Callister ch03 Crystal Structures Jkchen

Chapter 3: The Structure of Crystalline Solids
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?
Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 1
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.

3.2 Crystalline vs. Noncrystalline
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.
3.3 Unit Cells in Crystalline material
3.7 – Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems
14 crystal lattices
a, b, and c are the lattice constants
Fig. 3.4, Callister 7e.

七大晶系
立方
(等軸) 7 Crystal
Systems
六方
正方
四方
菱方
斜方
(長方)
單斜
三斜 Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 6
Section 3.4 – Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions
vs.
Close packed NOT so close packed

Now stack these 2-D layers to make 3-D structures
Metallic Crystal Structures

• Tend to be densely packed.
• 70% metallic elements belongs to fcc, bcc, or hcp.
• 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.
We will examine three such structures...
Simple Cubic Structure (SC)
• Rare due to low packing denisty (only Po has this structure)
• Close-packed directions are cube edges.
• 配位數Coordination # = 6
(# nearest neighbors)
Atomic Packing Factor (APF)原子堆積密度

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
4
a 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. 3.23,
Callister 7e. Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 10
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,

Callister 7e.
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:
Adapted from
R length = 4R = 3 a
Fig. 3.2(a), Callister 7e.
a
atoms volume
4 3
unit cell 2  ( 3a/4)
3 atom
APF =
volume
a3
unit2020,
Copyright J.K.Chen, MMRE, NTUT, cell
John Wiley & Sons, Callister Chapter 3 - 12
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 7e.
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 7e. atoms volume
4 3
unit cell 4 ( 2a/4)
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 7e.
• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 16
3.5 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 = Avogadro’s number
= 6.023 x 1023 atoms/mol
Theoretical Density, 
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol
1/2
Assignment: Based on the above structure,

calculate the APF and theoretical density of diamond.
Ferroelectric Ceramics
Ferroelectric Ceramics are dipolar below Curie TC = 120ºC
• cooled below Tc in strong electric field - make material
with strong dipole moment
Fig. 18.35, Callister 7e.
Densities of Material Classes

In general Metals/
Graphite/
Composites/
metals > ceramics > polymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
 (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
• intermediate values 0.3

Data from Table B1, Callister 7e.
Section 3.6 – Polymorphism 同素異型
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538ºC
BCC -Fe
carbon
diamond, graphite 1394ºC
FCC -Fe
912ºC
BCC -Fe
Carbon- Polymorphism by T & P
diamond sp3 bond
graphite sp2 bond
Carbon nanotube
C60, FullereneCopyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 24
1atm~1.013bar
粒度
1atm~101325 Pa
奈米尺寸可以在較低溫度、壓力下生成鑽石
Section 3.8 Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½
000
y
a b
Point coordinates for unit cell
x corner are 111
z 2c
Translation: integer multiple of

lattice constants  identical
b y position in another unit cell
b
3.9 Crystallographic Directions

z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
x [uvw]
ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no commas
a3
[uvtw] a2
a1
a2 -a3
Adapted from Fig. 3.8(a), Callister 7e.
2
ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
HCP Crystallographic Directions

• Hexagonal Crystals
– 4 parameter Miller-Bravais lattice coordinates are related to the
direction indices (i.e., u'v'w') as follows.
z [ u 'v 'w ' ]  [ uvtw ] (3.6)

1
u (2 u ' - v ')
3
1
a2 v  (2 v ' - u ') u’=2u+v
3
v’=2v+u
- t  - (u +v )
a3
w  w'
a1
Fig. 3.8(a), Callister 7e.
3.10 Crystallographic Planes
Adapted from Fig. 3.9, Callister 7e.
Crystallographic Planes
• Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.
• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no commas i.e., (hkl)
Finding (hkl) plane in any crystal system
Equation: hx + ky + lz = 1
z
[0,0,1/l]
(hkl) plane
y
[1/h,0,0] [0,1/k,0]
x Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 33
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (200) a b
x
z
example a b c c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 y
3. Reduction 6 3 4 a b
4. Miller Indices (634) x
Family of Planes {hkl}
Ex: in cubic {100} = (100), (010), (001), (100), (010), (001)

Crystallographic Planes (HCP)

• In hexagonal unit cells the same idea is used
z
example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2
3. Reduction 1 0 -1 1
a3
4. Miller-Bravais Indices (1011) a1
Adapted from Fig. 3.8(a), Callister 7e.
3.11 Linear Density
Number of atoms
• Linear Density of Atoms  LD =
Unit length of direction vector
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
a 2
LD   3.5 nm 1
length 2a
Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit
(100) 4 3
a R
3
Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms
= = 12.1 = 1.2 x 10 19 atoms
Planar Density = 2
area a2 4 3 nm2 m2
R
2D repeat unit 3
Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell
2a atoms in plane
atoms above plane
atoms below plane
3
h a
2
2
 4 3  16 3 2
area  2 ah  3 a 2  3  ÷  3 R
R÷
atoms  3 
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3
2 nm m2
R2
2D repeat unit 3
Planar d-Spacing in Cubic System

Dot product of [xyz] and [1/h,0,0],[0,1/k,0],[0,0,1/l]
x/h=y/k=z/l=cnst. z
• Conveniently, [xyz]=[hkl]
• Evaluating distance Op [0,0,1/l]

[xyz]
(by [1/h,0,0] dot product unit O
[0,1/k,0]
vector of [xyz])
Op= [1/h,0,0] y
p
• substituting [xyz] with [hkl], x
|Op|=1/(h2+k2+l2)^(1/2)
= planar spacing
• use lattice parameter, a, as the unit:
dhkl = planar spacing = a/(h2+k2+l2)1/2
= f(a,b,c,,h,k,l)
Copyrightcan beMMRE,
J.K.Chen, usedNTUT,to identify
2020, John Wiley & crystal
Sons, Callisterstructure
Chapter 3 - 40
3.13 Crystals as Building Blocks
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives
• Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
3.14/15 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
-Properties vary with
direction: anisotropic.異向性
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 m
vary with direction.
-If grains are randomly
oriented: isotropic. 等向性
(Epoly iron = 210 GPa)
-If grains are textured, 集合組織
anisotropic.
Anisotropic Properties 異向性質
fcc
fcc
bcc
bcc
Polycrystals多晶體
Anisotropic
• Most engineering materials are polycrystals.
1 mm
• Nb-Hf-W plate with an electron beam weld. Isotropic

• Each "grain" is a single crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Crystalline vs. Amorphous
Quartz glass
Three types of Si Solar Cells
PRINCIPLES OF
X-RAY DIFFRACTION (XRD)

X光繞射
3.16 - X-Ray Diffraction
E=h c/λ= hν
低能量高能量
• Diffraction gratings must have spacings comparable to
the wavelength of diffracted radiation.
• Can’t resolve spacings  , Cu K =1.5418A，He
atomic radius=0.49A, most solid atom radius>0.75A
• Spacing is the distance between parallel planes of
atoms. Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 - 51
Cu Kα =8.038 KeV = 1.54 Å λ

Constructive vs. destructive interference
建設性干涉-破壞性干涉
Bragg Law
Diffraction condition
(n)  = 2 d sin 
n  Integer
d sin 
X-Rays to Determine Crystal Structure

• Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal
extra
distance

travelled  
by wave “2” spacing
d between
planes
Measurement of X-ray
n
critical angle, c, intensity d
(from 2 sin c
allows computation of
detector)
planar spacing, d.

c
XRD Setup
FCC XRD spectrum
Structure Factors F and Peak Intensity I
Fhkl: structure factors of {hkl} planes.

un,vn,wn: coordinates of atoms in a unit cell
fn : atomic scattering factor of n-th atom和原子序有關
N: total number of atoms in a unit cell
I: intensity of XRD peaks
p: multiplicity factor
XRD Peaks of bcc Structures

• Each unit cell contains 2 atoms at
[0,0,0], [½,½,½]
h+k+l cos(h+k+l) 2+2cos(h+k+l) F I

1,3,5 odd -1 0 forbidden zones 0 0
2,4,6 even 1 4 2f 4f2
{hkl}bcc peaks
• Therefore, bcc shows peaks only when h+k+l=even.
{hkl} hkl / multiplicity h2+k2+l2 dhkl Sin/2d h+k+l XRD peak
{100} (100)(010)(001) 1 a/1 /2a -1/1 forbidden
{110} (110)(011)(101) 2 a/√2 √2 /2a -2/0/2 YES
(10-1)(1-10)(01-1)
{111} (111) (11-1)(1-11) (-111) 3 a/√3 √3 /2a -1/3/1 forbidden
{200} (200)(020)(002) 4 a/2 /2a -2/2 YES
{210} (210) (120) (201) (102) 5 a/√5 √5 /2a -1/3/1 forbidden
(012) (021) (-210) (1-20)
(-201) (10-2) (01-2) (0-21)
{211} (211)(121)(112) 6 a/√6 √6 /2a -4/-2 YES
(-211)(2-11)(21-1) /0/2/4
(-121)(1-21)(12-1) Increasing 2
(-112)(1-12)(11-2)
ASGN: Calculate structure factors/diffraction conditions for diamond

diamond has atoms at [0,0,0], [1/2,1/2,0], [1/2,0,1/2], [0,1/2,1/2],
[1/4,1/4,1/4],[1/4,3/4,3/4],[3/4,1/4,3/4],[3/4,3/4,1/4]
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 2
Diffraction pattern for polycrystalline -iron (BCC)
Consider
Special Conditions
• Powders (isotropic等向性的)
• Polycrystal (with preferred orientation)
• Single crystal
• Amorphous
• Nanocrystalline (Scherrer Eqn: B(2 θ)=Kλ / L cosθ)
• Thin film
• Texture analysis: 集合組織
– XRD -> Pole figures -> ODF
Powder diffraction file:

JCPDS card #27-1402 for Si
對應 peak位置、強度
GeSbTeBi Films
(111) (200) (220)
TTMC ARQ131 Profiled

inside (erosion area)
Texture Analysis 集合組織分析
• Phi2 = 45˚ ODF

• Strong (110)fiber
Pure Al Forging and HTed
As forged (20mm, GS >3mm) 2mm
400℃1hr heat treated (20mm, GS 390um)
• No recrystallized grains other than surface.

• Heat treatment to recrystallize , ~390um。
Rolling and Heat treatment
1mm 1mm 1mm

200℃ HT 1hr 300℃ HT 1hr 400℃ HT 1hr, 281um
• Treatment at different temperature to for different microstructures.
• Uniform structures may be controlled.
Varied process and textures
4n Al forging+
recrystallization C company 4n Al V company 5n Al
500um 500um 500um

• Different thermo-mechanical treatment gives rise to
different textures. Purity
Copyright J.K.Chen, also
MMRE, NTUT, affects.
2020, John Wiley & Sons, Callister Chapter 3 - 71
EBSD
背向散射電子繞射
鉬板 Mo sputtering targets
粉末燒結組織軋延組織再結晶組織

Powder sintered Rolled Recrystallized
Copyright J.K.Chen, MMRE, NTUT, 2020, John Wiley & Sons, Callister Chapter 3 -
SUMMARY
• Atoms may assemble into crystalline or
amorphous structures. 結晶 vs. 非晶
• Common metallic crystal structures are FCC, BCC, and HCP.
Coordination number 配位數 and atomic packing factor 原子堆
積密度 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).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.
SUMMARY
• Materials can be single crystals or polycrystalline.

Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
• Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
• X-ray diffraction (XRD) is used for crystal structure and
interplanar spacing determinations.
• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

Callister ch03 Crystal Structures Jkchen

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Chapter 3: The Structure of Crystalline Solids

• How does the density of a material depend on

• When do material properties vary with the

Energy and Packing

• Dense, ordered packing Energy

Dense, ordered packed structures tend to have lower energies.

3.3 Unit Cells in Crystalline material

a, b, and c are the lattice constants

Fig. 3.4, Callister 7e.

Close packed NOT so close packed

Metallic Crystal Structures

• Reasons for dense packing:

We will examine three such structures...

Atomic Packing Factor (APF)原子堆積密度

ex: Cr, W, Fe (), Tantalum, Molybdenum

Adapted from Fig. 3.2,

2 atoms/unit cell: 1 center + 8 corners x 1/8

Atomic Packing Factor: BCC

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Adapted from Fig. 3.1, Callister 7e.

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

Atomic Packing Factor: FCC

Hexagonal Close-Packed Structure

A sites Top layer

A sites Bottom layer

• Coordination # = 12 6 atoms/unit cell

Mass of Atoms in Unit Cell

where n = number of atoms/unit cell

Assignment: Based on the above structure,

Fig. 18.35, Callister 7e.

Densities of Material Classes

• intermediate values 0.3

Carbon- Polymorphism by T & P

diamond sp3 bond

graphite sp2 bond

Translation: integer multiple of

3.9 Crystallographic Directions

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

ex: ½, ½, -1, 0 => [ 1120 ] a3

HCP Crystallographic Directions

z [ u 'v 'w ' ]  [ uvtw ] (3.6)

Fig. 3.8(a), Callister 7e.

Adapted from Fig. 3.9, Callister 7e.

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: in cubic {100} = (100), (010), (001), (100), (010), (001)

Crystallographic Planes (HCP)

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(a), Callister 7e.

Planar Density of (100) Iron

Radius of iron R = 0.1241 nm

Planar d-Spacing in Cubic System

• Evaluating distance Op [0,0,1/l]

• Properties of crystalline materials

Anisotropic Properties 異向性質

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

Three types of Si Solar Cells

X-RAY DIFFRACTION (XRD)

Cu Kα =8.038 KeV = 1.54 Å λ

X-Rays to Determine Crystal Structure

FCC XRD spectrum

Fhkl: structure factors of {hkl} planes.

XRD Peaks of bcc Structures

粉末燒結組織軋延組織再結晶組織