined with the permissible
ways in which atoms can be stacked together in a
unit cell results in the 14 Bravais Lattices
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¾ Not to be confused with “crystal structure”

¾ “Crystal structure” is derived by combining
“Bravais Lattice” and “motif” or “basis”
¾ Motif or Basis: A group of one or more atoms or
ions, located in a particular manner with respect to
each other and associated with one lattice point
¾ aka: Number of atoms/ions per lattice point

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 Cubic system
¾ Translational symmetry?
¾ Number of lattice points in unit cell?
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 Coordinates, Directions & Planes

¾ Intercepts – not actual distances

¾ Coordinates of atoms/ions → (x,y,z)
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¾ Directions (x2, y2, z2) – (x1, y1, z1) → [xyz]

¾ Planes – Miller Indices (xyz)
¾ Determine intercepts
¾ Take reciprocals
¾ Clear fractions

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 G. Selvaduray – SJSU – Fall 2006
Coordinates

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Directions

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Equivalent Directions

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 G. Selvaduray – SJSU – Fall 2006
Planes

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 Elemental Cubic System - SC
¾ Coordinates of atoms
¾ Number of atoms/unit cell
Relationship between lattice
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¾
parameter & atomic radius
¾ Coordination number
¾ Distance to nearest neighbor

¾ Number of nearest neighbors

¾ Linear density
¾ Planar density
¾ Volume density (packing fraction)
¾ Interstitial site(s)

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 Lattice Parameter & Atomic
Radius
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 Coordination Number
aka Number of Nearest Neighbors
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 Linear Density
¾ Number of lattice points per unit length
(lattice parameter) in the direction of
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interest

Linear Density
¾ Fraction actually covered by atoms in the
direction of interest

[100] vs [110] vs [111]

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G. Selvaduray – SJSU – Fall 2006
Planar Density

Planar Density = atoms per face = number

area of face area
Planar Packing Fraction = area of atoms per face
area of face
= area
area
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 Volume Density
¾ aka Packing Factor
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¾ (Atomic) Packing Factor =

(# of atoms/cell)(Vol of each atom)

Vol of unit cell

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 G. Selvaduray – SJSU – Fall 2006
Interstitial Site

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 Elemental Cubic System - BCC
¾ Coordinates of atoms
¾ Number of atoms/unit cell
Relationship between lattice
G. Selvaduray – SJSU – Fall 2006

¾
parameter & atomic radius
¾ Coordination number
¾ Distance to nearest neighbor

¾ Number of nearest neighbors

¾ Linear density
¾ Planar density
¾ Volume density (packing fraction)
¾ Interstitial site(s)

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 Lattice Parameter & Atomic
Radius
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 G. Selvaduray – SJSU – Fall 2006
Coordination Number

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 ¾ Linear Density
¾ Linear Packing Fraction
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¾ Planar Density
¾ Planar Packing Fraction
¾ Volume Density
¾ (Atomic) Packing Fraction

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 G. Selvaduray – SJSU – Fall 2006
Interstitial Sites

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 Elemental Cubic System - FCC
¾ Coordinates of atoms
¾ Number of atoms/unit cell
Relationship between lattice
G. Selvaduray – SJSU – Fall 2006

¾
parameter & atomic radius
¾ Coordination number
¾ Distance to nearest neighbor

¾ Number of nearest neighbors

¾ Linear density
¾ Planar density
¾ Volume density (packing fraction)
¾ Interstitial site(s)
¾ Isotropy vs Anisotropy

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 Lattice Parameter & Atomic
Radius
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 G. Selvaduray – SJSU – Fall 2006
Coordination Number

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 ¾ Linear Density
¾ Linear Packing Fraction
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¾ Planar Density
¾ Planar Packing Fraction
¾ Volume Density
¾ (Atomic) Packing Fraction

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Interstitial Sites

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 Diamond Cubic
¾ Si, Ge, α-Sn, diamond
¾ Bravais Lattice = ?
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¾ Crystal Structure = ?
¾ Number of Lattice Points = ?
¾ Translational Symmetry = ?
¾ Motif/Basis = ?
¾ Number of atoms/lattice point

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G. Selvaduray – SJSU – Fall 2006
Crystallographic Directions

(x2, y2, z2) – (x1, y1, z1)

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G. Selvaduray – SJSU – Fall 2006
Equivalent Directions

Criterion:
Indistinguishable

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Equivalent Planes

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 Elemental Tetragonal System

a=b≠c
α = β = γ = 90
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Examples: In, α-Sn,

β-U

Isotropy vs Anisotropy

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 Hexagonal System
¾ a1 = a2 = a3 ≠ c
¾ α = β = 90; γ = 120
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¾ Examples: C
(graphite), Be, Cd, Mg,
α-Ti, etc

Isotropy vs Anisotropy

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G. Selvaduray – SJSU – Fall 2006
Hexagonal Close-Packed

Coordination Number = ?

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 Directions & Planes
¾ Cubic ¾ Hexagonal
¾ 3 axes ¾ 4 axes
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¾ x, y, z ¾ a1, a2, a3, z

¾ BUT a3 is redundant
¾ a1 + a2 = - a3

¾ h’, k’, l’ ¾ h, k, i, l

¾ x, y z

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 Planes

Intercepts
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Reciprocals

Clear Fractions

Miller Indices

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 G. Selvaduray – SJSU – Fall 2006
Directions

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 „ 3 axes: h’, k’, l’
„ 4 axes: h, k, i, l
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h = 1(2h’ – k’)
3
k = 1(2k’ – h’)
3
i = - 1(h’ + k’) [ h + k = - i]
3
l = l’
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 Polymorphism
¾ Phenomenon of the same chemical substance
(material) crystallizing in more than one crystal
structure
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¾ Allotropy: Elemental solids

¾ Polymorphism: Compounds

¾ Examples: Fe, Ti, Mn, Sn, BaTiO3

¾ Significance: Heat treatment of ferrous alloys;
magnetic transformation of BaTiO3
¾ Consequences: Change in volume and other physical
properties
¾ Chemical properties might be similar BUT physical
properties differ greatly
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 Examples

910oC 1400oC 1535oC

¾ α-Fe ↔ γ-Fe ↔ δ-Fe ↔ Liquid Fe
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882oC
¾ α-Ti ↔ β-Ti

¾ Crystal structures for each allotrope?

¾ Volume expansion/contraction?
¾ Solubility of gases

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 Types of Polymorphic
Transformations
¾ Enantiotropic: mutually transformable at the transition
(equilibrium) temperature
¾ Examples: H2O (s) ↔ H2O (l)
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α-Fe ↔ γ-Fe

¾ Monotropic: Proceeds only in one direction, from metastable

to stable
¾ Examples: SiO2 (glass) → SiO2 (quartz)

Fe (martensite) → Fe (ferrite)
C (diamond) → C (graphite)

¾ Stability criteria/regions
¾ Metastability

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G. Selvaduray – SJSU – Fall 2006

Source: R.E. Dickerson, Molecular Thermodynamics, p 224 49

 Phase Transformations
¾ At any given T, P, the phase with Gmin is the most
stable phase
Transition from one phase to another involves a
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¾
discontinuous change in (dG/dX)
¾ dG = dH –TdS → (dG/dT)P = dS

→ (dG/dP)T = dV
¾ 1st Order Phase Transformations: The free
energy function is continuous, but all of its 1st
derivatives are discontinuous, e.g., V, S, E, etc.
¾ 2nd Order Phase Transformations: The free
energy function and its 1st derivatives are
continuous, but the 2nd derivative is discontinuous,
e.g., Tg, cp, etc.
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 G. Selvaduray – SJSU – Fall 2006

Source: Wert & Thomson, p 445

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 Structural Aspects of Phase
Transformations - 1
¾ Transformation of 1st Coordination
¾ Dilatational: aka shear transformation
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¾ No breakage of bonds
¾ Austenite → Martensite
¾ BaTiO3 (cubic) → BaTiO3 (tetragonal)
¾ Low ∆G* (activation energy barrier)
¾ Reconstructive: Bonds broken and reformed
¾ Austenite → Ferrite
¾ High ∆G* (activation energy barrier)
¾ Possible to “bypass” phase transformation by very
rapid cooling

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G. Selvaduray – SJSU – Fall 2006
Dilatational Transformation

Source: Verma & Krishna, p 47 53

 Structural Aspects of Phase
Transformations - 2
„ Transformation of 2nd Coordination
„ Reconstructive:
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„ 1st coordination bonds broken,

„ 2nd coordination bonds broken and reformed,
„ Then 1st coordination bonds reformed in
original format
„ SiO2 (quartz) ↔ SiO2 (tridymite) ↔ SiO2
(cristobalite)
„ Displacive
„ Change in 2nd coordination without breaking 1st
coordination bonds

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 Structural Aspects of Phase
Transformations - 3
¾ Transformations of Bond Type
C (diamond) → C (graphite)
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covalent metallic

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 Compound Structures - 1

Coordinates of atoms
Number of ions/unit
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cell
Coordination number
Nearest
neighbor(s)
Interstitial site(s)
Charge neutrality

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 Compound Structures - 2
Coordinates of atoms
Number of ions/unit
cell
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Coordination number
Nearest
neighbor(s)
Interstitial site(s)
Charge neutrality

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G. Selvaduray – SJSU – Fall 2006
Compound Structures - 3

Coordinates of atoms
Number of ions/unit
cell
Coordination number
Nearest
neighbor(s)
Interstitial site(s)
Charge neutrality 58
G. Selvaduray – SJSU – Fall 2006
Compound Structures - 4

Coordinates of atoms
Number of ions/unit
cell
Coordination number
Nearest
neighbor(s)
Interstitial site(s) 59

Charge neutrality
G. Selvaduray – SJSU – Fall 2006
Perovskite Structure

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Source: Kingery, Bowen & Uhllman, p 68