Today

Short Quiz
The Structures of Crystalline Solids (Part 1)

ISSUES TO ADDRESS...
What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
What features of a metals/ ceramics atomic
structure determine its density?
How do the crystal structures of ceramic
materials differ from those for metals?
Under what circumstances does a material
property vary with the measurement direction?
Short Quiz
1. What do you call the electrons at the outer shell of the atom?
2. ____________ atoms readily give up electrons to become +
ions.
3. It is the tendency of an atom to acquire electrons.
4. It is the type of bonding that requires electron transfer.
5. It is the sum of attractive and repulsive energy.
6. Give the formula for percent ionic character.
7. It is the type of bonding caused by interaction between dipoles.
8. The higher the bond energy , the higher the melting point. T/F
9. The lower the bond energy, the lower the coefficient of linear
expansion. T/F
10. Which is more electronegative, Nitrogen or Oxygen?
X-ray Diffraction
Magnesiums HCP Structure
Application of Magnesium
Thought
for the
Day
 Energy and Packing
Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
 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.
 Metallic Crystal Structures
How can we stack metal atoms to minimize empty
space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

 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.
- Electron cloud shields cores from each other
Metals have the simplest crystal structures.

We will examine three such structures...

 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)

Click once on image to start animation

(Courtesy P.M. Anderson)
 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.
 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

Adapted from Fig. 3.2,

Click once on image to start animation Callister & Rethwisch 4e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
 Atomic Packing Factor: BCC
APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell
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

Adapted from Fig. 3.1, Callister & Rethwisch 4e.

Click once on image to start animation
(Courtesy P.M. Anderson) 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
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 =
volume
a3
unit cell
 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
Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence

3D Projection 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 4e.

Coordination # = 12 6 atoms/unit cell

APF = 0.74 ex: Cd, Mg, Ti, Zn
c/a = 1.633
 Theoretical Density,

Mass of Atoms in Unit Cell

Density = =
Total Volume of Unit Cell

nA
=
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol
 Theoretical Density,

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell

R a = 4R/ 3 = 0.2887 nm
a
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 4e.
atoms
g
unit cell 2 52.00 = 7.18 g/cm3
mol
= = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol
 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.
 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
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 mX p
m, p values to achieve charge neutrality
 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.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 3.5,
Callister & Rethwisch 4e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 3.6,
Adapted from Table 3.3, Callister & Rethwisch 4e.
Callister & Rethwisch 4e.
Computation of Minimum Cation-Anion
Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)
2ranion + 2rcation = 2a

a = 2ranion
2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion rcation = ( 2 -1)ranion

rcation
= 2 - 1 = 0.414
ranion
 Bond Hybridization

Bond Hybridization is possible when there is

significant covalent bonding
hybrid electron orbitals form
For example for SiC
XSi = 1.8 and XC = 2.5
% ionic character = 100 {1- exp[-0.25(X Si - X C )2 ]} = 11.5%

~ 89% covalent bonding

Both Si and C prefer sp3 hybridization
Therefore, for SiC, Si atoms occupy tetrahedral sites
 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.
For Next Meeting:
Crystal Materials (Part 2)
Reporters:
AmXp-Type Crystal Structure* (Karl Patrick)
AmBnXp-Type Crystal Structure* (Jemuel)
*Discuss sample problems (simple) from textbook
or other reference.
Assignment (9th edition) in Short Bond Paper
(stapled): 3.8, 3.10, ,3.12, 3.18
Reference:
Callister, W. and Rethwisch, D. (2014).
Fundamentals of Materials Science and
Engineering. 3rd edition. John Wiley & Sons.