CH 04
CH 04
CH 04
ISSUES TO ADDRESS...
• What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
2
Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges
• Coordination # = 6
In terms of the hard sphere (# nearest neighbors)
model we say the atoms are
touching in the close-packed
directions!
3
Atomic Packing Factor (APF)
No. of atoms * Volume of atoms in unit cell
APF =
Volume of unit cell
• Assume atoms are hard spheres
• volume in a crystal structure that is occupied by atoms
a volume
atoms atom
R=0.5a 4
unit cell 1 p (0.5a) 3
3
close-packed directions APF =
contains 8 x 1/8 = a3 volume
1 atom/unit cell unit cell
close packed directions : directions in which having a maximum atom or sphere packing
4
density
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.
ex: Cr, W, Fe (), Tantalum, Molybdenum
• Coordination # = 8
Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a
2a
Adapted from R
Fig. 3.2(a), Callister &
Rethwisch 8e.
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell
Close-packed directions: cube length and atomic
radius
Triangle lmn
step1 a2 + a2 = b2
m n b2 = 2a2
b l Triangle kln
4R step2 a2 + b2 = (4R)2
a
a2 + 2a2 = (4R)2
3a2 = (4R)2
k
a
Question
8
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 # = 12
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 8e. 4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
10
Example
11
12
Question
13
Hexagonal Close-Packed Structure
(HCP)
• Coordination # = 12
• APF = 0.74
A plane
B plane
C plane
A plane
…ABCABCABC… packing …ABABAB… packing
[Face Centered Cubic (FCC)] [Hexagonal Close Packing (HCP)]
FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites
A
• FCC Unit Cell B
C
17
Theoretical Density, r
atoms g
unit cell 2 52.00 mol rtheoretical = 7.18 g/cm3
r = a3 6.022 x
volume 23 atoms ractual = 7.19 g/cm3
unit cell 10 mol
22
Example
Question
Chapter 3 -
Question
Chapter 3 - 26
Question
27
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
28
Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
- - - - - -
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 X
m p
m, p values to achieve charge neutrality
Coordination # and Ionic Radii
r cation
• Coordination # increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord ZnS
r anion # (zinc blende)
< 0.155 2 linear
32
Example
Rock Salt Structure (AX Type)
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
rMg/rO = 0.514
35
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
rCs 0.170
0.939
rCl 0.181
Coordination number = 4
37
AX2 Crystal Structures
Fluorite structure Charges on the cations and
anions are not the same
Compound can exist with the
chemical formula AmXp,where
m and/or p 1
n(AC AA )
r
VC N A
Avogadro’s number
Volume of unit cell
40
Example
n(AC AA )
r
VC N A
41
Example
Chapter 3 - 42
Structure of Polymers
44
Crystallinity in Polymers
• Ordered atomic arrangements
involving molecular chains
• Example shown
– polyethylene unit cell
Polymer Crystallinity
• Crystalline regions
– thin platelets with chain folds at faces
– Chain folded structure
crystalline
region
Polymers rarely 100% crystalline
• Difficult for all regions of all chains to
become aligned
Chapter 3 - 48
Example
49
Example
51
DEMO: Heating & Cooling of Iron (Fe)
Wire
The same atoms can
• Demonstrates "polymorphism" have more than one
crystal structure
19
Linear Density
Number of atoms centered on
direction vector
• Linear Density of Atoms LD =
Unit length of direction vector
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
2
a LD 3.5 nm1
length 2a
55
56
57
Linear density expressions for BCC [110]
58
Planar Density
The units for planar density are reciprocal area (e.g., nm-2,
m-2).
59
Planar Density of (100) Iron
4 3
(100) a R
3
y z 2 x2
4R 2 4R 2
4 R 4 R 2 16 R 2 2 y (4 R) 2
Area (110) xy 3 3
3 3 3
number of atoms centered on (110) plane
PD110 =
area of(110) plane
2 atoms 3
16 R 2 2 8 R2 2
3 61
Planar Density of BCC (111) Iron
(111) plane 1 atom in plane/ unit surface cell
2a atoms in plane
atoms above plane
atoms below plane
3
h a
2
63
Planar Density FCC
4R
2R2
64
Planar Density of FCC (111)
65
Planar Density of FCC (100)
66
Linear & Planar Density
https://www.youtube.com/watch?v=VAP_SozPa8M
67
X-Ray Diffraction
69
X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal
extra
q q
distance
travelled
by wave “2” spacing
d between
planes
y (110) y y
a b a b a b
Intensity (relative)
x x x (211)
(200)
Diffraction angle 2q
71
Example
Chapter 3 - 72
Example
Chapter 3 - 73
Example
74