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The Structure of Crystalline Solids

Aula 3 - Crystalline Solids - 31 de marzo de 2014


Types of solids
!
Crystalline material: atoms self-
organize in a periodic array
!
Single crystal: atoms are in a
periodic array over the entire
extend of the material
!
Polycrystalline material: composed
of small crystals or grains
!
Amorphous: disordered, lack of a
systematic arrangement
2
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Crystal Structures
!
Consider atoms to be hard-spheres with well dened radii. The
shortest distance between two like atoms is one diameter of the
hard sphere
The way in which atoms or molecules
are arranged
2R
Crystalline Lattice: A
tridimensional matrix
representing the position of the
atoms
3
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Energy and Packing
4
Non dense, random packing
Chapter 3 - 2
Non dense, random packing
Dense, ordered packing
Dense, ordered packed structures tend to have
lower energies.
Energy and Packing
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Chapter 3 - 2
Non dense, random packing
Dense, ordered packing
Dense, ordered packed structures tend to have
lower energies.
Energy and Packing
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Dense, ordered packing
Chapter 3 - 2
Non dense, random packing
Dense, ordered packing
Dense, ordered packed structures tend to have
lower energies.
Energy and Packing
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Chapter 3 - 2
Non dense, random packing
Dense, ordered packing
Dense, ordered packed structures tend to have
lower energies.
Energy and Packing
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Energy
r
typical neighbor
bond length
typical neighbor
bond energy
Dense, ordered packed structures, tend to have lover
energies
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Unit Cells
!
The choice of origin of the repeating unit can vary
!
Most are represented by parallelepipeds or prisms
The smallest repeating unit which shows the full symmetry of the
crystal structure
2-Dimensional
Na+ Cl+
Na+ Cl+
Na+ Cl+
Na+
Cl+
Na+ Cl+
Na+ Cl+
3-Dimensional
5
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Metallic Crystal Structures
6
How can we stack atoms to minimize empty space?
Chapter 3 - 4
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
2 - dimensions
Stack these 2-D layers to make 3-D structures
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Metallic Crystal Structures
!
Metals are usually polycrystalline
!
Compact arrangements
!
Using the hard sphere model, each sphere represents a
ionic nucleus
!
Atomic (hard sphere) radius, R, dened by ion core
radius - typically 0.1 - 0.2 nm
7
fcc
hcp
bcc
face-center cubic
hexagonal close-packed
body-center cubic
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Simple Cubic Structure (SC)
8
Only Po has this estructure
Rare due to low packing density
Close-packed directions are cubic edges
Chapter 3 - 6
Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
Simple Cubic Structure (SC)
Click once on image to start animation
(Courtesy P.M. Anderson)
Chapter 3 - 6
Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
Simple Cubic Structure (SC)
Click once on image to start animation
(Courtesy P.M. Anderson)
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Atomic Packing Factor (APF)
9
APF = Sum of atomic volumes
Volume of cell
APF for a simple cubic structure = 0,52
Chapter 3 - 7
APF for a simple cubic structure = 0.52
APF =
a
3
4
3
! (0.5a)
3
1
atoms
unit cell
atom
volume
unit cell
volume
Atomic Packing Factor (APF)
APF =
Volume of atoms in unit cell*
Volume of unit cell
*assume hard spheres
Adapted from Fig. 3.3 (a),
Callister & Rethwisch 9e.
close-packed directions
a
R = 0.5a
contains 8 x 1/8 =
1 atom/unit cell
Chapter 3 - 7
APF for a simple cubic structure = 0.52
APF =
a
3
4
3
! (0.5a)
3
1
atoms
unit cell
atom
volume
unit cell
volume
Atomic Packing Factor (APF)
APF =
Volume of atoms in unit cell*
Volume of unit cell
*assume hard spheres
Adapted from Fig. 3.3 (a),
Callister & Rethwisch 9e.
close-packed directions
a
R = 0.5a
contains 8 x 1/8 =
1 atom/unit cell

APF: fraction of volume occupied by hard spheres


Aula 3 - Crystalline Solids - 31 de marzo de 2014
Body-Centered Cubic (bcc) Crystal Structures
!
Cubic geometry
!
Examples: Cr, Fe, W

Atoms are located at each of the corners and on one


another at the center of the cube
10
a

a: cube edge length

R: atomic radius
cubic edge length
a = 4R /"3
Two atoms are associated with each BCC unit cell: the equivalent of one atom
from the eight corners, each of which is shared among eight unit cells, and the sin-
gle center atom, which is wholly contained within its cell. In addition, corner and
center atom positions are equivalent. The coordination number for the BCC crys-
tal structure is 8; each center atom has as nearest neighbors its eight corner atoms.
Because the coordination number is less for BCC than FCC, so also is the atomic
packing factor for BCC lower0.68 versus 0.74.
The Hexagonal Close-Packed Crystal Structure
Not all metals have unit cells with cubic symmetry; the final common metallic crystal
structure to be discussed has a unit cell that is hexagonal. Figure 3.3a shows a reduced-
sphere unit cell for this structure, which is termed hexagonal close-packed (HCP); an
3.4 Metallic Crystal Structures 49
(a) ( b) (c)
Figure 3.2 For the body-centered cubic crystal structure, (a) a hard-sphere unit cell
representation, (b) a reduced-sphere unit cell, and (c) an aggregate of many atoms. [Figure
(c) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of
Materials, Vol. I, Structure, p. 51. Copyright 1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley & Sons, Inc.]
hexagonal close-
packed (HCP)
c
a
A
B
C
J
E
G
H
F
D
(b) (a)
Figure 3.3 For the hexagonal close-packed crystal structure, (a) a reduced-sphere unit
cell (a and c represent the short and long edge lengths, respectively), and (b) an aggregate
of many atoms. [Figure (b) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure
and Properties of Materials, Vol. I, Structure, p. 51. Copyright 1964 by John Wiley & Sons,
New York. Reprinted by permission of John Wiley & Sons, Inc.]
Crystal Systems and
Unit Cells for Metals
VMSE
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< -/
Two atoms are associated with each BCC unit cell: the equivalent of one atom
from the eight corners, each of which is shared among eight unit cells, and the sin-
gle center atom, which is wholly contained within its cell. In addition, corner and
center atom positions are equivalent. The coordination number for the BCC crys-
tal structure is 8; each center atom has as nearest neighbors its eight corner atoms.
Because the coordination number is less for BCC than FCC, so also is the atomic
packing factor for BCC lower0.68 versus 0.74.
The Hexagonal Close-Packed Crystal Structure
Not all metals have unit cells with cubic symmetry; the final common metallic crystal
structure to be discussed has a unit cell that is hexagonal. Figure 3.3a shows a reduced-
sphere unit cell for this structure, which is termed hexagonal close-packed (HCP); an
3.4 Metallic Crystal Structures 49
(a) ( b) (c)
Figure 3.2 For the body-centered cubic crystal structure, (a) a hard-sphere unit cell
representation, (b) a reduced-sphere unit cell, and (c) an aggregate of many atoms. [Figure
(c) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of
Materials, Vol. I, Structure, p. 51. Copyright 1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley & Sons, Inc.]
hexagonal close-
packed (HCP)
c
a
A
B
C
J
E
G
H
F
D
(b) (a)
Figure 3.3 For the hexagonal close-packed crystal structure, (a) a reduced-sphere unit
cell (a and c represent the short and long edge lengths, respectively), and (b) an aggregate
of many atoms. [Figure (b) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure
and Properties of Materials, Vol. I, Structure, p. 51. Copyright 1964 by John Wiley & Sons,
New York. Reprinted by permission of John Wiley & Sons, Inc.]
Crystal Systems and
Unit Cells for Metals
VMSE
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< -/
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Body-Centered Cubic (bcc) Crystal Structures
!
Cubic geometry
!
Examples: Cr, Fe, W
11
11 MSE 2090: Introduction to Materials Science Chapter 3, Structure of solids
Body-Centered Cubic (BCC) Crystal Structure (I)
Atom at each corner and at center of cubic unit cell
Cr, -Fe, Mo have this crystal structure
R
Atoms /Unit cell = 2
Coordination Number: 8
a
Aula 3 - Crystalline Solids - 31 de marzo de 2014
BCC - APF
12
Chapter 3 - 10
Atomic Packing Factor: BCC
APF =
4
3
! ( 3 a/4 )
3
2
atoms
unit cell
atom
volume
a
3
unit cell
volume
length = 4R =
Close-packed directions:
3 a
APF for a body-centered cubic structure = 0.68
a
R
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 9e.
a
a 2
a 3
APF = 0,68
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Face-Centered Cubic (fcc) Crystal Structures
13

All atoms in the unit cell are equivalent

FCC can be represented by a stack of


close-packed planes (planes with highest
density of atoms)
7 MSE 2090: Introduction to Materials Science Chapter 3, Structure of solids
Face-Centered Cubic (FCC) Crystal Structure (I)
Atoms are located at each of the corners and on the
centers of all the faces of cubic unit cell
Cu, Al, Ag, Au have this crystal structure
Two representations
of the FCC unit cell
R
a
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Face-Centered Cubic (fcc) Crystal Structures
!
Cubic geometry
!
Examples: Cu, Al, Ag, Au

Atoms are located at each of the corners and on the of all the
faces of cubic unit cell
14
a

a: cube edge length

R: atomic radius
cubic edge length
a = 2R"2
46 Chapter 3 / The Structure of Crystalline Solids 46 Chapter 3 / The Structure of Crystalline Solids
(a) ( b)
(c)
Figure 3.1 For the face-
centered cubic crystal
structure, (a) a hard-
sphere unit cell
representation, (b) a
reduced-sphere unit cell, and
(c) an aggregate of many
atoms. [Figure (c) adapted
from W. G. Moffatt, G. W.
Pearsall, and J. Wulff, The
Structure and Properties of
Materials, Vol. I, Structure, p.
51. Copyright 1964 by
John Wiley & Sons, New
York. Reprinted by
permission of John Wiley &
Sons, Inc.]
Cr ys t al Str uctur es
3.2 FUNDAMENTAL CONCEPTS
Solid materials may be classified according to the regularity with which atoms or ions
are arranged with respect to one another. A crystalline material is one in which the
atoms are situated in a repeating or periodic array over large atomic distances; that
is, long-range order exists, such that upon solidification, the atoms will position them-
selves in a repetitive three-dimensional pattern, in which each atom is bonded to its
nearest-neighbor atoms. All metals, many ceramic materials, and certain polymers
form crystalline structures under normal solidification conditions. For those that do
not crystallize, this long-range atomic order is absent; these noncrystalline or amor-
phous materials are discussed briefly at the end of this chapter.
Some of the properties of crystalline solids depend on the crystal structure of
the material, the manner in which atoms, ions, or molecules are spatially arranged.
There is an extremely large number of different crystal structures all having long-range
atomic order; these vary from relatively simple structures for metals to exceedingly
complex ones, as displayed by some of the ceramic and polymeric materials. The pres-
ent discussion deals with several common metallic crystal structures. Chapters 12 and
14 are devoted to crystal structures for ceramics and polymers, respectively.
When describing crystalline structures, atoms (or ions) are thought of as being
solid spheres having well-defined diameters. This is termed the atomic hard-sphere
crystalline
crystal structure
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< -=
46 Chapter 3 / The Structure of Crystalline Solids 46 Chapter 3 / The Structure of Crystalline Solids
(a) ( b)
(c)
Figure 3.1 For the face-
centered cubic crystal
structure, (a) a hard-
sphere unit cell
representation, (b) a
reduced-sphere unit cell, and
(c) an aggregate of many
atoms. [Figure (c) adapted
from W. G. Moffatt, G. W.
Pearsall, and J. Wulff, The
Structure and Properties of
Materials, Vol. I, Structure, p.
51. Copyright 1964 by
John Wiley & Sons, New
York. Reprinted by
permission of John Wiley &
Sons, Inc.]
Cr ys t al Str uctur es
3.2 FUNDAMENTAL CONCEPTS
Solid materials may be classified according to the regularity with which atoms or ions
are arranged with respect to one another. A crystalline material is one in which the
atoms are situated in a repeating or periodic array over large atomic distances; that
is, long-range order exists, such that upon solidification, the atoms will position them-
selves in a repetitive three-dimensional pattern, in which each atom is bonded to its
nearest-neighbor atoms. All metals, many ceramic materials, and certain polymers
form crystalline structures under normal solidification conditions. For those that do
not crystallize, this long-range atomic order is absent; these noncrystalline or amor-
phous materials are discussed briefly at the end of this chapter.
Some of the properties of crystalline solids depend on the crystal structure of
the material, the manner in which atoms, ions, or molecules are spatially arranged.
There is an extremely large number of different crystal structures all having long-range
atomic order; these vary from relatively simple structures for metals to exceedingly
complex ones, as displayed by some of the ceramic and polymeric materials. The pres-
ent discussion deals with several common metallic crystal structures. Chapters 12 and
14 are devoted to crystal structures for ceramics and polymers, respectively.
When describing crystalline structures, atoms (or ions) are thought of as being
solid spheres having well-defined diameters. This is termed the atomic hard-sphere
crystalline
crystal structure
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< -=
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Face-Centered Cubic (fcc) Crystal Structures
!
Cubic geometry
!
Examples: Cu, Al, Ag, Au, Pb,
Ni, Pt
15
CN: 12

Coordination number (CN): the


number of closest neighbors to which
an atom is bonded
Atoms /Unit cell = 4
46 Chapter 3 / The Structure of Crystalline Solids 46 Chapter 3 / The Structure of Crystalline Solids
(a) ( b)
(c)
Figure 3.1 For the face-
centered cubic crystal
structure, (a) a hard-
sphere unit cell
representation, (b) a
reduced-sphere unit cell, and
(c) an aggregate of many
atoms. [Figure (c) adapted
from W. G. Moffatt, G. W.
Pearsall, and J. Wulff, The
Structure and Properties of
Materials, Vol. I, Structure, p.
51. Copyright 1964 by
John Wiley & Sons, New
York. Reprinted by
permission of John Wiley &
Sons, Inc.]
Cr ys t al Str uctur es
3.2 FUNDAMENTAL CONCEPTS
Solid materials may be classified according to the regularity with which atoms or ions
are arranged with respect to one another. A crystalline material is one in which the
atoms are situated in a repeating or periodic array over large atomic distances; that
is, long-range order exists, such that upon solidification, the atoms will position them-
selves in a repetitive three-dimensional pattern, in which each atom is bonded to its
nearest-neighbor atoms. All metals, many ceramic materials, and certain polymers
form crystalline structures under normal solidification conditions. For those that do
not crystallize, this long-range atomic order is absent; these noncrystalline or amor-
phous materials are discussed briefly at the end of this chapter.
Some of the properties of crystalline solids depend on the crystal structure of
the material, the manner in which atoms, ions, or molecules are spatially arranged.
There is an extremely large number of different crystal structures all having long-range
atomic order; these vary from relatively simple structures for metals to exceedingly
complex ones, as displayed by some of the ceramic and polymeric materials. The pres-
ent discussion deals with several common metallic crystal structures. Chapters 12 and
14 are devoted to crystal structures for ceramics and polymers, respectively.
When describing crystalline structures, atoms (or ions) are thought of as being
solid spheres having well-defined diameters. This is termed the atomic hard-sphere
crystalline
crystal structure
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a
Aula 3 - Crystalline Solids - 31 de marzo de 2014
FCC - APF
16
Chapter 3 - 12
APF for a face-centered cubic structure = 0.74
Atomic Packing Factor: FCC
maximum achievable APF
APF =
4
3
! ( 2 a/4 )
3
4
atoms
unit cell
atom
volume
a
3
unit cell
volume
Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
2 a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.
APF= 0,74
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Closed-Packed Structures
17
A A A A A A
A A A A A A
A A A A A A
A
A A A A A
B B B B B B
B B B B B B
B B B B B B
B
B B B B B
C C C C C C
C C C C C C
C C C C C C
C
C C C C C
fcc: ABCABC... stacking sequence
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Closed-Packed Structures
18
A A A A A A
A A A A A A
A A A A A A
A
A A A A A
B B B B B B
B B B B B B
B B B B B B
B
B B B B B
A A A A A A
A A A A A A
A A A A A A
A
A A A A A
stacking sequence ABAB structure
hcp
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Hexagonal Closed-Packed (hcp) Crystal Structures
!
Hexagonal geometry
!
Composed with various hc
unit cells
!
Examples: Cd, Mg, Zn, Ti

Six atoms form regular hexagon, surrounding one atom in center.


Another plane is situated halfway up unit cell (c-axis), with 3


additional atoms situated at interstices of hexagonal (close-packed)
planes
19
13 MSE 2090: Introduction to Materials Science Chapter 3, Structure of solids
Hexagonal Close-Packed Crystal Structure (I)
HCP is one more common structure of metallic crystals
Six atoms form regular hexagon, surrounding one atom
in center. Another plane is situated halfway up unit cell
(c-axis), with 3 additional atoms situated at interstices of
hexagonal (close-packed) planes
Cd, Mg, Zn, Ti have this crystal structure
a
c

Two cell lattice parameters:


a and c
Two atoms are associated with each BCC unit cell: the equivalent of one atom
from the eight corners, each of which is shared among eight unit cells, and the sin-
gle center atom, which is wholly contained within its cell. In addition, corner and
center atom positions are equivalent. The coordination number for the BCC crys-
tal structure is 8; each center atom has as nearest neighbors its eight corner atoms.
Because the coordination number is less for BCC than FCC, so also is the atomic
packing factor for BCC lower0.68 versus 0.74.
The Hexagonal Close-Packed Crystal Structure
Not all metals have unit cells with cubic symmetry; the final common metallic crystal
structure to be discussed has a unit cell that is hexagonal. Figure 3.3a shows a reduced-
sphere unit cell for this structure, which is termed hexagonal close-packed (HCP); an
3.4 Metallic Crystal Structures 49
(a) ( b) (c)
Figure 3.2 For the body-centered cubic crystal structure, (a) a hard-sphere unit cell
representation, (b) a reduced-sphere unit cell, and (c) an aggregate of many atoms. [Figure
(c) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure and Properties of
Materials, Vol. I, Structure, p. 51. Copyright 1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley & Sons, Inc.]
hexagonal close-
packed (HCP)
c
a
A
B
C
J
E
G
H
F
D
(b) (a)
Figure 3.3 For the hexagonal close-packed crystal structure, (a) a reduced-sphere unit
cell (a and c represent the short and long edge lengths, respectively), and (b) an aggregate
of many atoms. [Figure (b) from W. G. Moffatt, G. W. Pearsall, and J. Wulff, The Structure
and Properties of Materials, Vol. I, Structure, p. 51. Copyright 1964 by John Wiley & Sons,
New York. Reprinted by permission of John Wiley & Sons, Inc.]
Crystal Systems and
Unit Cells for Metals
VMSE
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< -/
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Hexagonal Closed-Packed (hcp) Crystal Structures
!
Cubic geometry
!
Examples: Cr, Fe, W
20
Atoms /Unit cell = 6
Coordination Number:
12
APF: 0,74
13 MSE 2090: Introduction to Materials Science Chapter 3, Structure of solids
Hexagonal Close-Packed Crystal Structure (I)
HCP is one more common structure of metallic crystals
Six atoms form regular hexagon, surrounding one atom
in center. Another plane is situated halfway up unit cell
(c-axis), with 3 additional atoms situated at interstices of
hexagonal (close-packed) planes
Cd, Mg, Zn, Ti have this crystal structure
13 MSE 2090: Introduction to Materials Science Chapter 3, Structure of solids
Hexagonal Close-Packed Crystal Structure (I)
HCP is one more common structure of metallic crystals
Six atoms form regular hexagon, surrounding one atom
in center. Another plane is situated halfway up unit cell
(c-axis), with 3 additional atoms situated at interstices of
hexagonal (close-packed) planes
Cd, Mg, Zn, Ti have this crystal structure
a
c
Ideal c/a = 1,633
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Theoretical Density
21
# = nA
V
C
N
A
Where:
n = number of atoms in each number cell
A = atomic weight
V
C
= volume of the unit cell (a
3
for cubic)
N
A
= Avogadros number (6,022 x 102
3
atoms/mol)
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Theoretical Density, !
22
Chapter 3 - 17
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
!
theoretical

a = 4R/ 3 = 0.2887 nm
!
actual

a
R
! =
a
3
52.00 2
atoms
unit cell
mol
g
unit cell
volume atoms
mol
6.022 x 10
23

Theoretical Density, !
= 7.18 g/cm
3
= 7.19 g/cm
3
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 9e.
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Densities of Different Materials
23
Chapter 3 - 18
Densities of Material Classes
!
metals
>
!
ceramics
>
!
polymers
Why?
Data from Table B.1, Callister & Rethwisch, 9e.
!

(
g
/
c
m


)

3

Graphite/
Ceramics/
Semicond
Metals/
Alloys
Composites/
fibers
Polymers
1
2
2 0
30
B ased on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix). 10
3
4
5
0.3
0.4
0.5
Magnesium
Aluminum
Steels
Titanium
Cu,Ni
Tin, Zinc
Silver, Mo
Tantalum
Gold, W
Platinum
G raphite
Silicon
Glass - soda
Concrete
Si nitride
Diamond
Al oxide
Zirconia
H DPE, PS
PP, LDPE
PC
PTFE
PET
PVC
Silicone
Wood
AFRE *
CFRE *
GFRE*
Glass fibers
Carbon fibers
A ramid fibers
Metals have...
close-packing
(metallic bonding)
often large atomic masses
Ceramics have...
less dense packing
often lighter elements
Polymers have...
low packing density
(often amorphous)
lighter elements (C,H,O)
Composites have...
intermediate values
In general
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Single Crystals
!
Atoms are in a repeating or periodic array over the
entire extent of the material
24

All unit cells present the


same orientation and are
linked in the same way to
each other

Natural or articially
grown

Has a geometric regular


shape
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Polycrystalline material
!
Comprised of many small crystals or grains.
!
Grain sizes between 1nm - 2 cm
!
The grains have different crystallographic orientation.
!
Overall component properties are not directional
!
There exist atomic mismatch within the regions where grains meet. These regions
are called grain boundaries.
25
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Materials Solidification
26
20 MSE 2090: Introduction to Materials Science Chapter 3, Structure of solids
Single Crystals and Polycrystalline Materials
Single crystal: atoms are in a repeating or periodic array
over the entire extent of the material
Polycrystalline material: comprised of many small
crystals or grains. The grains have different
crystallographic orientation. There exist atomic mismatch
within the regions where grains meet. These regions are
called grain boundaries.
Grain Boundary
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Single Crystals vs Polycrystals
27
Single Crystals
Properties vary with direction:
anisotropic
Example: the modulus of
elasticity in BCC iron
Chapter 3 - 21
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Data from Table 3.4,
Callister & Rethwisch 9e.
(Source of data is R.W.
Hertzberg, Deformation and
Fracture Mechanics of
Engineering Materials, 3rd ed.,
John Wiley and Sons, 1989.)
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(E
poly iron
= 210 GPa)
-If grains are textured,
anisotropic.
200 m
Adapted from Fig.
4.15(b), Callister &
Rethwisch 9e.
[Fig. 4.15(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).]
Single vs Polycrystals
E (diagonal) = 273 GPa
E (edge) = 125 GPa
Polycrystals
Properties may/may not vary
with direction
If grains are randomly
oriented: isotropic
If grains are textured:
anisotropic
Chapter 3 - 21
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Data from Table 3.4,
Callister & Rethwisch 9e.
(Source of data is R.W.
Hertzberg, Deformation and
Fracture Mechanics of
Engineering Materials, 3rd ed.,
John Wiley and Sons, 1989.)
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(E
poly iron
= 210 GPa)
-If grains are textured,
anisotropic.
200 m
Adapted from Fig.
4.15(b), Callister &
Rethwisch 9e.
[Fig. 4.15(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).]
Single vs Polycrystals
E (diagonal) = 273 GPa
E (edge) = 125 GPa
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Polymorphism
!
Can be found in any crystalline materials, including metals,
minerals, polymers
!
Relevant to the elds of pharmaceuticals, agrochemicals,
pigments, dyestuffs, foods, and explosives
28

Polymorphism: When a material exist in more than one


crystal structure
quartz
cristobalite
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Allotropy
29

Allotropy: Polymorphisme in an elemental solid


In Carbon
Diamond
Graphite
Fullerenes Carbon Black
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Crystal Systems
30
Unit cell: smallest repetitive volume which contains the complete
lattice pattern of a crystal
Crystals Systems
Classication of crystal structures based on the geometry of the
unit cell, independent of the atomic positions in the cell
Substitution for the various parameters into Equation 3.5 yields
The literature value for the density of copper is 8.94 g/cm
3
, which is in very
close agreement with the foregoing result.
3.6 POLYMORPHISM AND ALLOTROPY
Some metals, as well as nonmetals, may have more than one crystal structure, a phe-
nomenon known as polymorphism. When found in elemental solids, the condition is
often termed allotropy. The prevailing crystal structure depends on both the temper-
ature and the external pressure. One familiar example is found in carbon: graphite is
the stable polymorph at ambient conditions, whereas diamond is formed at extremely
high pressures. Also, pure iron has a BCC crystal structure at room temperature, which
changes to FCC iron at 912C (1674F). Most often a modification of the density and
other physical properties accompanies a polymorphic transformation.
3.7 CRYSTAL SYSTEMS
Because there are many different possible crystal structures, it is sometimes conven-
ient to divide them into groups according to unit cell configurations and/or atomic
arrangements. One such scheme is based on the unit cell geometry, that is, the shape
of the appropriate unit cell parallelepiped without regard to the atomic positions in
the cell. Within this framework, an xyz coordinate system is established with its origin
at one of the unit cell corners; each of the x, y, and z axes coincides with one of the
three parallelepiped edges that extend from this corner, as illustrated in Figure 3.4.
The unit cell geometry is completely defined in terms of six parameters: the three edge
lengths a, b, and c, and the three interaxial angles a, b, and g. These are indicated in
Figure 3.4, and are sometimes termed the lattice parameters of a crystal structure.
On this basis there are seven different possible combinations of a, b, and c, and
a, b, and g, each of which represents a distinct crystal system. These seven crystal
systems are cubic, tetragonal, hexagonal, orthorhombic, rhombohedral,
2
monoclinic,
and triclinic. The lattice parameter relationships and unit cell sketches for each are
8.89 g/cm
3

14 atoms/unit cell 2 163.5 g/mol 2
[161211.28 10
8
cm2
3
/unit cell ] 16.022 10
23
atoms/mol 2
r
nA
Cu
V
C
N
A

nA
Cu
116R
3
122 N
A
52 Chapter 3 / The Structure of Crystalline Solids 52 Chapter 3 / The Structure of Crystalline Solids
polymorphism
allotropy
2
Also called trigonal.
z
y
x
a

b
c

Figure 3.4 A unit cell with x, y, and z coordinate axes,


showing axial lengths (a, b, and c) and interaxial angles
(, , and ).
lattice parameters
crystal system
Crystal Systems and
Unit Cells for Metals
VMSE
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< =>
Unit cell geometry dened by:
The three edge lengths: a, b, c
The three interaxial angles: #, $, %
Lattice Parameters
7 crystal systems
Aula 3 - Crystalline Solids - 31 de marzo de 2014
Crystal Systems
54 Chapter 3 / The Structure of Crystalline Solids
Table 3.2 Lattice Parameter Relationships and Figures Showing Unit Cell
Geometries for the Seven Crystal Systems
Axial
Crystal System Relationships Interaxial Angles Unit Cell Geometry
Cubic
Hexagonal
Tetragonal
Rhombohedral
(Trigonal)
Orthorhombic
Monoclinic
Triclinic a b g 90 a b c
a g 90 b a b c
a b g 90 a b c
a b g 90 a b c
a b g 90 a b c
a b 90, g 120 a b c
a b g 90 a b c
a
b
c

a
b
c

a
b
c
a
a
a

a
a
c
a
a
a
c
a
a
a
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< =-
54 Chapter 3 / The Structure of Crystalline Solids
Table 3.2 Lattice Parameter Relationships and Figures Showing Unit Cell
Geometries for the Seven Crystal Systems
Axial
Crystal System Relationships Interaxial Angles Unit Cell Geometry
Cubic
Hexagonal
Tetragonal
Rhombohedral
(Trigonal)
Orthorhombic
Monoclinic
Triclinic a b g 90 a b c
a g 90 b a b c
a b g 90 a b c
a b g 90 a b c
a b g 90 a b c
a b 90, g 120 a b c
a b g 90 a b c
a
b
c

a
b
c

a
b
c
a
a
a

a
a
c
a
a
a
c
a
a
a
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< =-
54 Chapter 3 / The Structure of Crystalline Solids
Table 3.2 Lattice Parameter Relationships and Figures Showing Unit Cell
Geometries for the Seven Crystal Systems
Axial
Crystal System Relationships Interaxial Angles Unit Cell Geometry
Cubic
Hexagonal
Tetragonal
Rhombohedral
(Trigonal)
Orthorhombic
Monoclinic
Triclinic a b g 90 a b c
a g 90 b a b c
a b g 90 a b c
a b g 90 a b c
a b g 90 a b c
a b 90, g 120 a b c
a b g 90 a b c
a
b
c

a
b
c

a
b
c
a
a
a

a
a
c
a
a
a
c
a
a
a
!"#$%&'()*+,(+--.+&/0123 %%5/5+/ /6,% 78 9:;< =-
Aula 3 - Crystalline Solids - 31 de marzo de 2014

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