1/25/2011

1
FundamentalStructure
of
CrystallineSolids y
Nondense,random packing
EnergyandPacking
Energy
typicalneighbor
bondlength
Dense,ordered packing
r
typicalneighbor
bondenergy
Energy
typicalneighbor
bondlength
2
Dense,orderedpackedstructurestendtohave
lowerenergies.
r
typicalneighbor
bondenergy
1/25/2011
2
atomspackinperiodic,3Darrays
Crystalline materials...
metals
many ceramics
MaterialsandPacking
typicalof:
manyceramics
somepolymers
atomshavenoperiodicpacking
Noncrystalline materials...
crystallineSiO2
Si
Oxygen
3
complexstructures
rapidcooling
"Amorphous"=Noncrystalline
occursfor:
noncrystallineSiO2
CrystalTerminalogy
Crystal:Regular,periodicandrepeatedarrangement
Lattice: Three dimensional array Lattice:Threedimensionalarray
ofpointscoincidingwithatom
positions.
Unitcell:smallestrepeatable
entitythatcanbeusedto
completely represent a crystal completelyrepresentacrystal
structure.Itisthebuilding
blockofcrystalstructure.
1/25/2011
3
7crystalsystems
A small group of lattice points which forms
a repetitive pattern is called a unit cell.
14Bravais/spacelattices
a,b,andc arethelatticeconstants
Cl ifi ti f C t l S t
5
Classification of Crystal Systems:
The angles ( ,,) between the lattice translation vectors and the
distance(a,b,c) between two successive points along these vectors
are used to classify the crystal structures into 7 systems
1/25/2011
4
1/25/2011
5
Rareduetolowpackingdensity (onlyPolonium(Po)hasthisstructure)
d
SimpleCubicStructure(SC)
Coordination# =6
(#nearestneighbors)
9
(CourtesyP.M.Anderson)
AtomicPackingFactor(APF)
APF=
Volumeofatomsinunitcell*
Volumeofunitcell
4
3
(0.5a)
3
1
atoms
unitcell
atom
volume
*assumehardspheres
a
R 0 5
10
APFforasimplecubicstructure=0.52
APF=
a
3
unitcell
volume
R=0.5a
contains8x1/8=
1 atom/unitcell
1/25/2011
6
Atomstoucheachotheralongcubediagonals.
Note:Allatomsareidentical;thecenteratomisshaded
differentlyonlyforeaseofviewing.
BodyCenteredCubicStructure(BCC)
Coordination#=8
ex:Cr,W,Fe(),Tantalum,Molybdenum
11
(CourtesyP.M.Anderson)
2atoms/unitcell:1center+8cornersx1/8
AtomicPackingFactor:BCC
APFforabodycenteredcubicstructure=0.68
a 3
a
length=4R =
Closepackeddirections:
3a
a
R
a 2
12
APF=
4
3
( 3 a/4 )
3
2
atoms
unitcell
atom
volume
a
3
unitcell
volume
1/25/2011
7
Atomstoucheachotheralongfacediagonals.
Note:Allatomsareidentical;thefacecenteredatomsareshaded
differentlyonlyforeaseofviewing.
FaceCenteredCubicStructure(FCC)
Coordination#=12
ex:Al,Cu,Au,Pb,Ni,Pt,Ag
13
(CourtesyP.M.Anderson)
4atoms/unitcell:6facex1/2+8cornersx1/8
APFforafacecenteredcubicstructure=0.74
AtomicPackingFactor:FCC
maximumachievableAPF
Closepackeddirections:
atoms
length=4R = 2a
Unitcellcontains:
6x 1/2+8x 1/8
= 4atoms/unitcell
a
2a
14
APF=
4
3
( 2 a/4 )
3
4
atoms
unitcell
atom
volume
a
3
unitcell
volume
1/25/2011
8
3D Projection
2DProjection
HexagonalClosePackedStructure
(HCP)
3DProjection
c
a
Asites
B sites
Asites
Bottomlayer
Middlelayer
Top layer
15
Coordination#=12
APF=0.74
6atoms/unitcell
ex:Cd,Mg,Ti,Zn
c/a =1.633
a
Possible Bravais lattices:
Cubic : Simple, BC, FC
Hexagonal : Simple
Tetragonal : Simple, BC
Orthorhombic : Simple Base C Body-C FC Orthorhombic : Simple, Base C, Body C, FC
Monoclinic : Simple, BC
Triclinic, Trigonal : Simple
Crystal System Axial relationships Interaxial Angles
Cubic a=b=c ===90
o
tetragonal a=bc ===90
o
Hexagonal a=bc ==90

=120

Rhomohedral/try
gonal
a=b=c ==90
o
Orthorhombic a b c ===90
o
Monoclinic a b c ==90
o

triclinic a b c 90
o
1/25/2011
9
Allotropy
1/25/2011
10
=
n A
V N
A
# atoms/unit cell Atomic weight (g/mol)
V l / it ll
THEORETICALDENSITY,
Example: Copper
V
c
N
A
Volume/unit cell
(cm
3
/unit cell)
Avogadro's number
(6.023 x 10
23
atoms/mol)
Data from Table inside front page of Callister :
crystal structure = FCC: 4 atoms/unit cell
atomic weight = 63 55 g/mol (1 amu = 1 g/mol) atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
atomic radius R = 0.128 nm (1 nm = 10
-7
cm)
V
c
= a
3
; For FCC, a = 4R/ 2 ; V
c
= 4.75 x 10
-23
cm
3
Compare to actual:
Cu
= 8.94 g/cm
3
Result: theoretical
Cu
= 8.89 g/cm
3
Element
Aluminum
Argon
Barium
Beryllium
Symbol
Al
Ar
Ba
Be
At. Weight
(amu)
26.98
39.95
137.33
9.012
Atomic radius
(nm)
0.143
------
0.217
0.114
Density
(g/cm
3
)
2.71
------
3.5
1.85
Crystal
Structure
FCC
------
BCC
HCP
CharacteristicsofSelectedElementsat20C
y
Boron
Bromine
Cadmium
Calcium
Carbon
Cesium
Chlorine
Chromium
Cobalt
B
Br
Cd
Ca
C
Cs
Cl
Cr
Co
9.01
10.81
79.90
112.41
40.08
12.011
132.91
35.45
52.00
58 93
------
------
0.149
0.197
0.071
0.265
------
0.125
0 125
2.34
------
8.65
1.55
2.25
1.87
------
7.19
8 9
Rhomb
------
HCP
FCC
Hex
BCC
------
BCC
HCP
15
Cobalt
Copper
Flourine
Gallium
Germanium
Gold
Helium
Hydrogen
Co
Cu
F
Ga
Ge
Au
He
H
58.93
63.55
19.00
69.72
72.59
196.97
4.003
1.008
0.125
0.128
------
0.122
0.122
0.144
------
------
8.9
8.94
------
5.90
5.32
19.32
------
------
HCP
FCC
------
Ortho.
Dia. cubic
FCC
------
------
1/25/2011
11

metals

ceramics

polymers

Graphite/
Ceramics/
Semicond
Metals/
Alloys
Composites/
fibers
Polymers
2 0
30
B ased on data in Table B1, Callister
*GFRE CFRE & AFRE are Glass
Platinum
DENSITIESOFMATERIALCLASSES
(
g
/
c
m
3
)
2 0
GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix). 10
3
4
5
Aluminum
Steels
Titanium
Cu,Ni
Tin, Zinc
Silver, Mo
Tantalum
Gold, W
Glass - soda
Concrete
Si nitride
Diamond
Al oxide
Zirconia
Glass fibers
16

1
2
0.3
0.4
0.5
Magnesium
G raphite
Silicon
Concrete
H DPE, PS
PP, LDPE
PC
PTFE
PET
PVC
Silicone
Wood
AFRE *
CFRE *
GFRE*
Carbon fibers
A ramid fibers
a)crystalSystem?
b)CrystalStructure?
c)Density?ifA
w
=141g/mol
3.2
Tetragonal
BCT
) y
w
g
1/25/2011
12
Crystallographic Points Coordinates
Fractionalmultiplesofunitcell,edgelengths.
Lessthanorequal1
Withoutseparationwithcommas(,)
PointCoordinates
Pointcoordinatesforunitcell
centerare
a/2 b/2 c/2
z
c
111
a/2,b/2,c/2
Pointcoordinatesforunitcell
cornerare111
x
y
a b
000
24
1/25/2011
13
CrystallographicDirections
1. Vector repositioned (if necessary) to pass
through origin.
2 R d ff j ti i t f
z Algorithm
2. Read off projections in terms of
unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
[uvw]
ex: 1 0 => 2 0 1 => [201]
x
y
25
ex: 1 0 => 2 0 1 => [201]
-1 1 1
families of directions <uvw>
where overbar represents a negative index [111] =>
How to draw the direction of [uvw]
1.Divide with the biggest integer among them.
2. Multiply with edge lengths.
3. Take corresponding length on ref. Axis/edges.
4. Farm a line by projection.
1/25/2011
14
3.9: Draw a [211] direction in Orthorhombic unit cell?
1 2 -1 1
U V W
_
4. Move along the edges / axis
2
2/2 -1/2 1/2
3 a - b/2 c/2
3.9: Draw a [211] direction in Orthorhombic unit cell?
1 2 -1 1
U V W
_
4. Move along the edges / axis
2
2/2 -1/2 1/2
3 a - b/2 c/2
a
-b/2
c/2
1/25/2011
15
HCPCrystallographicDirections
1. Vector repositioned (if necessary) to pass
through origin.
2 R d ff j ti i t f it
z
Algorithm
2. Read off projections in terms of unit
cell dimensions a
1
, a
2
, a
3
, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
[uvtw]
a
2
-a
3
a
2
-
a
3
a
1
a
2
30
[1120] ex: , , -1, 0 =>
dashed red lines indicate
projections onto a
1
and a
2
axes
a
1
a
3
a
3
2
a
2
2
a
1
1/25/2011
16
HCPCrystallographicDirections
HexagonalCrystals
4parameterMillerBravaislatticecoordinatesare
relatedtothedirectionindices(i.e.,u'v'w')asfollows.
= v
u
) ' u ' v 2 (
1
-
) ' v ' u 2 (
3
1
- =
] uvtw [ ] ' w ' v ' u [
a
2
z
31
=
=
=
' w w
t
v
) v u ( + -
) u v 2 (
3
-
-
a
3
a
1
3.17
1/25/2011
17
Crystallographic Planes
Crystallographic planes are specified by
Miller indices (hkl)
Indices are smallest Reciprocal of plane
Intercepts with edges (Axis) of unit cell.
A t l ll l t h th Any two planes parallel to each other are
equivalent and have identical indices.
Procedure:
1.Determine the intercepts made by the plane with
the three axes. If the plane passes through the
origin pick a parallel plane within the unit cell.
2 C l l t th i l f th i t t 2. Calculate the reciprocals of the intercepts.
3. Divide by a common factor to convert to
smallest possible integers.
4. Enclose in parentheses no
commas i.e., (hkl)
1/25/2011
18
1. Intercepts 1 1
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0
example a b c
z
y
c
4. Miller Indices (110)
1. Intercepts 1 1 1
2. Reciprocals 1/1 1/1 1/1
1 1 1
Example 2 a b c
x
y
a b
4. Miller Indices (111)
1 1 1
3. Reduction 1 1 1
z
c
example
1. Intercepts 1/2 1 3/4
a b c
x
y
a b

4. Miller Indices (634)

1. Intercepts 1/2 1 3/4
2. Reciprocals 1/ 1/1 1/
2 1 4/3
3. Reduction 6 3 4
36
(001) (010),
Family of Planes {hkl}
Same atomic arrangement
( 100), (010), (001), Ex: {100}= (100),
1/25/2011
19
(110) For FCC
Atomic Arrangements in planes
(110) For BCC
3.21: for cubic unit cell
a) (101), b) (211) c) (012) d) (313) e) (111) f) (212) g) (312) h) (301)
_ _ _ _ _ _ _
1/25/2011
20
4.3) c/a = 1.633
in HCP
Atom at M is midway between the top and
bottom so
Atom at M is midway between the top and
bottom so
1/25/2011
21
3.27: fallowing are the planes
a) What is crystal system?
b) What is crystal lattice?
Tetragonal
BCT
BCT
1/25/2011
22
4.20: fallowing are the planes
a) What is crystal system?
b) What is crystal lattice?
Orthorambic
FCO
1/25/2011
23
c) Determine atomic wt if = 18.91 ?
=
n A
# atoms/unit cell Atomic weight (g/mol)
=
V
c
N
A
Volume/unit cell
(cm
3
/unit cell)
Avogadro's number
(6.023 x 10
23
atoms/mol)
1/25/2011
24
LinearDensity
[110]
vector direction of length
vector direction on centered atoms of number
Density Linear =
ex: linear density of FCCl in [110]
direction
[110]
47
a
#atoms
length
1
2/a nm
a 2
2
LD

=
=
[111] 2/ 3 a
[100] 1/a
[110] 1/ 2 a
BCC
[ ]
a
R
FCC
[100] 1/a
a
2a
[111] 1/ 3 a
[100] 1/a
[110] 2/ a
1/25/2011
25
Planar Densities
plane of area
plane a on centered atoms of number
Density Planar =
plane of area
(001) plane
#atoms
length
2
2 /a
2
nm
a
2
2
PD

=
=
(111) 1/ 3a
2
(100) 1/a
2
(110) 2 /a
2
BCC
( )
a
R
FCC
(100) 2/a
2
a
2a
(111) 4/ 3 a
2
(100) 2/a
(110) 2/ a
2
1/25/2011
26
PlanarDensityof(100)Iron
Solution: AtT<912CironhastheBCCstructure.
4
2D repeat unit
(100) 1/a
2
Radius of iron R =0.1241 nm
R
3
4
a =
a
R
51
=
Planar Density =
a
2
1
atoms
2D repeat unit
=
nm
2
atoms
12.1
m
2
atoms
=1.21 x 10
19
1
2
R
3
4
area
2D repeat unit
LinearDensityof(111)Iron
[111] 2/ 3a [ ]
a
R
Radius of iron R =0.1241 nm
R
3
4
a =
52
2
=
=
nm
atoms
4.029
m
atoms
4.029 x 10
9
R
3
linear Density =
atoms
2D repeat unit
length
2D repeat unit
3
4
1/25/2011
27
[110] 2/ a
Highest planar & Linear density for FCC / CCP
(Cubic Closed Pack)
a
2a
(111) 4/ 3 a
2
Closed packed directions
Closed packed planes
ABCABC... Stacking Sequence
2D Projection
B B
C
A
A
FCCSTACKINGSEQUENCE
A sites
B sites
C sites
B
B
B B B
C
C
A
FCC Unit Cell A
B
11
B
C
1/25/2011
28
A
A
B
C
B
FCC Stacking sequence
C
1/25/2011
29
ABAB... Stacking Sequence
3D Projection 2D Projection
HEXAGONALCLOSEPACKED
STRUCTURE(HCP)
3D Projection 2D Projection
A sites
B sites
A sites
Bottom layer
Middle layer
Top layer
12
Bottom layer
B
A
A
B
A
A
A
HCP Stacking sequence
1/25/2011
30
Polymorphism
Twoormoredistinctcrystalstructuresforthe
samematerial(allotropy/polymorphism)
liquid
iron system
Titanium,Ti
carbon
diamond,graphite
BCC
FCC
1538C
1394C
912C
-Fe
-Fe
60
BCC
-Fe
"Existence of an elemental solid into more than
one physical forms is known as ALLOTROPY "
1/25/2011
31
Existence of substance into more than one
crystalline forms is known as
"POLYMORPHISM".
Example:
1) Mercuric iodide (HgI
2
) forms two types of crystals.
a. Orthorhombic
b. Trigonal
2) Calcium carbonate (CaCO3) exists in two types of
t lli f crystalline forms.
a. Orthorhombic (Aragonite)
b. Trigonal
Allotropy
1/25/2011
32
Some engineering applications require single crystals:
--diamond single
crystals for abrasives
--turbine blades
CRYSTALSASBUILDINGBLOCKS
Crystal properties reveal features
of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.
Most engineering materials are polycrystals.
Polycrystals
Anisotropic
Nb-Hf-Wplate with an electron beamweld.
1 mm
Isotropic
64
Nb Hf W plate with an electron beam weld.
Each "grain" is a single crystal.
If grains are randomly oriented,
overall component properties are not directional.
Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
1/25/2011
33
Poly crystals
Single Crystals
-Properties vary with
direction: anisotropic.
Example: the modulus
Singlevs Polycrystals
E (diagonal) =273 GPa
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
200 m
E (edge) =125 GPa
66
If grains are randomly
oriented: isotropic.
(E
poly iron
=210 GPa)
-If grains are textured,
anisotropic.