MATERIALS

ES011

SCIENCE AND
ENGINEERING
 3 THE STRUCTURE OF
chapter

CRYSTALLINE SOLIDS
MATERIALS SCIENCE AND ENGINEERING
THE STRUCTURE OF CRYSTALLINE SOLIDS
• How do atoms assemble into solid structures?
• How does the density of a material depend on its
structure?
• When do material properties vary with the sample
(i.e., part) orientation?
CRYSTALLINE SOLIDS
• Crystallinity: Repeating or
periodic array over large atomic
distances. 3-D pattern in which
each atom is bonded to its nearest
neighbors
• Crystal structure: the manner in
which atoms, ions, or molecules
are spatially arranged.
ENERGY AND PACKING
Energy
Non dense, random packing
typical neighbor
bond length

typical neighbor r
bond energy
Dense, ordered packing
Energy

typical neighbor
• Dense, ordered packed bond length

structures tend to have typical neighbor r

lower energies. bond energy

MATERIALS AND PACKING
Crystalline materials... Silicon
• atoms pack in periodic, 3D arrays
• typical of: -metals Oxygen
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
"Amorphous" = Noncrystalline
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
• Have the simplest crystal structures.
CRYSTAL SYSTEMS
• Unit cell - small repeating
entity of the atomic structure.
The basic building block of the
crystal structure. It defines the
entire crystal structure with the
atom positions within.
THE UNIT CELL
CRYSTAL SYSTEMS
• Lattice - 3D array of points
coinciding with atom positions
(center of spheres)
7 crystal systems
14 crystal lattices
a, b, and c are the lattice constants
Fig. 3.4, Callister & Rethwisch 8e.
CRYSTAL SYSTEMS
CRYSTAL SYSTEMS
SIMPLE CUBIC (SC)
BODY CENTERED CUBIC (BCC)
FACE CENTERED CUBIC (FCC)
HEXAGONAL CLOSE PACKED (HCP)
CRYSTAL STRUCTURES AND ATOMIC RADII
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)

(Courtesy P.M. Anderson)

ATOMIC PACKING FACTOR: SC
• APF for a simple cubic structure = 0.52

volume
a atoms atom
4
R=0.5a unit cell 1 p (0.5a) 3
3
APF =
close-packed directions a3 volume
contains 8 x 1/8 =
1 atom/unit cell
unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e.
BODY CENTERED CUBIC STRUCTURE (BCC)
• Atoms touch each other along cube diagonals.
ex: Cr, W, Fe (), Tantalum, Molybdenum
Coordination # = 8

(Courtesy P.M. Anderson)

Adapted from Fig. 3.2,
Callister & Rethwisch 8e.

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
Close-packed directions:
a length = 4R = 3 a

2a
atoms volume
4
R unit cell 2 p ( 3a/4 ) 3
Adapted from
Fig. 3.2(a), Callister & a 3 atom
Rethwisch 8e.
APF =
volume
a3
unit cell
FACE CENTERED CUBIC STRUCTURE (FCC)
• Atoms touch each other along face diagonals.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
Coordination # = 12

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

(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
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
2a
atoms volume
4
unit cell 4 p ( 2a/4 ) 3
3 atom
a APF =
Adapted from
volume
Fig. 3.1(a),
Callister & Rethwisch a3
8e. unit cell
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

c:a ratio a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

6 atoms/unit cell Coordination # = 12

ex: Cd, Mg, Ti, Zn APF = 0.74
FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
A
B B B
C C
A
A sites B B B
C C
B sites B B
C sites
FCC Unit Cell
2D Projection
DIFFERENCE IN STACKING SEQUENCE BET. HCP
AND FCC

HCP (Basal) FCC (111)

2 stacks 3 stacks
THEORETICAL DENSITY

mass of atoms in unit cell 𝑛𝐴

𝜌= =
total volume of unit cell 𝑉𝐶 𝑁𝐴
THEORETICAL DENSITY
• Example:
Calculate the theoretical density of Chromium.
CHARACTERISTICS OF SELECTED ELEMENTS AT 20°C

Adapted from
Table, "Charac-
teristics of
Selected
Elements",
inside front
cover,
Callister 6e.

𝑛𝐴
𝜌=
𝑉𝐶 𝑁𝐴
THEORETICAL DENSITY
• Example:
Calculate the theoretical density of Chromium. R
a
Crystal Structure: BCC (2 atoms/unit cell) Adapted from

R=0.125 nm A=52.00g/mol
Fig. 3.2(a),
Callister &
Rethwisch 8e.

a = 4R/ 3 = 0.2887nm actual = 7.19 g/cm3

atoms g
unit cell 2 52.00 mol
𝑛𝐴
𝜌= theoretical = = 7.18g/cm3
𝑉𝐶 𝑁𝐴 volume a3 6.022 x 1023 atoms
unit cell mol
DENSITIES OF MATERIAL CLASSES Metals/
Graphite/
Composites/
Ceramics/ Polymers
Alloys fibers
Semicond

In general, ρmetals> ρceramics> ρpolymers 30

20 Platinum
B ased on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on

• close-packing (metallic bonding) 10 Silver, Mo

Cu,Ni
60% volume fraction of aligned fibers
in an epoxy matrix).
Steels
• often large atomic masses Tin, Zinc
Zirconia
Ceramics have... 5

 (g/cm 3)
Titanium
4 Al oxide
Diamond
• less dense packing 3
Aluminum
Si nitride
Glass -soda
Concrete
Glass fibers

• often lighter elements 2

Magnesium
Silicon
Graphite
PTFE GFRE*
Carbon fibers
CFRE *
Polymers have... Silicone
PVC
PET
Aramid fibers
AFRE *
PC
• low packing density (often amorphous) 1 HDPE, PS
PP, LDPE

• lighter elements (C,H,O) 0.5

Composites have... 0.4
Wood

0.3
• intermediate values Data from Table B.1, Callister & Rethwisch, 8e.
POLYMORPHISM
• Capability of some materials to possess different
crystal structures
• Property changes accompany such
transformation(volume, density)
• Allotropy – elemental solids with more than one
crystal structure
POLYMORPHISM: GRAPHITE VS. DIAMOND
POLYMORPHISM: ALLOTROPY OF IRON
• Iron changes its structure
when heated.
• Iron has the ability to exist
as BCC or FCC depending
on the temperature.
• This ability is called the
allotropy of iron
MILLER INDEX
• notation used for expressing locations, directions
and planes in crystal lattice systems

Index of directions [uvw] Index of planes (hkl)

Family of direction <uvw> Family of planes {hkl}
LINEAR AND PLANAR DENSITY

number of atoms centered on direction vector

𝜌𝐿 =
length of direction vector

number of atoms centered on a plane

𝜌𝑃 =
area of plane
ISOTROPY VS ANISOTROPY
• Isotropy
−independence of a material’s
properties on crystallographic
direction
−same properties in all directions
• Anisotropy
−having different properties in
different directions
CRYSTALS AS BUILDING BLOCKS
• Some engineering
applications require
single crystals:
• Properties of crystalline
materials often related to
crystal structure.
Ex: Quartz fractures
more easily along some
crystal planes than others.
diamond single crystals
for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)
turbine blades
Fig. 8.33(c), Callister &
Rethwisch 8e. (Fig. 8.33(c)
courtesy of Pratt and
Whitney).
(Courtesy P.M. Anderson)
POLYCRYSTALS
• Most engineering materials are polycrystals.
1 mm
Nb-Hf-W plate with an electron beam weld.
• Each "grain" is a single
Anisotropic crystal.
Adapted from Fig. K, color
• If grains are randomly
inset pages of Callister 5e.
(Fig. K is courtesy of Paul
oriented, overall
E. Danielson, Teledyne Wah component properties
Chang Albany)
are not directional.
• Grain sizes typically
Isotropic range from 1 nm to 2 cm
(i.e., from a few to
millions of atomic layers).
SOLIDIFICATION OF A POLYCRYSTALLINE MATERIAL
SINGLE VS POLYCRYSTALS
E (diagonal) = 273 GPa
• Single Crystals Data from Table 3.3,

−Properties vary with direction:

Callister & Rethwisch 8e.
(Source of data is R.W.
Hertzberg, Deformation and
anisotropic. Fracture Mechanics of
Engineering Materials, 3rd

−Example: the modulus of elasticity (E) ed., John Wiley and Sons,
1989.)

in BCC iron E (edge) = 125 GPa

• Polycrystals 200 mm Adapted from Fig. 4.14(b),
Callister & Rethwisch 8e.
−Properties may/may not vary with (Fig. 4.14(b) is courtesy of
L.C. Smith and C. Brady,

direction. the National Bureau of

Standards, Washington, DC

−If grains are randomly oriented: [now the National

Institute of Standards and

isotropic. (Epoly iron = 210 GPa)

Technology, Gaithersburg,
MD].)

−If grains are textured, anisotropic.

CHARACTERIZATION OF CRYSTALS
• X-RAY DIFFRACTION
− Chief tool for investigating the atomic or crystal
structure of materials
− Uses x-rays as source of wavelength for crystal
diffraction
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.
 X-RAYS TO DETERMINE CRYSTAL STRUCTURE
• Incoming X-rays diffract from crystal planes.
X-ray
intensity n
d=
(from 2 sin qc
reflections must
be in phase for detector)
a detectable signal q
extra
distance
 qc
travelled q q Measurement of critical angle, qc,
by wave “2” spacing
d between allows computation of planar
planes spacing, d.
Adapted from Fig. 3.20,
Callister & Rethwisch 8e.
INTERPLANAR SPACINGS
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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