CHAPTER 3: The STRUCTURE of

Metals

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(for now, focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3-1
Chapter 3-2
Chapter 3-3
 single-crystal
structures poly-crystal
non-crystal(amorphous)

• regularity  long-range order

• hard sphere model ( Pauling’s model )
• three- Dimensional (3-D)

Chapter 3-4
 ENERGY AND PACKING
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, regular packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular-packed structures tend to have

lower energy.
Chapter 3-5
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.

Chapter 3-6
 3.1 Introduction

• Various types of atomic bonding

• Unit cell
• Three common crystal structures found in
metals
• Crystallographic points, directions, and
planes

Chapter 3-7
 Crystal Structures
3.2 Fundamental Concepts
• A crystalline material is one in which the atoms
are situated in repeating or periodic array over
large atomic distances.
• Lattice means a three-dimensional array of point
coinciding with atom positions.

Chapter 3-8
 3.3 Unit Cells

• Crystal structure is often convenient to

subdivide the structure into a small repeat
entities called unit cells.

Chapter 3-9
3.4 METALLIC CRYSTAL Structures
• tend to be densely packed.
• have several 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 look at three such structures...

Chapter 3-10
 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

Chapter 3-11
 ATOMIC PACKING FACTOR
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 (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. 3.19,
Callister 6e. Chapter 3-12
 FACE CENTERED CUBIC
STRUCTURE (FCC)
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.

(Courtesy P.M. Anderson)

Chapter 3-13
Chapter 3-14
 ATOMIC PACKING FACTOR: FCC
• APF for a FCC structure = 0.74
Close-packed directions:
length = 4R
= 2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4 3
unit cell 4 ( 2a/4)
3 atom
APF =
3 volume
a
unit cell
Chapter 3-15
 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

Chapter 3-16
 BODY CENTERED CUBIC
STRUCTURE (BCC)
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson) Chapter 3-17

4R

Chapter 3-18
 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
Unit cell contains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e. atoms volume
4 3
unit cell 2 ( 3a/4)
3 atom
APF =
3 volume
a
unit cell
Chapter 3-19
 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

Adapted from Fig. 3.3, a
Callister 6e. c/a=1.633
• Coordination # = 12
n=6=3+2×1/2+12×1/6
• APF = 0.74

Chapter 3-20
1
Chapter 3-21
Chapter 3-22
• Example Problem 3.2
Show that the atomic packing factor for the FCC crystal structure is 0.74

Solution
The APF is defined as the fraction of solid sphere volume in a unit cell, or

total sphere volume V

APF   S
total unit cell volume VC

Both the total sphere and unit cell volumes may be calculated in terms of
the atomic radius R. The volume for a sphere is 3 / 4 R 3 , and since there
are four atoms per FCC unit cell, the total FCC sphere volume is

VS  4  R 3  R 3
4 16
3 3
From Example Problem 3.1, the total unit cell volume is
VC  16 R 3 2
Therefore, the atomic packing factor is
VS 16 / 3R 3
APF   3
 0.74
VC 16 R 2
Chapter 3-23
 比較

FCC BCC HCP

a ∞R a=2√2R a=4/√3R a=2R

Atoms in unit 4=8×1/8+6 2=1+8×1/8 6=3+2×1/2

cell ×1/2 +12×1/6
Coordination 12 8 12
number
APF 0.74 0.68 0.74

Chapter 3-24
 3.5 DENSITY Computations, 
# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell VcNA Avogadro's number
(cm3/unit cell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see next slide):
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10-7cm)
Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3
Result: theoretical Cu = 8.89 g/cm3
Compare to actual: Cu = 8.94 g/cm3
Chapter 3-25
 求 FCC 的理論密度

Compare to actual: Cu = 8.94 g/cm3

Chapter 3-26
Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 2.34 Rhomb ------
10.81 Adapted from
------ Table, "Charac-
Bromine Br 79.90 ------ ------
0.149 teristics of
Cadmium Cd 112.41 8.65 HCP Selected
0.197 Elements",
Calcium Ca 40.08 1.55 FCC 0.071 inside front
Carbon C 12.011 2.25 Hex cover,
0.265 Callister 6e.
Cesium Cs 132.91 1.87 BCC ------
Chlorine Cl 35.45 ------ ------ 0.125
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.128
Copper Cu 63.55 8.94 FCC ------
Flourine F 19.00 ------ ------ 0.122
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.144
Gold Au 196.97 19.32 FCC ------
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ Chapter 3-27
DENSITIES OF MATERIAL CLASSES
Graphite/
metals? ceramics? polymers Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
Why? 30
Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).

• large atomic mass Steels

 (g/cm3)
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
• less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass-soda
Concrete
Glass fibers
PTFE
• often lighter elements 2 Magnesium
Silicon
Graphite
GFRE*
Carbon fibers
CFRE*
Polymers have... Silicone
PVC
PET
Aramid fibers
AFRE*
• poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
• lighter elements (C,H,O) 0.5
Wood
Composites have... 0.4
0.3
• intermediate values Data from Table B1, Callister 6e.
Chapter 3-28
 3.7 Crystal Systems

• X,Y,Z: axes
• Lattice parameters: a, b, c:three edge lengths
α，β，γ : three interaxial angles

Chapter 3-29
Chapter 3-30
 6 lattice parameters 簡單立方
立方 體心立力方
面心立方

六方

正方

菱方

斜方晶系

單斜

三斜
Chapter 3-31
3.8 Point Coordinates

Chapter 3-32
 3.9 Crystallographic Directions
A line between two points, or a vector

The steps are utilized in the determination of the three directional indices

1.A vector of convenient length is positional such that

it passes through the origin of the coordinate system.
Any vector may be translated throughout the crystal lattice PROJECTION
without alteration, if parallelism is maintained.
2.The length of the vector projection on each of the three axes is determined:
these are measured in terms of the unit cell dimensions a,b,c.
3.These three numbers are multiplied or divided by a common factor to reduce
them to the smallest inter values.
4.The three indices, not separated by commas, are enclosed in square brackets,
thus: [uvw]. The u, v, and w integers correspond to the reduced projections along
the x, y, and z axes, respectively.
Chapter 3-33
Miller indices
[direction]
( plane )

Chapter 3-34
Example Problem 3.6

Determine the indices for the direction shown in the accompanying figure.
z

Projection on
x axis (a/2) Projection on
y axis (b)

c
y

x
This procedure may be summarized as follows:
x y z
Projections a/2 b 0c
Projections (in terms of a, b, and c) 1/2 1 0
Reduction 1 2 0
Enclosure [120]
Chapter 3-35
HEXAGONAL CRYSTALS
A problem arises for crystals having hexagonal symmetry in that some crystallo-
graphic equivalent directions will not have the same set of indices. This is circum-
vented by utilizing a four-axis, or Miller-Bravais, coordinate system as shown in
Figure 3.7. The three a1 , a2 , and a3 axes are all contained within a single plane
(called the basal plane), and at 120o angles to one another.

Chapter 3-36
The z axis is perpendicular to this basal plane. Diretional indices, which are obtained
as described above, will be denoted by four indices,as [uvtw]; by convention, the
first three indices pertain to projections along the respective a1 , a2 , and a3 axes,z in
the basal plane.
Conversion from the three-index system to the four-index system,
[u’v’w’]  [uvtw]
is accomplished by the following formulas:
n
u  ( 2u'v ' ) (3.6a)
3
n
v  ( 2v ' u' ) (3.6b)
3
t  ( u  v ) (3.6c)
w  nw' (3.6d)

Where primed indices are associated with the three-index scheme and unprimed,
with the new Miller-Bravais four-index system; n is a factor that may be required
to reduce u ,v , t , and w to the smallest integers. For example, using this conversion,
the [010] direction becomes [1210]. Several different directions are indicated in the
hexagonal unit cell (Figure 3.7a)

Chapter 3-37
 Example 3.8:

• 試定出顯示於圖 (a)之六方單位晶胞的方向
指標。

決定方向向量在 a1、a2 和 z 軸的
投影量。其個別投影量分別為 a
（a1 軸），a（a2 軸）和 c（z 軸
），以單位晶胞參數來表示則變
成 1、1 和 1。因此：
u’ = 1 v’ = 1 w’ = 1

Chapter 3-38
將上面指標各乘以 3，得到
u、v、t 和 w 分別為 1、-1、-2
和 3。因此，顯示於圖中之方
向為 [1123]

Chapter 3-39
截距:1∞1
倒數=101=(hkl)
i=-(h+k)=-(1+0)=-1
(hkil)= 1011
Chapter 3-40
 3.10 Crystallographic Planes
The procedure determine the h, k, l Miller index numbers

• 1.If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be
established at the corner of another unit cell.
• 2.At this point the crystallographic plane either intersects or parallels each of the three
axes; the length of the planar intercept for each axis is determined in terms of the lattice
parameters a, b, and c.
• 3.The reciprocals of these numbers are taken. A plane that parallels an axis may be
considered to have an infinite intercept, and, therefore, a zero index.
• 4.If necessary, these three numbers are changed to the set of smallest integers by
multiplication or division by a common factor.
• 5.Finally, the integer indices, not separated by commas, are enclosed within parentheses,
thus: (hkl).

Chapter 3-41
Chapter 3-42
Example Problem 3.9

Determine the Miller indices for the plane shown in the accompanying
sketch (a)

x’ y’ z’
 -1 1/2
0 1 2
Chapter 3-43
 EXAM:3.10: 在一立方單位晶胞內畫出 011的平面
解
首先除去小括弧然後取倒數，分別得到∞、－1 和 1
。此意味這特定平面平行於 x 軸，同時與 y 軸和 z
軸分別交截於 －b 和 c ，如附圖 a 所示。

011

Chapter 3-44
 Hexagonal crystals
截距:1∞1
倒數=101=(hkl)
• Plane (hkil)
i=-(h+k)=-(1+0)=-1
(hkil)= 1011
• i= - (h+k)
• a1－h，a2－k，a3－i
，l－z

Chapter 3-45
Atomic Arrangement

FCC

Chapter 3-46
BCC

Chapter 3-47
 3.11 Linear and Planar Densities

• LD:linear density

• LD=number of atom centered on direction

vector/length of direction vector

Chapter 3-48
LD110 = 2 atoms/4R = 1/2R

Chapter 3-49
 PD = Planar density

• PD = number of atoms centered on a plane/area

of plane
2
• PD110 = 2atoms/(4R) ×(2√2R)= 1/4R √2
(Fig3.10b)

Chapter 3-50
3.12 Closed-packed crystal structures

Chapter 3-51
Chapter 3-52
Chapter 3-53
 3.13 Single Crystals

f16_03_pg64 garnet 石榴石 Chapter 3-54

 SINGLE VS POLYCRYSTALS
• Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Data from Table 3.3,
Callister 6e.
(Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley
and Sons, 1989.)
200 m Adapted from Fig.
4.12(b), Callister 6e.
(Fig. 4.12(b) is
courtesy of L.C. Smith
and C. Brady, the
National Bureau of
Standards,
Washington, DC [now
the National Institute
of Standards and
Technology,
Gaithersburg, MD].)
Chapter 3-55
3.14 Polycrystalline Materials

Chapter 3-56
 POLYCRYSTALS
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3-57
 DEMO: HEATING AND
COOLING OF AN IRON WIRE
The same atoms can
• Demonstrates "polymorphism" have more than one
crystal structure.
Temperature, C
Liquid
1536
BCC Stable
1391
longer
heat up
FCC Stable
shorter!
914 longer!
BCC Stable
cool down
Tc 768 magnet falls off
shorter
Chapter 3-58
3.15 Anisotropy

anisotropic

isotropic

Chapter 3-59
3.16 X-ray diffraction: Determination of
crystal structures

Acrobat 文件

Chapter 3-60
3.18
constructive

destructive

Chapter 3-61
 3.19

Bragg’s law
n = 2dhkl · sin
  1.5402 Å
[Cu K]

Chapter 3-62
Bragg’s law
n = 2dhkl · sin
  1.5402 Å
[Cu K]

Chapter 3-63
X-光繞射和布拉格定律

立方體:

Chapter 3-64
— diffraction techniques & apparatus
‧diffractometer 繞射儀
power diffraction
diffraction angle ( 2θ)
-
x-ray , e beam , neutron beams used as a source
3.20

sample

x-ray generator
閘

Chapter 3-65
determine : crystal structure
cell dimension
(Laue method) crystal orientation (single crystal)
residual stress (compression strain)
crystal size estimation (Scherrer formula)

B (unit : rad )  0.9 


補充  t B ×cos  
2B  B

BCC structure

FCC : all h , k , l odd or even ( 奇 or 偶數 )

BCC : ( h + k +l ) must be even ( 偶數 ) see Fig. 3.20 Chapter 3-66
Figure3.21 Diffraction pattern for powdered lead.

Chapter 3-67
例題 3.12 球平面間距離與繞射角

對 BCC 鐵而言，計算(220)平面組之 (a)平面間距離與 (b)繞

射角。Fe 的晶格參數為 0.2866nm。同時，假設所使用之單
光輻射波長為 0.1790nm，且反射級數為 1。
解：
(a) 平面間距dnkl之值可用 3.16 式決定，同時 a = 2.866nm，
且h = 2，k = 2 及 l = 0，由於我們考慮的是 (220) 平面，因此

Chapter 3-68
P. 83
(b) θ 值可以用 3.15 式來求得，由於是第一級反射，所以
n = 1。

繞射角是 2θ 或

Chapter 3-69
P. 83
example ()

‧Fe(BCC) a=0.2866 , h,k,l = (2,1,1)

a
d hkl   0.117nm
2 1 1
2 2 2

‧Cu Kα1 x-ray λ=0.1542nm

 n‧λ = 2‧dhkl‧sinθhkl n=1
1  0.1542
 sin   2  0.117  0.659
∴ 2  2  sin 1   82.44 o

Chapter 3-70
3.17 Noncrystalline Solids

3.22

Chapter 3-71
 SUMMARY

• Atoms may assemble into crystalline or

amorphous 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).
• Material properties generally vary with single
crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains.

Chapter 3-72