The Structure of Crystalline Solids

ISSUES TO ADDRESS...
• What is the difference in atomic arrangement
between crystalline and noncrystalline solids?

• What features of a material’s atomic

structure determine its density?

• Under what circumstances does a material

property vary with the measurement direction?

• Application of X-ray diffraction

 Metallic Crystal Structures
• Tend to be densely packed
• Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same

- Metallic bonding is not directional

- Nearest neighbor distances tend to be small in

order to lower bond energy

• Have the simplest crystal structures

We will examine three such structures...

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

• APF for a simple cubic structure = 0.52

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

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

 Atomic Packing Factor: FCC
• APF for a face-centered cubic structure = 0.74

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
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Example

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12
Question

13
 Hexagonal Close-Packed Structure
(HCP)

• Coordination # = 12

Number of atoms per unit cell, n = 6

3 mid-plane atoms shared by no other

cells: 3 x 1 = 3
12 hexagonal corner atoms shared by 6
cells: 12 x 1/6 = 2
2 top/bottom plane center atoms shared by
2 cells: 2 x 1/2 = 1

• APF = 0.74

Ideally, c/a = 1.633 for close packing

c/a ratio deviates from this value in most metals
Closed Packed Crystal Structures
APF = 0.74 for both FCC and HCP
 Closed Packed Crystal Structures

APF = 0.74 for both FCC and HCP

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

Density = r = Mass of Atoms in Unit Cell

Total Volume of Unit Cell

VC = Volume of unit cell = a3 for cubic

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Characteristics of Selected Elements at 20 oC
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------
Bromine Br 79.90 ------ ------
Cadmium Cd 112.41 8.65 0.149
Calcium Ca 40.08 1.55 0.197
Carbon C 12.011 2.25 0.071
Cesium Cs 132.91 1.87 0.265
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------ 12
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 Densities of Materials Classes
rmetals• rceramics• rpolymers
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values Data from Table B1, Callister 6e.
13
 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 8e.

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

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 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

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic
 EX: Predicting Structure of FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation • Answer:
Al3+ r cation 0.077
Fe 2+ 
r anion 0.140
Fe 3+
 0.550
Ca2+
based on this ratio,
--coord # = 6
Anion
--structure = NaCl
O2-
Cl-
F-
31
Example

a set of points in space are

coplanar if there exists a
geometric plane that contains
them all

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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

 cations (Na+) prefer octahedral sites

AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

 MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

 cations prefer octahedral sites

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

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 AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

rCs  0.170
  0.939
rCl  0.181

 Since 0.732 < 0.939 < 1.0,

Center cubic sites preferred
So each Cs+ has 8 neighbor Cl-
 AX Crystal Structures
Zinc blend
Corner and face positions of the
cubic cell are occupied by S atoms

Zn atoms fill interior tetrahedral

positions

Coordination number = 4

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 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

• Calcium Fluorite (CaF2)

• Cations in cubic sites
• UO2, ThO2, ZrO2, CeO2
• Antifluorite structure –
positions of cations and
anions reversed

Calcium ions are positioned at the centers

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of cubes, with fluorine ions at the corners
 ABX3 Crystal Structures
• Perovskite structure

Ex: complex oxide

BaTiO3
 Density Computations for Ceramics

Number of formula units/unit cell

n(AC  AA )
r
VC N A
Avogadro’s number
Volume of unit cell

AC = sum of atomic weights of all cations in formula unit

AA = sum of atomic weights of all anions in formula unit



40
 Example

n(AC  AA )
r
VC N A

41
Example

8 Cl units in corner ---> 8*1/8=1

6 Cl units in face ---> 6*1/2=3 ====> Totally 4 Cl atoms

12 Na units in edge ---> 12*1/4=3

1 Na units in body ---> 1*1=1 ====> Totally 4 Na atoms

Chapter 3 - 42
 Structure of Polymers

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene
Repeating Unit of Common Polymers

44
 Crystallinity in Polymers
• Ordered atomic arrangements
involving molecular chains

• Crystal structures in terms of

unit cells

• Example shown
– polyethylene unit cell
 Polymer Crystallinity
• Crystalline regions
– thin platelets with chain folds at faces
– Chain folded structure

Degree of crystallinity expressed as % ≈ 10

crystallinity nm

r s = density of a specimen for which the percent crystallinity is to be determined,

r a = density of the totally amorphous polymer
rc = density of the perfectly crystalline polymer
 Polymer Crystallinity

crystalline
region
Polymers rarely 100% crystalline
• Difficult for all regions of all chains to
become aligned

-- Some physical properties depend

on % crystallinity

-- Heat treating causes crystalline

regions to grow and % crystallinity to
increase
amorphous
region
Example

Chapter 3 - 48
Example

49
 Example

r s = density of a specimen for which the percent crystallinity is to be determined,

r a = density of the totally amorphous polymer 50
rc = density of the perfectly crystalline polymer
 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
 Ti, -Ti
1538ºC
BCC -Fe
Carbon
Diamond, graphite 1394ºC
FCC -Fe
912ºC
BCC -Fe

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 nm1
length 2a

Units of linear density are reciprocal length (e.g., nm -1, m -1)

53
Linear Density for BCC

Calculate the linear density for the

following directions in terms of R:
a. [100]
b. [110]
c. [111]
Question

55
56
57
Linear density expressions for BCC [110]

58
 Planar Density

Number of atoms per unit area that are centered on a

particular crystallographic plane

The units for planar density are reciprocal area (e.g., nm-2,
m-2).

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 Planar Density of (100) Iron

Solution: At T < 912ºC iron has the BCC structure

2D repeat unit

4 3
(100) a R
3

atoms Radius of iron R = 0.1241 nm

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
60
 Planar Density of BCC (110)

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

Plane does not pass through the center of

atom D.

One sixth of each of the three atoms

labeled A, B, and C is associated with this
plane, which gives an equivalence of one-
half atom
62
 2
 4 3  16 3 2
area  2 ah  3 a  3 
2
R  R
 3  3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit 0.5
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
area 16 3 2
R
2D repeat unit 3

63
Planar Density FCC

4R

2R2

Area of Planar region = 8R22

64
Planar Density of FCC (111)

Atomic radius for nickel is 0.125

nm. Therefore, the planar
density for the (111) plane is

65
 Planar Density of FCC (100)

Atomic radius for nickel is 0.125 nm. Therefore, the planar

density for the (100) plane is

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 Linear & Planar Density

https://www.youtube.com/watch?v=VAP_SozPa8M

67
 X-Ray Diffraction

• Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation
• Can’t resolve spacings  
• Spacing is the distance between parallel planes of
atoms.
68
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

Bragg’s Law: 2d hkl Sinq  n

Measurement of X-ray
n
critical angle, 2qc,
intensity d
(from 2 sinqc
allows computation of detector)
planar spacing, d. q
Additional Conditions: 2qc
BCC: h+k+l = even 70
FCC: h,k,l is either odd or even
 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

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

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Example

Chapter 3 - 72
Example

Chapter 3 - 73
Example

74