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Crystal Geometry,
Structure and Defects
Minta Yuwana
2009
Learning Objectives
1. Describe the difference in atomic/molecular structure
between crystalline and noncrystalline materials.
2. Draw unit cells for face-centered cubic, bodycentered
cubic, and hexagonal close-packed crystal structures.
3. Derive the relationships between unit cell edge length
and atomic radius for face-centered cubic and bodycentered cubic crystal structures.
4. Compute the densities for metals having facecentered
cubic and body-centered cubic crystal structures given
their unit cell dimensions.
Learning Objectives
5. Given three direction index integers, sketch the direction
corresponding to these indices within a unit cell.
6. Specify the Miller indices for a plane that has been
drawn within a unit cell.
7. Describe how face-centered cubic and hexagonal closepacked crystal structures may be generated by the
stacking of close-packed planes of atoms.
8. Distinguish between single crystals and polycrystalline
materials.
9. Define isotropy and anisotropy with respect to material
properties.
Crystal
solids which have a regular periodic
arrangement in their component parties,
bounded by flat faces, orderly arranged in
reference to one another, which converge
at the edges and vertices.
Crystal
A crystal is symmetrical about its certain
elements like points, lines or planes
if crystal rotated about these elements, it is not possible to
distinguish its new position from the original position.
Basis
Basis
Basis
Basis
Note:
the number of atoms in a basis may vary from
one to several thousands,
the number of space lattices possible is only
fourteen
one can obtain a large number of crystal structures
from just fourteen space lattices because of the
different types of basis available.
If the basis consists of a single atom only, a mono
atomic crystal structure is obtained.
Copper is an example of mono atomic face-centered cubic
structures.
Examples of complex bases are found in biological materials.
Unit Cell
The smallest repetitive division of crystal
structure.
The smallest component of the space
lattice.
The basic structural unit or building block
of the crystal structure by virtue of its
geometry and atomic positions within.
Unit Cell
Space lattices of various substances differ
in the size and shape of their unit cells.
The distance from one atom to another
atom measured along one of the axis is
called the space constant.
The unit cell is formed by primitives or
intercepts a, b and c along X, Y and Z
axes respectively.
Unit Cell
A unit cell can be completely described by the three
vectors a, b, and c ( OP, OQ and OR) when the length
of the vectors and the angles between them (, , ) are
specified.
The three angles , and are called interfacial angles.
Taking any lattice point as the origin, all other points on
the lattice, can be obtained by a repeated of the lattice
vectors a, b and c.
These lattice vectors and interfacial angles constitute the
lattice parameter of a unit cell.
If the values of these intercepts and interfacial angles
are known, one can easily determine the form and actual
size of the unit cell.
Primitive Cell
Defined as a geometrical shape which, when
repeated indefinitely in 3-dimensions, will fill all
space and is equivalent of one lattice point, i.e.
the unit cell that contains one lattice point only at
the corners.
Note that in some cases the unit cell may coincide
with the primitive cell, but in general the former differs
from the latter in that it is not restricted to being the
equivalent of one lattice point.
Primitive Cell
The units cells, which contain more than
one lattice point are called non-primitive
cells.
The unit cells may be primitive cells, but all
the primitive cells need not to be unit cells.
Crystal Classes
The atoms or molecules or ions in
crystalline state are arranged in a regular,
repetitive and symmetrical pattern,
but the crystal will have the external
symmetrical shape only, if no restraint is
imposed during crystal growth.
Crystal Classes
Crystals possess symmetry
The symmetry of crystals is investigated
by means of symmetry operations,
as a result of which the crystal coincides
with itself in various positions.
Crystal Classes
The simplest of such operations
(rotation, reflection and translationparallel displacement) are associated
with the elements of symmetry.
The simplest elements of symmetry are
the axis and planes of symmetry.
Crystal Classes
The shape of the crystal is said to be
symmetrical if it possesses one or more
elements of symmetry.
A group of symmetry operations,
consisting commonly of a combination of
rotations, reflections and rotations with
reflection, is called a symmetry class.
Crystal Classes
The elements of symmetry are:
(i) The Symmetry Plane
(ii) The Symmetry Axis
(iii) The Centre of Symmetry
Crystal Classes
(i) The Symmetry Plane:
The shape of the crystal is said to be
symmetrical about a plane if it divides
the shape into two identical halves or
into two halves which are mirror images
of one another.
Note that only in an ideal crystal the faces
are of exactly same size.
Crystal Classes
(ii) The Symmetry Axis:
If the shape can be rotated about an axis so
that the shape occupies the same relative
position in space more than once in a
complete revolution, such an axis is called to
be axis of symmetry.
Such axes may be either 2, 3, 4 or 6 fold. The axis
of symmetry causes the crystal to occupy more
than one congruent position during rotation about
that axis during rotation by 360.
Crystal Classes
(iii) The Centre of Symmetry:
Within a crystal, there is some point about
which crystallographically similar faces are
arranged in parallel and corresponding
positions, e.g., the centre of the cube is a
centre of symmetry.
Note that a tetrahedron has no such centre. A
cube has highly symmetrical shape and contains
many planes and axis of symmetry.
Crystal Classes
The principal axes of a cube are four fold,
i.e. during each complete rotation about the
axis, the crystal passes four through identical
positions.
Crystal Classes
A symmetry operation is one that leaves the
crystal and its environment invariant.
Symmetry operations performed
about a point or a line are called point group
symmetry operations
by translations are called space group symmetry
operations.
Crystal Classes
The different point group symmetry
elements that are exhibited by crystals:
(i) centre of symmetry or inversion centre
(ii) reflection symmetry
(iii) rotation symmetry.
Crystal System
If all the atoms at the lattice points are
identical, the lattice is said to be Bravais
lattice.
There are four systems and five possible
Bravais lattices in two dimensions.
Crystal System
The rectangular crystal system has two
Bravais lattices,
rectangular primitive and
rectangular centered.
Crystal System
Crystal System
Based on pure symmetry considerations,
there are only fourteen independent ways
of arranging points in three-dimensional
space,
such that each arrangement is in accordance
or in confirmation with the definition of a
space lattice.
Crystal System
Each space lattice can be defined by
reference to a unit cell which, when
repeated in space an infinite number of
times, will generate the entire space
lattice.
Crystal System
To describe basic crystal structures,
the 14 types of unit cells are grouped in seven
different classes of crystal lattices,
i.e. to describe basic crystal structures, seven
different co-ordinate systems of reference axes are
required.
Crystal System
The number of lattice points in unit cell can be
calculated as:
Contribution of lattice point at the corner = th of the
point
Contribution of the lattice point at the face = of the
point
Contribution of the lattice point at the centre = 1 of the
point
Crystal System
For example, the number of lattice points
per unit cell for
simple cubic (SC) is 1
body centered cubic (BCC) is 2
Face centered cubic (FCC) is 4
Crystal System
Volume of a unit cell can be calculated with the
help of the relation
Atomic Packing Factor (APF):
defined as the ratio of total volume of atoms in a unit
cell to the total volume of the unit cell.
also called relative density of packing (RDP).
METALLIC CRYSTALS
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.
Coordination # = 12
a
Adapted from
Fig. 3.1(a),
Callister 6e.
Crystal System:
Coordination # = 8
R
Adapted from
Fig. 3.2,
Callister 6e.
HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
ABAB... Stacking Sequence
3D Projection
2D Projection
A sites
B sites
A sites
Coordination # = 12
APF = 0.74
Crystal System
Crystal System
Crystal System
Crystal System
Crystallographic Points,
Directions, and Planes
POINT COORDINATES
The position of any point
located within a unit cell
specified in terms of
fractional multiples of the
unit cell edge lengths
(a,b, and c).
POINT COORDINATES
POINT COORDINATES
Solution
From the sketch (a), edge lengths for this unit
cell are:
a = 0.48 nm, b = 0.46 nm, and c = 0.40 nm.
Fractional lengths are: q=1/4, r=1, s=1/2
The location of point:
the x axis (to point N) = *0.48 = 0.12 nm
the y axis (to point O) = 1*0.46 = 0.46 nm
The z axis (to point P) = *0.40 = 0.20 nm
POINT COORDINATES
POINT COORDINATES
CRYSTALLOGRAPHIC DIRECTIONS
Defined as a line between two points, or a
vector.
The steps utilized in the determination of
the three directional indices are:
1. A vector of convenient length is positioned
such that it passes through the origin of the
coordinate system.
Any vector may be translated throughout the
crystal lattice without alteration, if parallelism is
maintained.
CRYSTALLOGRAPHIC DIRECTIONS
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, and c.
CRYSTALLOGRAPHIC DIRECTIONS
CRYSTALLOGRAPHIC DIRECTIONS
CRYSTALLOGRAPHIC DIRECTIONS:
Hexagonal
CRYSTALLOGRAPHIC DIRECTIONS:
Hexagonal
CRYSTALLOGRAPHIC DIRECTIONS:
Hexagonal
CRYSTALLOGRAPHIC DIRECTIONS:
Hexagonal
CRYSTALLOGRAPHIC DIRECTIONS:
Hexagonal
CRYSTALLOGRAPHIC PLANES
The orientations of planes for a crystal
structure are represented in a similar manner.
The unit cell is the basis, with the threeaxis coordinate system.
Except the hexagonal crystal system,
crystallographic planes are specified by three
Miller indices as (hkl).
CRYSTALLOGRAPHIC PLANES
CRYSTALLOGRAPHIC PLANES
2. At this point the crystallographic plane either
intersects or parallels each of the three
axes;
CRYSTALLOGRAPHIC PLANES
3. If necessary, these three numbers are
changed to the set of smallest integers by
multiplication or division by a common
factor.
4. Finally, the integer indices, not separated by
commas, are enclosed within parentheses,
thus: (hkl).
CRYSTALLOGRAPHIC PLANES
An intercept on the negative side of the
origin is indicated by a bar or minus sign
positioned over the appropriate index.
Reversing the directions of all indices
specifies another plane parallel to, on the
opposite side of and equidistant from, the
origin.
CRYSTALLOGRAPHIC PLANES
One interesting and unique characteristic
of cubic crystals is
that planes and directions having the same
indices are perpendicular to one another;
Atomic Arrangements
The atomic arrangement for a crystallographic
plane, depends on the crystal structure.
The (110) atomic planes for FCC and BCC crystal
structures are represented in the next figures;
reduced-sphere unit cells are also included.
Note that the atomic packing is different for each
case.
The circles represent atoms lying in the
crystallographic planes as would be obtained from a
slice taken through the centers of the full-sized hard
spheres.
Atomic Arrangements
A family of planes contains all those
planes that are crystallographically
equivalentthat is, having the same
atomic packing; and a family is designated
by indices that are enclosed in braces
such as {100}.
For example, in cubic crystals the (111),
(111), (111 ), (111 ), (111 ), (111), (111 ), and
(111 ) planes all belong to the {111} family.
Atomic Arrangements
On the other hand, for tetragonal crystal
structures,
the {100} family would contain only the (100), (100),
(010), and (010)
the (001) and (001) planes are not crystallographically
equivalent.
CRYSTALLOGRAPHIC PLANES
Hexagonal Crystals
The MillerBravais system of the fourindex (hkil) scheme is favored.
There is some redundancy in that i is
determined by the sum of h and k through
i = -(h + k)
Otherwise the three h, k, and l indices are
identical for both indexing systems.
CRYSTALLOGRAPHIC PLANES
Linear Density
For example: determine the linear density of the
[110] direction for the FCC crystal structure.
An FCC unit cell (reduced sphere) and the [110]
direction therein are:
Linear Density
Represented in the figure (b) are those five
atoms that lie on the bottom face of this unit
cell; here the [110] direction vector passes
from the center of atom X, through atom Y,
and finally to the center of atom Z.
With regard to the numbers of atoms, it is
necessary to take into account the sharing of
atoms with adjacent unit cells (as discussed in
the atomic packing factor computations).
Linear Density
X
Y
Z
Linear Density
Each of the X and Z corner atoms are also shared
with one other adjacent unit cell along this [110]
direction (i.e., one-half of each of these atoms
belongs to the unit cell being considered), while
atom Y lies entirely within the unit cell.
Planar Density
Planar density (PD) is taken as the
number of atoms per unit area that are
centered on a particular crystallographic
plane, or
Planar Density
For example, consider the section of a
(110) plane within an FCC unit cell.
Planar Density
Although six atoms have centers that lie on
this plane,
only one-quarter of each of atoms A, C,D, and F,
one-half of atoms B and E,
total equivalence of just 2 atoms are on that plane.
CLOSE-PACKED CRYSTAL
STRUCTURES
Face-centered cubic and hexagonal closepacked crystal structures have atomic packing
factors of 0.74,
the most efficient packing of equal-sized spheres or
atoms.
CLOSE-PACKED CRYSTAL
STRUCTURES
CLOSE-PACKED CRYSTAL
STRUCTURES
Both crystal structures may be generated by the
stacking of these close-packed planes on top of
one another;
the difference between the two structures lies in the
stacking sequence.
Let the centers of all the atoms in one closepacked plane be labeled A.
Associated with this plane are two sets of equivalent
triangular depressions formed by three adjacent
atoms, into which the next close-packed plane of
atoms B may rest.
The remaining depressions are those with the down
vertices, which are marked C.
CLOSE-PACKED CRYSTAL
STRUCTURES
A second close-packed plane may be
positioned with the centers of its atoms
over either B or C sites; at this point both
are equivalent.
Suppose that the B positions are arbitrarily
chosen; the stacking sequence is termed AB.
The centers of the third plane are situated
over the C sites of the first plane, This yields
an ABCABCABC . . .
CLOSE-PACKED CRYSTAL
STRUCTURES
20
21
CLOSE-PACKED CRYSTAL
STRUCTURES
The real distinction between FCC and HCP lies
in the position of the third close-packed layer.
For HCP, the centers of this layer are aligned directly
above the original A positions.
This stacking sequence, ABABAB . . . , is repeated
over and over. (the ACACAC . . . is equivalent).
These close-packed planes for HCP are (0001)-type
planes.
The correspondence between this and the unit cell
representation is shown in following figure.
CLOSE-PACKED CRYSTAL
STRUCTURES
--General form:
Stable structures:
--maximize the # of nearest oppositely charged neighbors.
Adapted from Fig. 12.1,
Callister 6e.
15
16
Cation
Al3+
Fe 2+
Fe 3+
Ca 2+
Anion
O 2Cl F-
Answer:
r cation 0.077
r anion
0.140
0.550
based on this ratio,
--coord # = 6
--structure = NaCl
17
AmXp STRUCTURES
Consider CaF2 :
r cation 0.100
0.8
r anion
0.133
18
19
Solid Bodies
Solids exist in nature in two principal
forms:
Crystalline:
Single
Poly
non-crystalline (amorphous)
Crystalline bodies
Remain solid up to a definite temperature
(melting point) at which they change from
the solid to liquid state.
During cooling, the inverse process of
solidification takes place, again at the
definite solidifying temperature, or point.
In both cases, the temperature remains
constant until the material is completely
melted or respectively solidified.
Crystalline bodies
Characterized by an ordered arrangement
of their ions, atoms or molecules.
The properties of crystals depend on
the electronic structure of atoms
the nature of their interactions in the crystal,
the spatial arrangement of their ions, atoms or
molecules,
the composition, size and shape of crystals.
Crystalline bodies
may be either in the form of
single crystal (grain) or
an aggregate of many crystals usually
known as polycrystalline separated by
well-defined grain boundaries.
Crystalline bodies
Polycrystalline material is stronger than
ordinary one
Tiny crystals (grains) have different
orientations with respect to each other and
grain boundaries obstruct the movement of
dislocations.
Amorphous Bodies
Amorphous substances have no crystalline
structure in the condensed state
ordinary glass, sulphur, selenium, glycerin and most
of the high polymers can exist in the amorphous
state.
SINGLE VS POLYCRYSTALS
Single Crystals
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.)
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
200 mm
24
Amorphous Bodies
On repeated heating, long holding at 20-25C or,
in some cases, deformation of an amorphous
body, the instability of the amorphous state may
result in a partial or complete change to the
crystalline state.
Examples of such changes are the turbidity effect
appearing in inorganic glasses on heating or in optical
glasses after a long use, partial crystallization of
molten amber on heating, or additional crystallization
and strengthening of nylon fibers on tension.
crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.
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.
26
GLASS STRUCTURE
Basic Unit:
4Si0 4 tetrahedron
Si 4+
O2-
Glass is amorphous
Amorphous structure
occurs by adding impurities
(Na+,Mg2+,Ca2+, Al3+)
Impurities:
interfere with formation of
crystalline structure.
Quartz is crystalline
SiO2:
(soda glass)
Adapted from Fig. 12.11,
Callister, 6e.
28
Single crystal
No matter how large, is a single grain.
Regular polyhedrons whose shape
depends upon their chemical composition.
Single crystals of metals of many cubic
centimeters in volume are relatively easy to
prepare in the laboratory.
Single crystal
--turbine blades
22
Whiskers
Very thin filaments, hair-like single crystals
of about 13 mm length and perhaps 104
cm diameter.
Produced as dislocations of free crystals
and are without any structural defect.
Far stronger than polycrystals of same
material.
Whiskers
Used as reinforcements in materials to increase
strength by embedding fibers of one material in
a matrix of another.
The properties of fiber or whisker-reinforced
composites can often be tailored for a specific
application.
Whiskers
Whiskers are the most defect-free crystalline
solids available today.
Whiskers can bear considerably high stresses
both at low and relatively elevated temperatures.
The best-known composite are probably, fiber
glass,
consists of glass-reinforcing fibers in a matrix of either
an epoxy polymer or polyester
Whiskers
Whiskers of a wide variety of substances,
e.g., mercury, graphite, sodium and
potassium chlorides, copper, iron, and
aluminium oxide, have been grown from
super saturated media.
Whiskers grown in this way are usually a few
micrometers in diameter and up to a few
inches long.
Some are exceptionally strong, both in bend
tests and in tension tests.
Whiskers
In addition to exceptional strength,
whiskers often have unique electrical,
magnetic, or surface properties.
This behavior can be interpreted to mean that
the crystal structure of whiskers is virtually
perfect, particularly with respect to line
defects.
Actually it appears that some whiskers contain line
defects whereas others do not. However, no
general correlation between whisker properties
and whisker structure have been established.
Polycrystalline
Most crystalline solids
made up of millions of grains
each grain constitutes microstructure
commonly said as polycrystalline.
Grain
a tiny single crystals
oriented randomly with respect to each other
POLYCRYSTALS
Most engineering materials are polycrystals.
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.
23
DENSITY COMPUTATIONS
DENSITY COMPUTATIONS
Symbol
Al
Ar
Ba
Be
B
Br
Cd
Ca
C
Cs
Cl
Cr
Co
Cu
F
Ga
Ge
Au
He
H
At. Weight
(amu)
26.98
39.95
137.33
9.012
10.81
79.90
112.41
40.08
12.011
132.91
35.45
52.00
58.93
63.55
19.00
69.72
72.59
196.97
4.003
1.008
Density
(g/cm 3 )
2.71
-----3.5
1.85
2.34
-----8.65
1.55
2.25
1.87
-----7.19
8.9
8.94
-----5.90
5.32
19.32
-----------
Atomic radius
(nm)
0.143
-----0.217
0.114
Adapted from
-----Table, "Charac-----teristics of
0.149 Selected
0.197 Elements",
inside front
0.071 cover,
0.265 Callister 6e.
-----0.125
0.125
0.128
-----0.122
0.122
0.144
----------12
s polymer s
Why?
Metals have...
close-packing
(metallic bonding)
large atomic mass
Ceramics have...
less dense packing
(covalent bonding)
often lighter elements
Polymers have...
poor packing
(often amorphous)
lighter elements (C,H,O)
Composites have...
intermediate values
13
Measurement of:
Critical angles, qc,
for X-rays provide
atomic spacing, d.
25
XRD pattern
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.
27
Alloy Systems
Phase Diagrams and Phase Transformations
Heat Treatment
Deformation of Materials
Corrosion
Organic Materials:
Polymers and Elastomers
Wood
Composites