METALS &
CERAMICS
Chapter 3 - 1
Chapter 3: Structures of Metals & Ceramics
ISSUES TO ADDRESS...
• What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
Chapter 3 - 2
Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.41(a),
Callister & Rethwisch 4e.
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.41(b),
Callister & Rethwisch 4e.
Chapter 3 - 3
Energy and Packing
• Non dense, random packing Energy
typical neighbor
bond length
typical neighbor r
bond energy
typical neighbor
bond length
typical neighbor r
bond energy
Chapter 3 - 5
Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)
Chapter 3 - 6
Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.43,
Callister & Rethwisch 4e. Chapter 3 - 7
Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
2a
Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 4e.
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell Chapter 3 - 9
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.
Chapter 3 - 10
Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister & atoms volume
Rethwisch 4e. 4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
3 volume
a
unit cell
Chapter 3 - 11
Theoretical Density, r
nA
r =
VC NA
Chapter 3 - 12
Theoretical Density, r
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 4e.
atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 13
Atomic Bonding in Ceramics
• Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.
• Degree of ionic character may be large or small:
CaF2: large
SiC: small
Adapted from Fig. 2.7, Callister & Rethwisch 4e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition. Copyright 1939 and 1940, 3rd edition copyright © 1960 by Cornell University.
Chapter 3 - 14
Ceramic Crystal Structures
Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions
Chapter 3 - 15
Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
Adapted from Fig. 3.4,
Callister & Rethwisch 4e.
- - - - - -
unstable stable stable
2. Maintenance of
Charge Neutrality : F-
CaF 2 : Ca 2+ +
--Net charge in ceramic
cation anions
should be zero.
--Reflected in chemical F-
formula:
A m Xp
m, p values to achieve charge neutrality
Chapter 3 - 16
Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord. ZnS
r anion Number (zinc blende)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 4e.
rCl = 0.181 nm
rNa/rCl = 0.564
Chapter 3 - 19
MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm
rMg/rO = 0.514
Chapter 3 - 20
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
rCs + 0.170
= = 0.939
rCl- 0.181
Chapter 3 - 21
AX2 Crystal Structures
Fluorite structure
• Antifluorite structure –
positions of cations and
anions reversed
Chapter 3 - 22
Density Computations for Ceramics
n¢(SAC + SAA )
r=
VC N A
Avogadro’s number
Volume of unit cell
Chapter 3 - 23
Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*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
Steels
• often large atomic masses Tin, Zinc
Zirconia
r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
Chapter 3 - 25
Polycrystals Anisotropic
• Most engineering materials are polycrystals.
Chapter 3 - 27
Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
Iron
liquid
1538ºC
carbon
BCC -Fe
diamond, graphite
1394ºC
FCC -Fe
912ºC
BCC -Fe
Chapter 3 - 28
Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems
14 crystal lattices
000
y
a b
Point coordinates for unit cell
x · corner are 111
z 2c
·
Translation: integer multiple of
· · lattice constants identical
b y position in another unit cell
b
Chapter 3 - 30
Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x [uvw]
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
a 2
LD = = 3.5 nm-1
Adapted from
Fig. 3.1(a),
length 2a
Callister &
Rethwisch 4e.
Chapter 3 - 32
Drawing HCP Crystallographic Directions (i)
Chapter 3 - 33
Drawing HCP Crystallographic Directions (ii)
• Draw the [1 2 13] direction in a hexagonal unit cell.
Adapted from p. 62, Algorithm a1 a2 a3 z
Callister &
Rethwisch 8e. 1. Remove brackets -1 -2 1 3
1 2 1
[1213] 2. Divide by 3 - - 1
s 3 3 3
3. Projections
4. Construct Vector
start at point o
proceed –a/3 units along a1 axis to point p
p –2a/3 units parallel to a2 axis to point q
r q a/3 units parallel to a3 axis to point r
c units parallel to z axis to point s
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of three-
axis (a1, a2, and z) unit cell dimensions
a and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas,
for three-axis coordinates
5. Convert to four-axis Miller-Bravais lattice
coordinates using equations below:
1 1
Adapted from p. 74, Callister & u= (2u¢ - v ¢) v = (2v ¢ - u¢)
Rethwisch 4e. 3 3
t = -(u +v) w = w¢
6. Adjust to smallest integer values and
enclose in brackets [uvtw] Chapter 3 - 35
Determination of HCP Crystallographic Directions (ii)
Adapted
from p. 74, Determine indices for green vector
Callister &
Rethwisch Example a1 a2 z
4e.
1. Reposition not needed
2. Projections a a 0c
1 1 0
3. Reduction 1 1 0
4. Brackets [110]
5.
Convert to 4-axis parameters
1 1 1 1
u = [(2)(1) - (1)] = v = [(2)(1) - (1)] =
3 3 3 3
1 1 2
t = -( + ) = - w =0
3 3 3
6. Reduction & Brackets
• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)
Chapter 3 - 38
Crystallographic Planes
z
example a b c
1. Intercepts 1 1 c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 39
Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4 ·
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 · y
·
3. Reduction 6 3 4 a b
example a1 a2 a3 c
1. Intercepts 1 -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2
3. Reduction 1 0 -1 1
a3
Chapter 3 - 41
Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.
Chapter 3 - 42
Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit
(100) 4 3
a= R
3
Adapted from Fig. 3.2(c), Callister & Rethwisch 4e. 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
Chapter 3 - 43
Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell
2a atoms in plane
atoms above plane
atoms below plane
3
h= a
2
2
4 3 16 3 2
area = 2 ah = 3 a = 3
2
R÷
÷ = R
atoms 3 3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
area 16 3 2
R
2D repeat unit 3
Chapter 3 - 44
X-Ray Diffraction
reflections must
be in phase for
a detectable signal
extra Adapted from Fig. 3.38,
q q
distance
Callister & Rethwisch 4e.
travelled
by wave “2” spacing
d between
planes
Measurement of X-ray
n
critical angle, qc, intensity d=
(from 2 sin qc
allows computation of
detector)
planar spacing, d.
q
qc
Chapter 3 - 46
X-Ray Diffraction Pattern
z z z
c c c
y (110) y y
a b a b a b
Intensity (relative)
x x x (211)
(200)
Diffraction angle 2q
Chapter 3 - 47
SUMMARY
• Atoms may assemble into crystalline or amorphous 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, atomic radius, and crystal geometry (e.g., FCC,
BCC, HCP).
• Interatomic bonding in ceramics is ionic and/or covalent.
• Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.
• 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.
Chapter 3 - 48
SUMMARY
Chapter 3 - 49
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 3 - 50