1. Chapter 3: The Structure of Crystalline Solids 2 Fundamental Concepts Crystalline:...
Transcript of 1. Chapter 3: The Structure of Crystalline Solids 2 Fundamental Concepts Crystalline:...
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Chapter 3: The Structure of Crystalline Solids 2
Fundamental Concepts
Crystalline: Repeating/periodic array of atoms; each atom bonds to nearest neighbor atoms.
Crystalline structure:
Results in a lattice or three-dimensional arrangement of atoms
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Chapter 3: The Structure of Crystalline Solids 3
Unit cellsSmallest repeat unit/entity of a lattice.
Represents symmetry of the crystal structure.
Basic structure unit/building block of crystal structure
Defines the crystal structure by its geometry and atom positions
Co-ordination number
For each atom, it is the number of nearest-neighbors or touching atoms
e.g. FCC:12, HCP:12, BCC:8
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Chapter 3: The Structure of Crystalline Solids 4
Atomic packing factor (APF):
APF =
= 0.74 (FCC or HCP)
= 0.68 (BCC)
C
S
VV
volumecellunitTotalcellunitainatomsofVolume
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Chapter 3: The Structure of Crystalline Solids 5
Atoms per unit cell FCC Face atoms= 6 x ½ =3 4
Corners atoms = 8 x 1/8 =1
e.g., Al, Ni, Cu, Au, Ag, Pb, Gamma (γ)-Iron
BCC Body atom=1 2
Corners atoms = 8 x 1/8 =1
e.g., Cr, W, Alpha (α)-Iron, Delta (δ)- Iron, Mo, V, Na
SC Corners atoms = 8 x 1/8 =1 } 1
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Chapter 3: The Structure of Crystalline Solids 6
SC (Simple Cubic) BCC (Body-Centred Cubic)
FCC (Face Centred Cubic)
Metallic crystal structure
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Chapter 3: The Structure of Crystalline Solids 7
where, R: Radius of atom
a: cube edge
a2 + a2 = (4R)2
2a2 = (4R)2 = 16R2
a = 2R √2
APF=
Metallic Crystal Structure continue …….
C
S
VV
volumecellunitTotalcellunitainatomsofVolume
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Chapter 3: The Structure of Crystalline Solids 8
Unit cell volume = Vc = a3
= (2R√2)3 = 16 R3 √2
Vs = 4/3 π R3 x 4 4 atoms/unit cell
=16/3 π R3
Total cell volume, Vc =16 R3 √2
APF = = 0.74
Metallic Crystal Structure continue …….
2R16
R3
16
VV
3
3
C
S
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Chapter 3: The Structure of Crystalline Solids 9
a√3
a√2
Body Centered Cubic
All sides are equal to dimension “a”
a2 + a2 = 2a2
(a√2)2 + a2 = 3a2 = (4R)2
a√3= 4R
Metallic Crystal Structure continue …….
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Chapter 3: The Structure of Crystalline Solids 10
The Hexagonal Close-Packed
6 Atoms at top 12
6 Atoms at bottom
2 Centre face atoms
3 Midplane atoms
12 x 1/6 = 2
2 x 1/2 = 1 6 atoms/unit cell
Midplane 3Co-ordinate number: 12 (HCP or FCC)Atomic packaging factor (APF): 0.74
e.g., Cd, Zn, Mg, Ti
Metallic Crystal Structure continue …….
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Chapter 3: The Structure of Crystalline Solids 11
Density Computations
Density, ρ=
n= No. of atoms/unit cell
A= Atomic weight
Vc=Volume of unit cell
NA= Avogadro’s number (6.023 x 1023/mole)
ACNVnA
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Chapter 3: The Structure of Crystalline Solids 12
Problem:
Copper has an atomic radius of 0.128 nm, an FCC crystal
structure, and an atomic weight of 63.5 g/mol. Compute
its theoretical density and compare the answer with its
measured density.
Given:
Atomic radius = 0.128 nm (1.28 Ǻ)
Atomic weight = 63.5 g/mole
n = 4 ACU = 63.5 g/mol
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Chapter 3: The Structure of Crystalline Solids 13
Solution:
Unit cell volume = 16 R3√2
R = Atomic Radius
= 8.89 g/cm3
Close to 8.94 g/cm3 in the literature
)atoms103cell](6.02/unit cm)10(1.282[16
63.5g/mole4ρ 2338
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Chapter 3: The Structure of Crystalline Solids 14
Crystal system
x, y, z : Coordinate systems
a, b, c : Edge lengths
α, β, γ : Inter axial angles
Cubic system: a=b=c α=β=γ=90°
Lattice parameter (e.g., a,b,c, α, β, γ) determine the crystal system. There are seven crystal systems which are Cubic, Tetragonal, Hexagonal, Rhombohedral (Trigonal), Monoclinic, Triclinic.
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Chapter 3: The Structure of Crystalline Solids 15
Source: William D. Callister 7th edition , chapter 3 page 47
Crystal system
“C” (vertical axis) is elongatedOne side not equal
One side not equal
Equal sidesNot at 90°
Three unequal sides
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Chapter 3: The Structure of Crystalline Solids 16
Crystallographic Direction Steps:
1.Choose a vector of convenient length
2.Obtain vector projection on each of three axes (for the direction to be drawn, if necessary)
3.Divide the three numbers by a common factor (if the indices are to be assigned) to reduce to the smallest integer values
4.Use square brackets [ ]
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Chapter 3: The Structure of Crystalline Solids 17
Crystallographic Planes
Miller Indices (hkl)
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Chapter 3: The Structure of Crystalline Solids 18
Crystallographic Planes
Steps:
1.Obtain lengths of planar intercepts for each axis.
2.Take reciprocals
3.Change the three numbers into a set of smallest integers (use a common factor )
4.Enclose within parenthesis e.g., (012)
Tips: 1. Parallel planes have the same indices
2. An index 0(zero) implies the plane is parallel to that axis.
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Chapter 3: The Structure of Crystalline Solids 19
Crystallographic Planes continue.....
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Chapter 3: The Structure of Crystalline Solids 20
Crystallographic Planes continue.....
Cubic Crystal system
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Chapter 3: The Structure of Crystalline Solids 21
( ) Plane { } Family of planes
[ ] Direction < > Family of directions
e.g., {111}:
)111( )111( )111(
)111( )111( )111( )111(
Crystallographic Planes continue.....
Cubic Crystal system
)111(
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Chapter 3: The Structure of Crystalline Solids 22
Crystallographic Planes continue.....
Hexagonal Crystal system
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Chapter 3: The Structure of Crystalline Solids 23
[u’v’w’] -------> [u v t w]
[0 1 0] -------> ]0121[
u = n/3 (2u’ – v’)
e.g., u = n/3 (2 x0 – 1)
Where, n=factor to convert into indices = 3
u= = n/3 (0 -1)1
Crystallographic Planes continue.....
Hexagonal Crystal system
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Chapter 3: The Structure of Crystalline Solids 24
Crystallographic Planes continue.....
Hexagonal Crystal system
v = n/3 (2v’ – u’)
e.g., v = n/3 (2 x 1 -0)
= n/3 (2)
Where, n=factor to convert into indices = 3
v=2
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Chapter 3: The Structure of Crystalline Solids 25
Crystallographic Planes continue.....
Hexagonal Crystal system
t = - (u’ + v’) u v t w = 0121
e.g., t = -(0 + 1)
= -1 =
w = w’
1
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Chapter 3: The Structure of Crystalline Solids 26
Crystallographic Planes continue.....
Hexagonal Crystal system
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Chapter 3: The Structure of Crystalline Solids 27
Crystallographic Planes continue.....
Hexagonal Crystal system
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Chapter 3: The Structure of Crystalline Solids 28
a1, a2, a3 axes: all in basal plane (at 120° to each other)
Z-axis: Perpendicular to basal plane
[u’v’w’] -------> [u v t w]
a b c a b z c
Miller -------> Miller-Bravais
Crystallographic Planes continue.....
Hexagonal Crystal system
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Chapter 3: The Structure of Crystalline Solids 29
u = n/3 (2u’ – v’) [0 1 0] ------->
Crystallographic Planes continue.....
Hexagonal Crystal system
]0121[
v = n/3 (2v’ – u’) u’v’w’ ----> u v t w
t = - (u’ + v’) u = (0 -1), t = -(1), v = 2, w = 0
w = nw’
n=factor to convert into indices
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Chapter 3: The Structure of Crystalline Solids 30
a√3
a√2
Linear and Planar Atomic Densities
Linear density
BCC
4R = a√3a = 4R/√3
a
N M
BCC LD [100] = [(Distance occupied)/ (distance available)]
= (2R)/ a= 2R/(4R/√2) = 0.866
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Chapter 3: The Structure of Crystalline Solids 31
Source: William D. Callister 7th edition, chapter 3 page 67
X- Ray Diffraction
In phase: reinforcement
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Chapter 3: The Structure of Crystalline Solids 32
Source: William D. Callister 7th edition, chapter 3 page 67
X- Ray Diffraction Continue…
Cancel
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Chapter 3: The Structure of Crystalline Solids 33
Interplanar spacing
Source: William D. Callister 7th edition, chapter 3 page 67
X- Ray Diffraction Continue…
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Chapter 3: The Structure of Crystalline Solids 34
nλ = dhkl sinθ + dhklsinθ
= 2dhkl sinθ
Where, n = an integer, order of reflection = 1 (unless stated otherwise)
Bragg’s law of diffraction
nλ = QTSQ
X- Ray Diffraction Continue…
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Chapter 3: The Structure of Crystalline Solids 35
For cubic system,
a2/d2 = h2 + k2 + l2
X-Ray Diffraction
nλ =
= path difference where n = integer = 1
= dhkl sinθ + dhklsinθ
= 2dhkl sinθ
a2/d2 = h2 + k2 + l2
QTSQ
X- Ray Diffraction Continue…
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Chapter 3: The Structure of Crystalline Solids 36
(h + k + l) must be even: BCC 2, 4, 6, 8, 10, 12……
h k l: all odd or all even FCC 3, 4, 8, 11, 12, 16……..
If the ratio of the sin2θ values of the first two diffracting
planes is 0.75, it is FCC structure. If it is 0.5, it is BCC
structure
X- Ray Diffraction Continue…
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Chapter 3: The Structure of Crystalline Solids 37
λ = 2 d sinθ a2/d2 = h2 + k2 + l2
λ = (2 a sinθ)/ √ (h2 + k2 + l2)
sin2θ = λ2(h2 + k2 + l2)/4a2
“ λ” and “a” are constants
X- Ray Diffraction Continue…
22
22
22
21
21
21
22
12
lkh
lkh
sin
sin
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Chapter 3: The Structure of Crystalline Solids 38
Problem: Given: {211} PlanesaFe = 0.2866 nm (2.866Å)
λ = 0.1542 nm (1.542Å)
Determine dhkl, 2θ (diffraction angle)
n = 1a) dhkl = a/ √ (h2 + k2 + l2)
= 0.2866 nm /√ (22 + 12 + 12) = 0.1170 nm (1.170Å)
b) n =1 sinθ = n λ/2dhkl =
θ = sin-1(0.659) = 41.22°2θ = 82.44°
)nm1170.0)(2()1542.0)(1(
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Chapter 3: The Structure of Crystalline Solids 39
Crystalline and Non-crystalline materialsSingle crystal: No grain boundary
Polycrystalline: Several crystals
Anisotropy: Directionality in properties
Isotropy: No directionality
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Chapter 3: The Structure of Crystalline Solids 40
[100] [110] [111]
FCC Al9.2 10.5 11.0
(63.7) (72.6) (76.1)
FCC Cu9.7 18.9 27.7
(66.7) (130.3) (191.1)
BCC
Fe18.1 30.5 39.6(125) (210.5) (272.7)
BCC
W55.8 55.8 55.8
(384.6) (384.6) (384.6)
Modulus of elasticity (E), psi x 106 (MPa x 103)
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Chapter 3: The Structure of Crystalline Solids 41
Non-Crystalline
•Amorphous
•No systematic arrangement (regular) of atoms
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Chapter 3: The Structure of Crystalline Solids 42
Summary
•Crystalline –lattice
•Crystal system: BCC, FCC, HCP
•Planes, directions, packing
•X-Ray diffraction
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Chapter 3: The Structure of Crystalline Solids 43
Source: Wiliam D. Callister 7th edition, chapter 3 page 42
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Chapter 3: The Structure of Crystalline Solids 44
Source: William D. Callister 7th edition, chapter 3 page 59
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Chapter 3: The Structure of Crystalline Solids 45
Source: William D. Callister 7th edition, chapter 3 page 40
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Chapter 3: The Structure of Crystalline Solids 46
Source: William D. Callister 7th edition, chapter 3 page 43
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Chapter 3: The Structure of Crystalline Solids 47
Source: William D. Callister 7th edition, chapter 3 page 54
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Chapter 3: The Structure of Crystalline Solids 48
Source: William D. Callister 7th edition, chapter 3 page 57