3.metal and Ceramic Structures

8/25/2008
MSE 280: Introduction to Engineering Materials
Metal and Ceramic Structures

Reading: Chapter 3 Part 1
Defining ordered atoms in crystalline solids. Unit cells, unit vectors, Coordinates, directions, planes, close packing Densities: Crystal density, Line density, Planar density Crystal symmetry and families Crystallography
Part 2
Ionic crystals. Lattice energy. Silica & silicates. Carbon
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2007, 2008 Moonsub Shim, University of Illinois
MSE280
ENERGY AND PACKING

Non dense, random packing
Energy typical neighbor bond length typical neighbor bond energy r
Dense, regular packing
Energy typical neighbor b dl bond length h
typical neighbor bond energy
Dense, regular-packed structures tend to have lower energy.

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From Callister 6e resource CD.
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Packing atoms together

Crystalline materials... atoms pack in periodic, 3D arrays typical t i l of: f -metals -many ceramics -some polymers
crystalline SiO2
Adapted from Fig. 3.18(a), Callister 6e.
Noncrystalline materials... atoms have no periodic packing occurs for: -complex structures -rapid cooling "Amorphous" = Noncrystalline
Si
Oxygen
noncrystalline SiO2
Adapted from Fig. 3.18(b), Callister 6e.
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Crystalline materials: Unit Cell

Unit Cell: The basic structural unit of a crystal structure. Its geometry and atomic positions define the crystal structure. Note: more than one unit cell can be chosen for a given crystal but by convention/convenience the one with the highest symmetry is chosen.
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Unit cells and unit vectors

Lattice parameters axial lengths: a, b, c interaxial angles: , , v v v unit vectors: a b c In general: abc
v c
v b
v a
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Unit Cells: Bravais Lattices
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(trigonal)
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Unit cell types

Primitive Face-centered
Body-centered
End-centered
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Number of atoms in a unit cell
Simple cubic
8 atoms but each atom is shared by 8 unit cells. 1 atom p per unit cell
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Coordination Number
Number of nearest neighbor atoms
Simple cubic: coordination number = 6

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Atomic Packing Factor (APF)

APF = Vol. of atoms in unit cell Vol. of unit cell Depends on: Crystal structure. How close p packed the atoms are. In simple close-packed structures with hard sphere atoms, independent of atomic radius
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Close packing of atoms

Consider atoms as hard spheres.
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Face-Centered Cubic (FCC)
Atoms at the corners of the cube + Atoms at the center of each face
4R
a = ||unit vector||
R = atomic radius
a 2 + a 2 = ( 4 R )2
a
a = 2 2R
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Face-Centered Cubic (FCC)
Adapted from Fig. 3.1(a), Callister 6e.
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Number of atoms in an FCC unit cell
Each corner atom contributes as 1/8. There are 8 corner atoms in an FCC unit cell. Each face atom contributes as 1/2. There are 6 face atoms.
1 1 8( corner _ atoms ) + 6( face _ atoms ) = 4 atoms / unit _ cell 2 8

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Coordination number for FCC
2 2R
2R
9 2 1 12 8 7 6 5 4 11 10 3
2 2R
Total 12 nearest neighbor atoms Coordination number = 12

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Atomic packing factor (APF) for FCC

2 2R
2R
2 2R
a 4R
4 Vatoms = 4 R 3 3 3 3 Vunit _ cell = a = (2 2 R) = 16 2 R 3
APF =
Vatoms Vunit _ cell
16 3 R 3 = = 0.74 Independent of R and a! = 3 16 2 R 3 2

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Summary for FCC
||unit vector|| = a = 2 4 atoms/unit cell

a 4R
2R
Coordination number = 12 APF = 0.74
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Body-Centered Cubic (BCC)
2a
Atoms at the corners of the cube + Atom at the center of the cube
a
4R
a2 + 2 a 4R a= 3
( )
= (4 R )2
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Body-Centered Cubic (BCC)
From Callister 6e resource CD.
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Number of atoms in a BCC unit cell
Each corner atom contributes as 1/8. There are 8 corner atoms in an FCC unit cell. The center atom contributes as 1. There is only 1 center atom atom.
1 8( corner _ atoms ) + 1 1( center _ atom ) = 2 atoms / unit _ cell 8

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Coordination number for BCC
2 1 4
Total 8 nearest neighbor atoms Coordination number = 8
6 8
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Atomic packing factor (APF) for BCC

2a
4 Vatoms = 2 R 3 3
a 2 + ( 2a ) 2 = (4 R) 2 4R a= 3 64 R 3 4R Vunit _ cell = a 3 = ( )3 = 3 3 3
8 3 R Vatoms 3 = 3 = 0.68 APF = = 3 64 R Vunit _ cell 8 3 3
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4R
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Summary for BCC

2a
||unit vector|| =
a=
4R 3
4R
2 atoms/unit cell Coordination number = 8 APF = 0.68
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Hexagonal Close-Packing (HCP)
Find a, c, number of atoms/unit cell, coordination number, and APF for HW.
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Point Coordinates
to define a point within a unit cell. Essentially same as Cartesian coordinates except values of x, y, and z are expressed as fractions of the magnitude of unit vector(s) (and x, y, and z not necessarily orthogonal) orthogonal). pt. coord. z x (a) y (b) z (c ) b a A B c y = point A = origin = point B x = point C = point D 2007, 2008 Moonsub Shim, University of Illinois
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0 1 1 1/2
0 0 1 0
0 0 1 1/2
C D
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Crystallographic Directions
To define a vector: 1. Start at the origin. 2 Determine length of vector projection in each of 3 axes in units 2. (or fractions) of a, b, and c. 3. Multiply or divide by a common factor to reduce the lengths to the smallest integer values. 4. Enclose in square brackets: [u v w] where u, v, and w are integers.
Along unit vectors: a b c
Note: in any of the 3 directions there are both positive and negative directions. Negative directions are denoted with a bar over the number. e.g. [1 1 1]
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Example 1: Assign the coordinates to the following crystallographic direction Along x: 1 a

b a c
y
Along y: 1 b Along z: 1 c
[1 1 1]
x
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Example 2: draw [1 1 0] direction. 1 unit vector length along x -1 unit vector length g along gy z 0 unit vector length along z
b a c
[1 1 0] y
origin
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Note: for some crystal structures, different directions can be equivalent. e.g. For cubic crystals: [1 0 0], [ 1 0 0], [0 1 0], [0 1 0], [0 0 1], [0 0 1 ] are all equivalent Families of crystallographic directions e.g. <1 0 0> Angled brackets denote a family of crystallographic directions.
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Families and Symmetry

Which directions belong in the same family is determined by the crystal symmetry. What is symmetry? Which Whi h one i is more symmetric? ti ? c a a a a
1
The more symmetry operations there are the more symmetric it is.
3 and 3 2 2 1 equivalent 3 2 2 3 equivalent
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1 etc
Which is more symmetric, cubic or tetragonal?

2007, 2008 Moonsub Shim, University of Illinois MSE280
Families and Symmetry

z
Cubic symmetry
Rotate 90o about z-axis

[100] x y x z [001]
[010] y
Rotate 90o about y y-axis Symmetry operation can generate all the directions within in a family.
Similarly for other equivalent directions

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x 2007, 2008 Moonsub Shim, University of Illinois
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Crystallographic directions for hexagonal crystals

Consider vectors q and r.
z
If we keep the 3-coordinate system: v q = [1 0 0] v r = [1 1 0] Different set of indices. However, these two vectors are equivalent by symmetry (i.e. via 60o rotation).
v q
v r
x
Choose a 4-coordinate system!

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In the Miller-Bravais (4 axes) coordinate system, We
have:
z
v q = [2
1 1 0]
a2
a3
v q
2 along a1 -1 along a2
a1
Although the length is different the direction is the same.

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-1 along a3
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Similarly for r, in the Miller-Bravais (4 axes) coordinate system, we now have: v r = [1 1 2 0]
z
a2
-2 along a3
a3
v r
1 along a1
a1
1 along a2
Again, consistent direction.
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Miller-Bravais (4 axes) coordinate system
We now have:
z
v q = [2 1 1 0] v r = [1 1 2 0]
a2
a3
v q
v r
a1
Indices are now consistent within the family, but where do these numbers come from?
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To transform 3 indices to 4 indices

[u v w] [u v t w] May need to factor to reduce u, v, t, and w to their smallest integers.
z
e.g. convert q = [1 0 0] to 4-coord. system.
u = 1/3 ( (2u v) ) v = 1/3 (2v u) t = - (u + v) w = w

x3 x3 x3 x3
u = 1/3 (2x1 0) = 2/3 v = 1/3 (2x0 1) = -1/3 1/3 t = -(2/3 + (-1/3)) = -1/3 w=0
2 -1 1 -1 0
a3
[2 1 1 0]
a2
v q
a1
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transforming 3 indices to 4 indices

convert
v r
= [1 1 0] to 4-coord. system. u = 1/3 (2x1 1) = 1/3 v = 1/3 (2x1 1) = 1/3 t = -(1/3 + 1/3) = -2/3 w=0 x3 x3 x3 x3 1 1 -2
z
[1 1 2 0]
0
a2
a3 2007, 2008 Moonsub Shim, University of Illinois
v r
a1 38 MSE280
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Crystallographic Planes
z
b a
To define a plane (i.e. to assign Miller Indices): 1. If the plane passes through the origin, either a) Construct a parallel plane translated or b) choose another origin at the corner of adjacent unit cell y 2. Now, the plane either intersects or parallels each of the three axes axes. 3. Determine length in terms of lattice parameters a, b and c. Parallel to x-axis = length along x Parallel to y-axis = length along y Intercepts z-axis at z = c
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origin
origin
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Crystallographic Planes
4. Take the reciprocal of the lengths e.g. Along Al x-axis: i l length th = Along y-axis: length = Along z-axis: length = 1 0 0 1
5. If necessary, factor to get the smallest integers. divide through by 3 e g if we had 0 e.g. 0, 0 0, 3 0 0 0, 0, 1 6. Enclose indices in parentheses w/o commas In the example on previous slide, the Miller index would be (0 0 1)
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Example 1
Assign Miller indices 1 Shift origin 1. i i f from O t to O z z 2. Determine lengths along each axis Along x = Intersects y at -1 Intersects z at 1/3 O
b a c c/3
y O x x
3. Take the reciprocal: 0, -1, 3 4. No need to factor. 5. (0 1 3)

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Example 2
Draw the (0
1 1) plane.
z
1 along x = 0 1. The plane runs parallel to x-axis 2. along y = -1 (in units of b) take reciprocal: -1 y-intercept at -1 3. along z = 1 (in units of c) take reciprocal: 1 z intercept at 1 z-intercept
|c| |b|
y
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Crystallographic planes in FCC

z
Look down this direction (perpendicular to the plane)
(1 0 0) plane
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Crystallographic planes in FCC

z
Look down this direction (perpendicular to the plane)
(1 1 1) plane
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Note: similar to crystallographic directions, planes that are parallel to each other are equivalent
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Crystallographic Planes for Hexagonal Crystals

Similar to crystallographic directions for hexagonal crystals, 4-coordinate system is used. i.e. instead of (h k l) for 3-coordinate systems, use (h k i l). For integers h, k, and l, same procedure as 3-coordinate systems is used and i = - (h+k)
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Crystallographic planes in HCP

z
Name this plane
a2
a3 a1
(0 0 0 1) plane Parallel to a1, a2 and a3 -> h = k = i = 0 Intersects at z = 1

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Crystallographic planes in HCP

z
a2
a3 -1 in a2
+1 in a1 (1 1 0 0) plane
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a1 h = 1, k = -1, i = -(1+-1) = 0, l = 0 2007, 2008 Moonsub Shim, University of Illinois
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(1 1 1) plane of FCC
y x z
(0 0 0 1) plane of HCP
SAME THING!*
a2 a3 a1 2007, 2008 Moonsub Shim, University of Illinois

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Close Packing
Note: whether the atoms of 2nd layer fills B-sites or C-sites does not matter. They are equivalent until the 3rd layer is added! 50
2007, 2008 Moonsub Shim, University of Illinois MSE280
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FCC
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HCP
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Difference between FCC and HCP
Looking down (0001) plane
FCC ABCABC Looking down (111) plane!

HCP ABABAB
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Densities
Crystals C t l d density it (i.e. (i 3D d density) it ) i in units it of f mass 3 per volume (e.g. g/cm ). Linear density: number of atoms per unit length (e.g. cm-1). Planar density: number of atoms per unit area (e (e.g. g cm-2).
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Crystals density ()
Mass of unit cell
=
M=
M V
nA NA
Volume of unit cell
n = number of atoms in unit cell A = atomic weight NA = Avogadros number
nA N AV
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Density example
Calculate density of copper given: R = 0.128 nm A = 63.5 g/mol FCC structure Recall for FCC, there are 4 atoms per unit cell. Express unit cell volume in terms of atomic radius R.
V = a 3 = (2 2 R )3 = 16 2 R 3
Then we have:
=
=
M nA = V N A16 2 R 3 4(65.3 g / mol ) (6.022 x10 23 mol 1 )(16 2 )(1.28 x10 8 cm)3
= 8.89 g/cm3
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Compare to actual value of 8.94 g/cm3!

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Linear Density (LD)

LD = Number of atoms centered on a direction vector Length of the direction vector Example: calculate the linear density of an FCC crystal along [1 1 0]. Length = 4R Effectively 2 atoms along the [1 1 0] vector. LD = 2/4R = 1/2R
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Planar Density (PD)

PD = Number of atoms centered on a given plane Area of the plane Example: calculate the planar density on (1 1 0) plane of an FCC crystal.
a = 2 2R
4R
Count only the parts of the atoms within the plane: 2 atoms
area = 2 2 R 4 R
PD =
2 1 = (4 R)(2 2 R) 4 2 R 2
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Example problem
(110) 0.2 nm (101) 0.32 nm (011) 0.36 nm
0.39 nm 0.3 nm 0.253 nm
Given above information answer the following gq questions. A) What is the crystal structure? B) If atomic radius is 0.08 nm, what is APF? C) If atomic weight is 43 g/mol, calculate density. D) What is the linear density along [210]? E) What is the planar density of (210)?
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How to determine crystal structure

The two slit experiment Same idea with crystals - Light gets scattered off atoms
d
Incoming light
Constructive interference when n = 2d sin (Braggs Law) and d have to be comparable lengths.
But since d (atomic spacing) is on the order of angstroms: x-ray diffraction
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Diffraction Experiment and Signal

Diffraction Experiment Scan versus 2x Angle: Polycrystalline Cu
Measure 2
Diffraction collects data in reciprocal p space p since it is the equivalent q of a Fourier transform of real space, i.e., eikr, as k ~ 1/r. How can 2 scans help us determine crystal structure type and distances between Miller Indexed planes (I.e. structural parameters)?
D.D. Johnson 2004, 2006-08
Crystal Structure and Planar Distances

Bravais Lattice Constructive Interference
Reflections present BCC FCC HCP (h + k + l) = Even (h,k,l) All Odd or All Even Any other (h,k,l)
Destructive Interference
Reflections absent (h + k + l) = Odd (h,k,l) Not All Odd or All Even h+2k=3n, l = Odd n= integer
h, k, l are the Miller Indices of the planes of atoms that scatter! So they determine the important planes of atoms, or symmetry.
Distances between Miller Indexed planes For cubic crystals: For hexagonal crystals:
dhkl = a
4
a (h 2 + hk + k 2 ) + l 2 c 3
D.D. Johnson 2004, 2006-08
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Allowed (hkl) in FCC and BCC for principal scattering (n=1)

(h k l) h2+k2+l2 1 2 3 4 5 6 8 9 9 10 11 12 13 14 h+k+l 1 2 3 2 3 4 4 5 3 4 5 6 5 6
Self-Assessment: From what crystal structure is this?
h,k,l all even or odd? No No Yes Yes No No Yes No No No Yes Yes No No
100 110 111 200 210 211 220 221 300 310 311 222
h + k + l was even and gave the labels on graph above, so crystal is BCC.
320 321
D.D. Johnson 2004, 2006-08
Example problem: X-ray crystallography

Given the information below, determine the crystal structure. Consider only FCC and BCC structures as possibilities.
Lattice parameter: a = 0.4997nm Powder x-ray: = 0.1542 nm
2 ( o) 31 36 51.8 61.6 64.8
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Diffraction of Single 2D Crystal Grain

Lattice of Atoms: Crystal Grain Diffraction Pattern in (h,k) plane
Powder diffraction figures taken from Th. Proffe and R.B. Neder (2001) http://www.uni-wuerzburg.de/mineralogie/crystal/teaching/pow_a.html
D.D. Johnson 2004, 2006-08
Diffraction of Multiple Single 2D Crystal Grains (powders)

Multiple Crystal Grains: Diffraction Pattern 4 Polycrystals in (h,k) plane (4 grains) Diffraction Pattern in (h,k) plane (40 grains)
D.D. Johnson 2004, 2006-08
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Example from Graphite
Single Crystal Grain
Mutlple Grains: Polycrystal
D.D. Johnson 2004, 2006-08
Concepts to remember
Unit cell, unit vector, and lattice parameters. Bravais Lattices. Counting number of atoms for a given unit cell. Coordination number = number of nearest neighbor atoms. Atomic Packing Factor (APF) = Volume of atoms in a unit cell/Volume of unit cell. Close-packing FCC BCC FCC, BCC, HCP Crystallographic coordinates, directions, and planes. Densities X-ray crystallogrphy
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3.metal and Ceramic Structures

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8/25/2008

MSE 280: Introduction to Engineering Materials

Metal and Ceramic Structures

2007, 2008 Moonsub Shim, University of Illinois

ENERGY AND PACKING

Dense, regular packing

Energy typical neighbor b dl bond length h

typical neighbor bond energy

Dense, regular-packed structures tend to have lower energy.

2007, 2008 Moonsub Shim, University of Illinois

From Callister 6e resource CD.

Packing atoms together

Crystalline materials: Unit Cell

2007, 2008 Moonsub Shim, University of Illinois

Unit cells and unit vectors

2007, 2008 Moonsub Shim, University of Illinois

Unit Cells: Bravais Lattices

2007, 2008 Moonsub Shim, University of Illinois

2007, 2008 Moonsub Shim, University of Illinois

Unit cell types

2007, 2008 Moonsub Shim, University of Illinois

Number of atoms in a unit cell

2007, 2008 Moonsub Shim, University of Illinois

Simple cubic: coordination number = 6

2007, 2008 Moonsub Shim, University of Illinois

Atomic Packing Factor (APF)

2007, 2008 Moonsub Shim, University of Illinois

Close packing of atoms

2007, 2008 Moonsub Shim, University of Illinois

Face-Centered Cubic (FCC)

2007, 2008 Moonsub Shim, University of Illinois

Face-Centered Cubic (FCC)

Adapted from Fig. 3.1(a), Callister 6e.

2007, 2008 Moonsub Shim, University of Illinois

Number of atoms in an FCC unit cell

1 1 8( corner _ atoms ) + 6( face _ atoms ) = 4 atoms / unit _ cell 2 8

Coordination number for FCC

Total 12 nearest neighbor atoms Coordination number = 12

2007, 2008 Moonsub Shim, University of Illinois

Atomic packing factor (APF) for FCC

4 Vatoms = 4 R 3 3 3 3 Vunit _ cell = a = (2 2 R) = 16 2 R 3

Vatoms Vunit _ cell

16 3 R 3 = = 0.74 Independent of R and a! = 3 16 2 R 3 2

2007, 2008 Moonsub Shim, University of Illinois

Summary for FCC

||unit vector|| = a = 2 4 atoms/unit cell

Coordination number = 12 APF = 0.74

2007, 2008 Moonsub Shim, University of Illinois

Body-Centered Cubic (BCC)

Body-Centered Cubic (BCC)

From Callister 6e resource CD.

2007, 2008 Moonsub Shim, University of Illinois

Number of atoms in a BCC unit cell

1 8( corner _ atoms ) + 1 1( center _ atom ) = 2 atoms / unit _ cell 8

Coordination number for BCC

Total 8 nearest neighbor atoms Coordination number = 8

2007, 2008 Moonsub Shim, University of Illinois

Atomic packing factor (APF) for BCC

2007, 2008 Moonsub Shim, University of Illinois

Summary for BCC

2 atoms/unit cell Coordination number = 8 APF = 0.68

2007, 2008 Moonsub Shim, University of Illinois

Hexagonal Close-Packing (HCP)