Chapter 3: 결정의 구조와 결함

ISSUES TO ADDRESS...

• How do atoms assemble into solid structures?

• How does the density of a material depend on

its structure?

• How do the crystal structures of ceramic

materials differ from those for metals?

• When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3 - 1
 Crystals
• 고체상태에서 원자들은 규칙성을 가지고 배열
• 재료의 특성은 재료의 배열된 재료의 결정구조에
직접적으로 관련

• 결정내에서 작은 기본 단위구조 (unit cell)가 반복되는데,

이는 비교적 간단한 7개의 결정시스템 (crystal system)과
14개의 결정격자(crystal lattice)로 구분이 가능함.

2
 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.
Chapter 3 - 3
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.40(a),
Callister & Rethwisch 3e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.40(b),
Callister & Rethwisch 3e.

Chapter 3 - 4
 Metallic Crystal Structures
• How can we stack metal atoms to minimize empty space?
• (Treat the atoms as solid sphere)

2-dimensions

vs.

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

5
 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.

We will examine three such structures...

Chapter 3 - 6
입방정계 Crystal Systems
정방정계

사방정계

능면정계

육방정계

단사정계 Unit cell & lattice parameter

삼사정계
7
 Crystal Lattices
• From the seven crystal 입방정계
systems, Bravais showed
that the following 14 lattices
can represents all crystal 정방정계

structures.
– Body-centered (체심)
사방정계
– Face-centered (면심)
– Base-centered (상하면심)

능면정계 육방정계

• What about other forms?

– Face-centered tetragonal? 단사정계 삼사정계
– Can be represented by these
forms 8
 Simple Cubic Structure (SC)
• Rare due to low packing density
• (only Po (polonium) has this structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

Chapter 3 - 9
 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 (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. 3.42,
Callister & Rethwisch 3e. 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

QuickTime?and a
Cinepak decompressor
are needed to see this picture.

Adapted from Fig. 3.2,

Callister & Rethwisch 3e.

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

(Courtesy P.M. Anderson)
Chapter 3 - 11
 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 &
Rethwisch 3e.
a
atoms volume
4
unit cell 2  ( 3a/4) 3
3 atom
APF =
3 volume
a
unit cell 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

QuickTime?and a
Cinepak decompressor
are needed to see this picture.

Adapted from Fig. 3.1, Callister & Rethwisch 3e.

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

(Courtesy P.M. Anderson)
Chapter 3 - 13
 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 3e. 4
unit cell 4 ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
Chapter 3 - 14
 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

15
 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 3e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 Chapter 3 - 16
 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
= 6.022 x 1023 atoms/mol

17
 Theoretical Density, 
• 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 3e.
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 18
 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 3e. (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. Chapter 3 - 19
 Ceramic Crystal Structures
Ceramic structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions

20
 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 3e.
- - - - - -
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 m Xp
m, p values to achieve charge neutrality
Chapter 3 - 21
 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)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 3e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 3.5,
Callister & Rethwisch 3e.

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 3e.
Callister & Rethwisch 3e.
Chapter 3 - 22
 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
23
 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

24
 Example Problem: Predicting the Crystal
Structure of FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077

Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069  0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is NaCl
Cl - 0.181
Data from Table 3.4,
F- 0.133 Callister & Rethwisch 3e.
Chapter 3 - 25
 Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt, sodium chloride) structure
rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 cations (Na+) prefer octahedral sites

FCC Structure

Adapted from Fig. 3.5,

Callister & Rethwisch 3e.

26
 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

Adapted from Fig. 3.5,

Callister & Rethwisch 3e.

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

27
 AX (or MX) Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride (염화세슘) structure:

rCs  0.170
  0.939
rCl 0.181

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred

Adapted from Fig. 3.6,

So each Cs+ has 8 neighbor Cl-
Callister & Rethwisch 3e.

28
 AX (or MX) Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Zinc Blende (ZnS, 황화아연) structure:

4 S atoms at vertices and faces

4 Zn atoms inside the cube

1 Zn atom bonds to 4 S atoms

or vice versa.

Coordination# = 4

Adapted from Fig. 3.6, ZnS, ZnTe, SiC

Callister & Rethwisch 3e.

29
 AX2 (MX2) Crystal Structures
Fluorite structure

• Calcium Fluorite (CaF2) 형석

• Cations in cubic sites

• UO2, ThO2, ZrO2, CeO2

• Antifluorite structure –
positions of cations and
anions reversed

Adapted from Fig. 3.8,

Callister & Rethwisch 3e.

30
 ABX3 Crystal Structures
• Perovskite structure

Ex: complex oxide

BaTiO3

Adapted from Fig. 3.9,

Callister & Rethwisch 3e.

31
Density Computations for Ceramics

Number of formula units/unit cell

n(AC  AA )

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

32
 Densities of Material Classes
In general Graphite/
metals > ceramics > polymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
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 Carbon fibers
Polymers have... Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 3e.
33
 Silicate (규산염) Ceramics
Most common elements on earth are Si & O

Si4+

O2-

Adapted from Figs.

3.10-11, Callister &
Rethwisch 3e
crystobalite

• SiO2 (silica) polymorphic forms are quartz,

crystobalite, & tridymite
• The strong Si-O bonds (strong covalence bonding
character) lead to a high melting temperature
(1710ºC) for this material
34
 Silicates
Bonding of adjacent SiO44- accomplished by the
sharing of common corners, edges, or faces

Adapted from Fig.

3.12, Callister &
Rethwisch 3e.
Mg2SiO4 Ca2MgSi2O7

Presence of cations such as Ca2+, Mg2+, & Al3+

1. maintain charge neutrality, and
2. ionically bond SiO44- to one another
35
 Glass Structure
• Basic Unit: Glass is noncrystalline (amorphous)
4- • Fused silica is SiO2 to which no
Si0 4 tetrahedron impurities have been added
Si 4+ • Other common glasses contain
O2- impurity ions such as Na+, Ca2+,
Al3+, and B3+

• Quartz is crystalline
Na +
SiO2:
Si 4+
O2-

(soda glass)
Adapted from Fig. 3.41,
Callister & Rethwisch 3e.

Chapter 3 - 36
 Layered Silicates
• Layered silicates (e.g., clays, mica, talc)
– SiO4 tetrahedra connected
together to form 2-D plane

• A net negative charge is associated

with each (Si2O5)2- unit
• Negative charge balanced by
adjacent plane rich in positively
charged cations

Adapted from Fig.

3.13, Callister &
Rethwisch 3e.

37
 Layered Silicates (cont)
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+
layer

Adapted from Fig. 3.14,

Callister & Rethwisch 3e.

Note: Adjacent sheets of this type are loosely bound to

one another by van der Waal’s forces.
38
 Polymorphic Forms of Carbon
Diamond
– tetrahedral bonding of
carbon
• Covalence bonding
bewteen atoms
• hardest material known
• very high thermal
conductivity
– large single crystals –
gem stones
– small crystals – used to
grind/cut other materials Adapted from Fig. 3.16,
Callister & Rethwisch 3e.
– diamond thin films
• hard surface coatings –
used for cutting tools,
medical devices, etc. Chapter 3 - 39
Polymorphic Forms of Carbon (cont)
Graphite
– layered structure – parallel hexagonal arrays of
carbon atoms

Adapted from Fig.

3.17, Callister &
Rethwisch 3e.

– Strong covalence bonding inside each layer

– weak van der Waal’s forces between layers
– planes slide easily over one another -- good
lubricant 40
 Polymorphic Forms of Carbon (cont)
Fullerenes and Nanotubes
• Fullerenes – spherical cluster of 60 carbon atoms, C60
– Like a soccer ball
• Carbon nanotubes – sheet of graphite rolled into a tube
– Ends capped with fullerene hemispheres

Adapted from Figs.

3.18 & 3.19, Callister
& Rethwisch 3e.

41
 Crystals as Building Blocks
• Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives Fig. 9.40(c), Callister &
Rethwisch 3e. (Fig. 9.40(c)
(Courtesy Martin Deakins,
courtesy of Pratt and
GE Superabrasives,
Whitney).
Worthington, OH. Used with
permission.)

• Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 42
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
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).
Chapter 3 - 43
 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 3.7,
Callister & Rethwisch
3e. (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.
5.19(b), Callister &
Rethwisch 3e.
(Fig. 5.19(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 - 44
 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. 3.20, Callister & Rethwisch 3e.

45
 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
46
 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

47
Crystallographic Directions

48
 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] a
a1
2
Adapted from Fig. 3.24(a),
Callister & Rethwisch 3e. a2 -a3
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
Chapter 3 - 49
 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 ]

1
u  (2 u ' - v ')
3
a2
1
v  (2 v ' - u ')
- 3
a3
t  - (u +v )
w  w'
a1

Fig. 3.24(a), Callister & Rethwisch 3e.

50
 Before we start…
• I could not find a way to send emails to all students at the
same time.
– Actually, I could not find a way to find the email addresses of the
students.
• If one of the students can collect the email addresses and
send them to me…

51
 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)

[In cubic system, this is a normal vector direction]

52
 Crystallographic Planes
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 (100) a b
x
53
 Crystallographic Planes
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: {100} = (100), (010), (001), (100), (010), (001)

54
 Crystallographic Planes

Adapted from Fig. 3.25,

Callister & Rethwisch 3e.
55
 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. 3.24(b),

Callister & Rethwisch 3e.

56
 Linear Density
Number of atoms
• Linear Density of Atoms  LD =
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

57
Planar Density
Number of atoms centered on a plane

Area of plane

length = 4R = 2 a

58
 Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• [Ex]
a) Draw (100) and (111) crystallographic planes
for Fe (Iron).
b) Calculate the planar density for each of these
planes.

59
 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 3e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms
= 19 atoms
Planar Density = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm2 m2
R
2D repeat unit 3
60
 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  3 
2
R÷
÷  R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
area 16 3 2
R
2D repeat unit 3
61
 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.
62
X-Ray Diffraction

63
X-Rays to Determine Crystal Structure

64
 X-Rays to Determine Crystal Structure
• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra  Adapted from Fig. 3.37,
 
distance
Callister & Rethwisch 3e.
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
65
 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)

Adapted from Fig. 3.20, Callister 5e.

66
 Imperfections in Solids

• Solidification- result of casting of molten material

– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig. 5.19 (b), Callister & Rethwisch 3e.

• Crystals grow until they meet each other

67
 Polycrystalline Materials

Grain Boundaries
• regions between crystals
• transition from lattice of
one region to that of the
other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
– high chemical reactivity
Adapted from Fig. 5.12,
Callister & Rethwisch 3e.
68
 Imperfections in Solids
There is no such thing as a perfect crystal.
• What are these imperfections?

Many of the important properties of materials are due to

the presence of imperfections.

69
 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

Chapter 3 - 70
 Point Defects in Metals
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

Chapter 3 - 71
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration (평형개수) varies with
temperature!
No. of defects Activation energy
 Q 
 exp 
Nv
 v
No. of potential
N  kT 
defect sites
Temperature
Boltzmann's constant
-23
(1.38 x 10 J/atom-K)
-5
(8.62 x 10 eV/atom-K)
Each lattice site
Activation energy: Energy needed for
is a potential
a vacnacy formation
vacancy site
Chapter 3 - 72
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu (copper) at
1000C.
• Given:  = 8.4 g /cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
Q 
Nv   v
exp  -4
N  kT = 2.7 x 10
1273 K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N=  x = 8.0 x 1028 sites (atoms/m3)
A Cu
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
Chapter 3 - 73
 Point Defects in Ceramics (i)
• Vacancies (공격자점)
-- vacancies exist in ceramics for both cations and anions
• Interstitials (자차삽입점)
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy
Adapted from Fig. 5.2, Callister &
Rethwisch 3e. (Fig. 5.2 is from
W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Anion
Chapter 3 - 74
Vacancy
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig. 5.3, Callister &
Rethwisch 3e. (Fig. 5.3 is from
W.G. Moffatt, G.W. Pearsall, and
J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Frenkel
Defect

QD /kT
• Equilibrium concentration of defects e

Chapter 3 - 75
 Point Defects in Ceramics (iii)
• Stoichiometry : when there is exact ratio of cations
and anions predicted by chemical formula
– For NaCl, if number of Na+ and Cl- is equal.
• Nonstoichiometric: if there is deviation from the exact ratio
– It can occur if there could exists two ionic states for one of the ions.
– FeO: O2- but F3+ or F2+.
– Still, the electric neutrality should be satisfued

76
 Imperfections in Metals (i)
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
-- different composition
-- often different structure.

Chapter 3 - 77
 Imperfections in Metals
• Solid Solutions
– Second atoms are added to the host material, but the crystal
structure is maintained and no new structures are formed
– Solvent (용매)
• The material present in the greatest amount
– Solute (용질)
• That exists in a minor concentration

• Phase
– The physically and/or chemically distinct material regions

78
 Imperfections in Metals (ii)
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 1. r (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valency
• All else being equal, a metal will have a greater tendency
to dissolve a metal of higher valency than one of lower
valency

79
 Imperfections in Metals (iii)
Application of Hume–Rothery rules – Solid
Solutions Element Atomic Crystal Electro- Valence
Radius Structure nega-
(nm) tivity
1. Would you predict Cu 0.1278 FCC 1.9 +2
C 0.071
more Al or Ag H 0.046
O 0.060
to dissolve in Zn? Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
2. More Zn or Al Fe 0.1241 BCC 1.8 +2
Ni 0.1246 FCC 1.8 +2
in Cu? Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 159, Callister & Rethwisch 3e.

80
 Imperfections in Ceramics
• Substutional impurity
• Interstitial impurity
• There could be anion, cation impurities
– Electroneutrality!

81
 Imperfections in Ceramics
• Electroneutrality (charge balance) must be maintained
when impurities are present
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
without impurity Ca 2+ impurity with impurity
• Substitutional anion impurity anion vacancy
O2-

Cl - Cl -
without impurity O2- impurity with impurity
Chapter 3 - 82
 Impurities in Solids
• Specification of composition
m1
– weight percent C1  x 100
m1  m2
m1 = mass of component 1

n m1
– atom percent C 
'
x 100
n m1  n m 2
1

nm1 = number of moles of component 1

83
 Impurities in Solids
• Specification of composition
m1
– weight percent C1  x 100
m1  m2
m1 = mass of component 1

n m1
– atom percent C 
'
x 100
n m1  n m 2
1

nm1 = number of moles of component 1

[or number of atoms since 1 mole includes
same number of atoms for all materials]

84
 Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

Chapter 3 - 85
 Imperfections in Solids
Linear Defects (Dislocations)
– Are one-dimensional defects around which atoms are
misaligned
• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b perpendicular () to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b parallel () to dislocation line
Burger’s vector, b: measure of lattice distortion

86
 Imperfections in Solids
• Burger’s Vector
– Represents the direction of dislocation

87
 Imperfections in Solids
Edge Dislocation
Burgers vector & dislocation line are normal to each other

Fig. 5.8, Callister & Rethwisch 3e.

88
 Motion of Edge Dislocation
• Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right here).
• Bonds across the slipping planes are broken and
remade in succession.

QuickTime?and a
Cinepak decompressor Atomic view of edge
are needed to see this picture.
dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

Chapter 3 - 89
 Imperfections in Solids
Screw Dislocation
- Dislocation line & Burgers Vector are parallel
to each other

Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 5.9, Callister & Rethwisch 3e. Chapter 3 - 90
 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 5.10, Callister & Rethwisch 3e.

Screw

91
 Planar Defects Solid

• External Surface
– Surface atoms are not
bounded to the maximum
no. of nearest boundaries
– Have a higher energy
states
• Grain Boundaries
– regions between crystals
– transition from lattice of
one region to that of the
other

Adapted from Fig. 5.12,

Callister & Rethwisch 3e.
92
 Planar Defects in Solids
• Twin boundary (plane)
– Special try of grane boundary.
– Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 5.14,

Callister & Rethwisch 3e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
93
– Ex: ABCABABC
 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.
• 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.

Chapter 3 - 94
 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 is used for crystal structure and
interplanar spacing determinations.

Chapter 3 - 95
 Summary
• Point, Line, and Area defects exist in solids.

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• Defects affect material properties (e.g., grain

boundaries control crystal slip).

Chapter 3 - 96
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 3 - 97