 Crystals

Crystals
y
Atoms and crystals

HYPOTHESIS: Structural units = atoms

Example: NaCl Atomic masses: Na 38.12 x 10-24 g

Cl 58.85 x 10-24 g

Cubic structure
1 cm3 m = 2.165 g
N = 44.6 x 1021 atoms

0.28 nm = 2.8 Å

Inter-atomic distances
CONCLUSION: ≈ X-ray wavelengths
Atomic dimensions
Crystal structure

Bravais lattice + Basis

1-D
1-D Atom

Molecule

2-D
2-D

3-D
3-D Protein
Bravais lattice + basis

1-D

2-D

3-D
 Crystal lattices
 Translation vectors (2D)

2-D

r
R
For every lattice point
r r r
r R = n1a + n2b
b
r €
a
integers primitive
Arbitrary origin € vectors

€
 Primitive vectors (2D)

r r r 2-D

R = n1a + n2b

r r
R r R
R
€
r
b
r € €
a €

€ r r
Different choices of primitive vectors a, b
 Non-primitive vectors (2D)

2-D
r r
Not all a, b pairs are primitive

r r
R r R
R
€
r
b €
r € €
a

r r r
€
R ≠ n1a + n2b
Primitive vectors (3D)

r r r r 3-D
R = n1a + n2b + n3c

€
r r
c b
r
a
€ € r r r
Different choices of primitive vectors a , b , c

€
 Primitive unit cells (2D)

2-D

r
b
r
a
Different choices of primitive unit cells

Primitive cell = 1 lattice point

 Conventional unit cells (2D)

2-D

r
b
r
a

€ More than 1 lattice point per unit cell

Unit cell

• Primitive Unit
Cell: A, C, and
E

• Non-primitive
Unit Cell: B
and D

• Wigner-Seitz
Cell: F
Non-Bravais lattices

Atoms 2-D

r r r
R ≠ n1a + n2b

Un-equivalent
sites €
Bravais lattices

Bravais
lattice

Basis
 Non-Bravais Lattices
• In a Bravais Lattice, not only the atomic arrangement but also
the orientations must appear exactly the same from every
llattice
tti point.
i t

2 Dimensional Honeycomb Lattice

• The red dots each have a neighbour

to the immediate left
left. The blue dot
has a neighbor to its right. The red
((& blue)) sides are equivalent
q &
have the same appearance. But, the
red & blue dots are not equivalent. If
the blue side is rotated through 180º
the lattice is invariant. Honeycomb
 The Honeycomb Lattice is NOT a Bravais Lattice
Lattice!!
Non-Bravais Lattices
 Classification of cells

2-D 3-D

r r
b c
γ
r r
a α b
€
γ
€ r
β a
a b c
€ latin
€ €
α β γ greek
€
2D Bravais Lattice: 5
3D Bravais Lattice: 14
Cubic

Tetragonal
 3D Bravais Lattice: 14
Orthorhombic

Monoclinic
3D Bravais Lattice: 14
Trigonal Triclinic

Hexagonal
 Coordinates

2 (3, 2)
Lattice points:
integer
coordinates
€ r r
r
€ R = n1a + n2b
1
1
2
1 €
4
€
1 3
€
0 4 4 1 2 3
€
Inside cell: fractional coordinates
€ €
1 1  3 1
 ,   , 
4 4
€ 4 2
€ €
€
Translational Vector and Translational operator

o A basis of atoms is attached to a lattice point and each atom in

the basis is specified by:
rj  x j a  y jb  z j c
where 0  xj, yj, zj  1.
o The basis consists of one or several atoms.
o The primitive cell in 3D is a parallelepiped specified by the
primitive translation vectors. It is a minimum volume cell and
there is one lattice point per primitive cell.
o The volume of the primitive cell is:

Vc  a  b  c 

o Basis associated with a primitive cell is called a primitive basis

and contains the least # of atoms.
Translational Vector and Translational operator

o The lattice and the lattice translation vectors a, b and c are

primitive if any two points satisfy:
r'  r  n1a  n2b  n3c
where n1, n2 and n3 are integers.
o The primitive lattice translation vectors specify unit cell of
smallest volume.
o A lattice translation operator is defined as a displacement of a
crystal with a crystal translation operator.
R or T  n1a  n2b  n3c
o To describe a crystal, it is necessary to specify three things:
• What is the lattice
• What are the lattice translation vectors
• What is the basis
 Crystal planes
Crystal planes

2-D
Miller indices, 2-D (a)

2-D

r
b
r
a

€
€

(hk) = (21) (hk) = (11)

Miller indices, 2-D (b)

(hk) = (01) (hk) = (1 1 )

€ €

(hk) = (10) (hk) = (2 1 )

Miller indices, cubic lattices

sc

(100) (110) (111)

€ € €
bcc

(200) (110) (222)

€ € €
fcc

(200) (220) (111)

Crystallographic Planes
Crystallographic Planes

• Miller Indices: Reciprocals of the (three) axial intercepts for a

plane,
l cleared
l d off fractions
f ti & common multiples.
lti l All parallelll l
planes have same Miller indices.

• Algorithm
g
1. If the plane passes through the selected origin, choose
another plane or move the origin.
2. Read off intercepts of plane with axes in terms of a, b, c
3. Take reciprocals
p of intercepts
p
4. Reduce to smallest integer values
5 Enclose in parentheses,
5. parentheses no commas i.e.,
i e (h k l) not (h,
(h k,
k l)
Example 1: (100) Plane

Axis X Y Z
Intercept
points 1 ∞ ∞
Reciprocals 1/1 1/ ∞ 1/ ∞
Smallest
R ti
Ratio 1 0 0

((1,0,0)
, , ) Miller İndices ((1 0 0))
Example 2: (110) Plane

Axis X Y Z
Intercept
points 1 1 ∞
Reciprocals 1/1 1/ 1 1/ ∞
Smallest
(0 1 0)
(0,1,0) R ti
Ratio 1 1 0

((1,0,0)
, , ) Miller İndices ((1 1 0))
Example 3: (111) Plane

Axis X Y Z
Intercept
(0,0,1)
points 1 1 1
R i
Reciprocals
l 1/1 1/ 1 1/ 1
Smallest
(0 1 0)
(0,1,0) Ratio
1 1 1
(1,0,0) Miller İndices (1 1 1)
Example 4: (210) Plane

Axis X Y Z
Intercept
points 1/2 1 ∞
Reciprocals 1/(½)
/( ) 1// 1 1// ∞
Smallest
R ti
Ratio 2 1 0
(0,1,0)
(1/2, 0, 0)
Miller İndices ((2 1 0))
Example 5: (120) Plane z

a b c c
1. Intercepts 1 1 
2. Reciprocals 1/1 1/2 1/
1 2 0
y
3. Reduction 1 2 0
a b
4. Miller Indices (1 2 0) x

Example 6: (100) another Plane

z
a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 1 0 0 y
4. Miller Indices (1 0 0) a b

x
Example 7: (634) Plane

z
example
a b c
c
1. Intercepts 1/2 1 3/4 
2
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3  y
a  b
3. Reduction 6 3 4
x
4. Miller Indices (6 3 4)

Family of Planes {h k l}

Ex: {1 0 0} = (1 0 0), (0 1 0), (0 0 1), (1 0 0), (0 1 0), (0 0 1)

 Indices of a Family of Planes

• Sometimes. when the unit cell has rotational symmetry,

several nonparallel planes may be equivalent by virtue of
this symmetry, in which case it is convenient to lump all
these planes in the same Miller Indices,
Indices but with curly
brackets.
{100}  (100), (010), (001), (0 1 0), (001), (1 00)
{111}  (111),
) (111),
) (1 1 1),
) (1 11),
) (1 1 1),
) (1 1 1),
) (1 1 1),
) (1 1 1)

• So,
So indices {h k l} represent all of the planes equivalent
to the plane (h k l) through rotational symmetry.
 Lattice Sites in a Cubic Unit Cell

• The standard notation is shown in the figure. It is

understood that all distances are in units of the cubic lattice
constant a, which is the length of a cube edge for the material
of interest.
 Directions in a Crystal: Standard Notation

• See Figure. Choose an origin, O. This choice

i arbitrary,
is bit b
because every lattice
l tti pointi t has
h
identical symmetry. Then, consider the lattice
vector joining O to any point in space,
space say
point T in the figure. As we’ve seen, this
vector can be written
T = n1a + n2b + n3c [111] direction
• In order to distinguish a Lattice Direction from a Lattice
Point, (n1n2n3), the 3 integers are enclosed in square brackets
[ ...] instead of parentheses (...), which are reserved to indicate
a Lattice Point. In direction [n1n2n3], n1n2n3 are the smallest
i
integers possible
ibl for
f the
h relative
l i ratios.i
Directions in a Crystal: Examples

210

X = 1, Y = ½, Z = 0 X=½ ,Y=½,Z=1
[1 ½ 0] [2 1 0] [½ ½ 1] [1 1 2]
 Directions in a Crystal: Negative Directions

• When we write the direction [n1n2n3] depending

on the origin,
g , negative
g directions are written as
R = n1a + n2b + n3c
With a bar above the negative integers.
T specify
To if the
th direction,
di ti the th smallest
ll t possible
ibl
integers must be used.

13
Examples: Negative Directions

X = 1, Y = 0, Z = 0
[1 0 0] X = -1, Y = -1, Z = 0
[[1 1 0]]
 t can be
A vector b movedd to
t the
th origin
i i .

X = -1, Y = 1, Z = -1/6
[[-1
1 1 -1/6]
1/6] [6 6 1]
 Indices of a Family of Directions

• Sometimes. when the unit cell has rotational symmetry,

several nonparallel directions may be equivalent by
virtue of this symmetry, in which case it is convenient to
lump all these directions in the same Miller Indices,
Indices but
with triangular brackets.
 100 [100],[010],[001],[0 1 0],[001],[1 00]
 111
111[111],
] [111],
] [1 1 1],
] [1 11],
] [1 1 1],
] [1 1 1],
] [1 1 1],
] [1 1 1]

• So,
So indices <h k l> represent all of the directions
equivalent to the direction [h k l] through rotational
symmetry.
symmetry
Salient Features of Miller Indices

o The separation between adjacent parallel planes

in a cubic crystal is given by:
a
d
h2  k 2  l 2
o The angle  between (h1 k1 l1) and (h2 k2 l2 )
planes (or [h1 k1 l1] and [h2 k2 l2 ] directions) is
given by:
h1h2  k1k 2  l1l2
cos  
h
1
2

 k12  l12 h22  k 22  l22 
o The [h1 k1 l1] direction is normal to (h1 k1 l1)
plane
Interplanar distance

dhkl Cubic lattices

2 a2
dhkl = 2 2 2
h + k +l

Copper, fcc, a=3.61 Å

a a a
d200 = = 1.805 Å d220 = = 1.276 Å d111 = = 2.084 Å
2 2 2 3
Equivalent planes and directions

Equivalent directions < 100 >

[010] [001]
€
[100]
€ €

€ (100) (010) (001)

€ € €
Equivalent planes {100}
Planes and directions

Perpendicular direction

[hkl]
Family of planes

(hkl)

€
Periodic table (crystal structure)
Crystal Structure of Metals – of engineering
interest
Simple
p Cubic Structure ((SC))
• Rare due to low packing density (only Po – Polonium --
has this structure))
• Close-packed directions are cube edges.

• Coordination No. = 6
((# nearest neighbors)
g ) for
each atom as seen
(Courtesy P.M. Anderson)
Atomic Packing Factor (APF): SC
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres

• APF for a simple cubic structure = 0.52

0 52
volume
atoms atom
a 4
unit cell 1 (0.5a) 3
R=0.5a 3
APF =
a3 volume
close-packed directions
unit cell
contains ((8 x 1/8)) =
1 atom/unit cell Here: a = Rat*2
Adapted from Fig. 3.23, Where Rat is the ‘handbook’
Callister 7e.
atomic radius
Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube (body) diagonals.
--Note: All atoms are identical; the center atom is shaded
diff
differently
tl only
l ffor ease off viewing.
i i

ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: (1 center) + (8 corners x 1/8)

(Courtesy P.M. Anderson)
 Atomic Packing
g Factor: BCC

3a

2a
Close-packed directions:
R
a l
length
th = 4R = 3 a

atoms volume
4
unit cell 2  ( 3a/4)
3 /4) 3
3 atom
APF =
3 volume
Adapted from
Fig. 3.2(a), Callister 7e.
a
unit cell
• APF for a body-centered cubic structure = 0.68
Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination
C di ti # = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit
t / it cell:
ll (6 face
f x ½) + (8 corners x 1/8)
(Courtesy P.M. Anderson)
Atomic Packing
g Factor: FCC
• APF for a face-centered cubic structure = 0.74
The maximum achievable APF !
Close-packed directions:
2a length = 4R = 2 a
(a = 22*R)
Unit cell contains:
6 x 1/2 + 8 x 1/8
a = 4 atoms/unit cell
Adapted from
atoms volume
Fig. 3.1(a),
4
Callister 7e.
unit cell 4 ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell
 Hexagonal Close-Packed
Close Packed Structure (HCP)
ex: Cd, Mg, Ti, Zn
• ABAB... Stacking
g Sequence
• 3D Projection • 2D Projection

A sites
Top layer
c
B sites
Middle layer
A sites
a Adapted from Fig. 3.3(a),
Bottom layer
Callister 7e
7e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74
• c/a = 1.633 (ideal)
Both FCC & HCP are highest density packing schemes (APF = 0.74)
Theoretical Density, 
Mass of Atoms in Unit Cell
Density =  =
Total Volume of Unit Cell

nA
 =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume
V l it cellll = a3 for
off unit f cubic
bi
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol
 y, 
Theoretical Density,
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
 a = 4R/3 = 0.2887 nm
R
a
atoms theoretical = 7.18 g/cm3
g
unit cell 2 52.00
52 00
mol actual 7 19 g/cm3
= 7.19
=
a3 6.023 x 1023
volume
l atoms
t
unit cell mol
Linear Density – considers equivalance and is
important in Slip
Number of atoms
 Linear Density of Atoms  LD =
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2 
LD   3.5
3 nm 1
length 2a

# atoms CENTERED on the direction of interest!

Length is of the direction of interest within the Unit Cell
 Planar Densityy of (100)
( ) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms atoms
= 19
Planar Density = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm 2 m2
R
2D repeat unit 3
Atoms: wholly contained and centered in/on plane within U.C., area of plane in U.C.
Planar Density of (111) Iron
Solution (cont): (111) plane 1/2 atom centered on plane/ unit cell

2a atoms in plane
atoms above plane
atoms below plane

3
h a
2

Area 2D Unit: ½ hb = ½*[(3/2)a][(2)a]=1/2(3)a2=8R2/(3)

atoms
2D repeat unit 3*1/6
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
2
nm m2
area 8R
8 R2
2D repeat unit 3
 Densities of Material Classes
In general Graphite/
metals > ceramics > polymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum *GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu Ni
Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

 (g/ccm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less
ess de
dense
se pac
packing
g 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low p packing
g density
y PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites
p have... 04
0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 7e.
SUMMARY
• Atoms may assemble into crystalline or
amorphous structures.
structures
• Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal structures.
• We can predict the density of a material, provided we
know the atomic weight
weight, atomic radius
radius, and crystal
geometry (e.g., FCC, BCC, HCP).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.
SUMMARY
• Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure.
t t This
Thi is
i referred
f d to
t as polymorphism
l hi (
(or
allotropy).
• X-ray diffraction is used for crystal structure and
interplanar spacing determinations.