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Part 2
Ionic crystals. Lattice energy. Silica & silicates. Carbon
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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
2007, 2008 Moonsub Shim, University of Illinois
Si
Oxygen
noncrystalline SiO2
Adapted from Fig. 3.18(b), Callister 6e.
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v c
v b
v a
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(trigonal)
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Body-centered
End-centered
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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
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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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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.
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2 2R
2R
9 2 1 12 8 7 6 5 4 11 10 3
2 2R
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2 2R
a 4R
APF =
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2R
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2a
Atoms at the corners of the cube + Atom at the center of the cube
a
4R
a2 + 2 a 4R a= 3
2007, 2008 Moonsub Shim, University of Illinois
( )
= (4 R )2
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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.
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2 1 4
6 8
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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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a=
4R 3
4R
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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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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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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
Cubic symmetry
[010] y
Rotate 90o about y y-axis Symmetry operation can generate all the directions within in a family.
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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
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v q = [2
1 1 0]
a2
a3
v q
2 along a1 -1 along a2
a1
-1 along a3
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a2
-2 along a3
a3
v r
1 along a1
a1
1 along a2
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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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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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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
v r
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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
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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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(1 0 0) plane
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(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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a2
a3 a1
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a2
a3 -1 in a2
+1 in a1 (1 1 0 0) plane
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(1 1 1) plane of FCC
y x z
(0 0 0 1) plane of HCP
SAME THING!*
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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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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
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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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
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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Incoming light
Constructive interference when n = 2d sin (Braggs Law) and d have to be comparable lengths.
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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)?
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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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
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Powder diffraction figures taken from Th. Proffe and R.B. Neder (2001) http://www.uni-wuerzburg.de/mineralogie/crystal/teaching/pow_a.html
Powder diffraction figures taken from Th. Proffe and R.B. Neder (2001) http://www.uni-wuerzburg.de/mineralogie/crystal/teaching/pow_a.html
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Powder diffraction figures taken from Th. Proffe and R.B. Neder (2001) http://www.uni-wuerzburg.de/mineralogie/crystal/teaching/pow_a.html
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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