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REAL CRYSTALS- IMPERFECTIONS,

ANIZOTROPY AND MATERIALS
ALLOTROPY
COURSE 2
Materials Science
Prof.dr.ing. Brndua GHIBAN
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A. REAL CRISTALS CRYSTALLINE IMPERFECTIONS
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Crystals are like people, have flaws (DEFECTC),
making them more attractive and interesting!
Scheme of a polycrystalline material
with many defects
Real crystals
are never
perfect, they
always
contain
defects !
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These faults (defects) have a significant impact on the
macroscopic properties materials.
Atomic bond
Structure
Defects
PROPERTIES
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MATERIALS PROCESSING MAY DETERMINE
DEFECTS FORMATION
Chemical
composition
Crystalline
structure
Ineratomic
bond
Thermo-
mechanical
processing
Microstructure
Introduction and
directing the defects
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CRYSTALLINE IMPERFECTIONS IN REAL CRYSTALS
From the point of view of its location in the crystal, crystalline
imperfections are classified :
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Point defects
(located at the crystals network nodes);
2
Linear defects
(limitated at chains and ionic lines);
3
Interfacial defects
(formed on surfaces or atomic planes);
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Bulk or volume defects
(concentrated in small volumes).
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1. Point defects
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Vacancy
Interstitial
foreign atom
Interstitial
atom
Foreign substitution
atom
simple
complex
Point defects are characterized by measures of about the size of an
interatomic distance.
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DEFECTS IN IONIC CRISTALS
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Schottky Defect
(the absence of ion pairs)
Frenkel Defect
(cathion in an interstitial space)


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Linear imperfections are strings (lines) of atoms, straight or curved, of limited length that are "deployed" in
the particular ideal crystal, for which they are called dislocations. To explain the formation and location of
dislocations in real crystals resort to a mechanical model based on the possibility that their crystallographic
planes to slide over each other along a slip plane imaginary planes parallel to the plane crystallographic
centers of two neighboring cathions (common tangent plane of the two atomic planes.)
2. Linear Imperfections - Dislocations
8 Building an edge dislocations with Burgers vector perpendicular to the dislocation line.
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Building a screw dislocations with Burgers vector parallel to the
dislocation.
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Dislocations Properties
al interstiti
T
1 1
lattice perfect

1
1
vacance

T
1
1
tion poligoniza

1
1
Have a great mobility, either by sliding or by
climbing, allowing the plastic deformation of
metals,
Have a specific material density, depending on
its condition,
i.e. 10
4
10
5
cm
-2
in semiconductors,
10
6
10
8
cm
-2
in annealed materials, 10
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10
12
cm
-2
in plastic formed materials,
Up to 10
12
cm
-2
for materials during fracture.

Dislocations may interact between them,
Dislocations may be multiply-
mechanism Frank Read Source
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3. Plane Imperfections- Interfacial Defects
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Plane imperfections have a single size of the same order as the interatomic distance,
and the other two higher. They are areas within the body of material separating the
portions that differ in some respect: after the crystalline structure after
crystallographic orientation as the orientation of spontaneous magnetization, etc..
External Surfaces
Grain Boundaries
Twin Boundaries
Stacking faults
Phase Boundaries
Interfacial
defects include
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3.1 EXTERNAL SURFACES
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One of the most obvious boundaries
is the external surface, along which
the crystal structure terminates.
Surface atoms are not bonded to the
maximum number of nearest
positions. The bonds of these surface
atoms that are not satisfied give rise
to a surface energy, expressed in
units of energy per unit area (J/m
2
or
erg/cm
2
). To reduce this energy,
materials tend to minimize, if at all
possible, the total surface area. For
example, liquids assume a shape
having a minimum area, the droplets
become spherical. Of course, this is
not possible with solids which are
mechanically rigid.
Liquid droplet
Metal droplet
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3.2 GRAINS BOUNDARIES
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Represents separations of two small grains or
crystals having different crystallographic orientation
in polycrystalline materials. Various degrees of
crystallographic misalignment between adjacent
grains are possible. When the orientation mismatch is
slight, on the order of a few degrees, then the term
small (or low) angle grain boundary is used.
Schematic diagram showing small and high-angle
grain boundaries and the adjacent atom positions
Demonstration of how a tilt boundary having
an angle of misorientation results from an
alignment of edge dislocations
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3.3 TWIN BOUNDARIES
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Twin boundary is a special type of grain
boundary, across which there is a
specific mirror lattice symmetry; that is,
atoms on one side of the boundary are
located in mirror-image positions of the
atoms on the other side. The region of
materials between these boundaries is
appropriately termed twin. Twins result
from atomic displacements that are
produced from applied mechanical shear
forces (mechanical twins), and also
during annealing heat treatments
following deformation (annealing twins).
Twinning occurs on a definite
crystallographic plane and in a specific
direction, both of which depend on the
crystal structure. Annealing twins are
typically found in metals that have FCC
crystal structure, while mechanical twins
are observed in BCC and HCP metals.
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3.4 PHASE BOUNDARIES
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Incoherent boundary
interface between phases
Coherent boundary interface
between phases
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CLOSE PACKED CRYSTAL STRUCTURES
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Close-packed plane stacking sequence for hexagonal close-packed
The real distinction between FCC and HCP lies in where
the third close-packed layer is positioned. For HCP, the
centers of this layer are aligned directly above the
original A positions. This stacking sequence,
ABABAB, is repeated over and over. Also, ACACAC
arrangement would be equivalent.
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 B positions are arbitrarily chosen; the
stacking sequence is termed AB.
If we note all the atoms of a close packed plane with
A, and the following plane with atom in close packed
situation with B, the remaining depressions are
those with the down vertices, which are marked C.
A portion of a close-packed plane of A, B, and C atoms
The AB stacking sequence for close-packed atomic plane
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3.5 Stacking faults and twining
Stacking faults and twinning in FCC metals.
(100) plane is parallel with (111) twin boundary.
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Stacking faults occur in a number of crystal
structures, but the common example is in close-
packed structures. Face-centered cubic (fcc)
structures differ from hexagonal close packed (hcp)
structures only in stacking order: both structures
have close packed atomic planes with sixfold
symmetrythe atoms form equilateral triangles.
When stacking one of these layers on top of
another, the atoms are not directly on top of one
anotherthe first two layers are identical for hcp
and fcc, and labelled AB. If the third layer is placed
so that its atoms are directly above those of the first
layer, the stacking will be ABAthis is the hcp
structure, and it continues ABABABAB. However,
there is another possible location for the third layer,
such that its atoms are not above the first layer.
Instead, it is the atoms in the fourth layer that are
directly above the first layer. This produces the
stacking ABCABCABC, and is actually a cubic
arrangement of the atoms. A stacking fault is a one
or two layer interruption in the stacking sequence,
for example, if the sequence ABCABABCAB were
found in an fcc structure.
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4. Bulk or volume defects
In real metals may appear imperfections which may be
extended in small or even big volumes, often called defects
of compactity.
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Pores - can greatly affect optical,
thermal, mechanical properties
Cracks - can greatly affect
mechanical properties
Foreign inclusions - can greatly
affect electrical, mechanical, optical
properties.
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Due to the geometric
distribution of atoms
arranged in crystalline
bodies, the matter will
be found unevenly
distributed according to
different directions.
Therefore her behavior
towards physical action
determined to be
different from one
direction to another
The consequences of atomic arrangements

Crystalline bodies are
anisotropic, i.e. the
different properties in
different directions.
Anisotropy
Amorphous bodies are
isotropic, it will deal
physical actions without
any dependence on the
direction considered.
Isotropy
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B. Anisotropy of materials
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Hardness
Diffusion rate
Forjability
Degradation rate in
corrosive media
Electric and thermal
conductivity
Magnetic permeability
Crystals anisotropy throughout the whole elastic and plastic
properties :
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Anisotropic behavior
Generally, the properties of materials are the same in all direction, which is called isotropy. For
example, the electrical conductivity for materials having a cubic lattice structure is completely
isotropic.
Because of differences in atomic arrangement in the planes and direction within a crystal, the
properties may vary with the direction. A material is anisotropic if its properties depend on the
crystallographic directions along with the property is measured.
Anisotropy in natural materials
Wood is a good example of an anisotropic material. In a tree, the cells are arranged
parallel to the trunk (axially). Consequently the strength is different along different
directions (axial, radial). This is because the tree is commonly loaded in the direction of
the trunk e.g. by wind.
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These graphs illustrate the effect of direction on two important mechanical
properties: the Young modulus and the compressive strength. Note that for
dense woods such as oak, the directional effect is less pronounced, whereas
'light' woods such as balsa are extremely anisotropic - the Young modulus is
about 100 times higher in the axial direction than the transverse.
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STRUCTURAL ANISOTROPY OF MAN-MADE COMPOSITES (1)
Ceramic fibres have a higher strength than metals. By combining two phases
(ceramic fibre and metal matrix), a mixture of both properties is obtained.
If the fracture strain of metal and ceramics are of the same magnitude the following
formula holds:

L
= V
f

fb
+ (1 V
f
)
mb

L
=fracture stress in longitudinal direction

fb
=fracture stress of the ceramic fibre

mb
=fracture stress of the metal
V
f
=volume fraction of the ceramic fibres
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STRUCTURAL ANISOTROPY OF MAN-MADE COMPOSITES (2)
If the fibres are not all oriented in the same direction (i.e. short-fibre-reinforced
composites) the properties depend on the distribution of their orientations. If the fibres
are distributed randomly (mean orientation = 45), the composite is isotropic. With
increasing orientation in loading direction the strength increases parallel to the loading
direction but decreases in the transverse direction.
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ANISOTROPY IN ALUMINIUM
Compared to wood and fibre-reinforced composites, aluminium and its alloys tend to possess less
pronounced anisotropic mechanical properties.
Nevertheless, the properties of aluminium are never completely isotropic - some degree of
anisotropy is always present.
This can have very important consequences on both the processing/production of aluminium,
and on the in-service performance of an aluminium structure or component. Sometimes this
anisotropy can be beneficial, at other times problematic.
Anisotropy in the mechanical properties can cause
'earing' in the can body. The ears must be cut off,
leading to wastage.
The following graph shows the anisotropic nature of the Young modulus of a single
crystal of aluminium (as calculated by Nye). As the cube axis is rotated from 0/90 to
45 to the tensile axis, the modulus increases from 63 to 72 GPa, or about 15%.
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ANISOTROPY IN ALUMINUM
STRESS-STRAIN BEHAVIOUR
The stress-strain curve clearly
illustrates the anisotropic nature
of two important mechanical
properties: namely strength (UTS)
and elongation to failure.
The highest strength is obtained
for the sample cut parallel to the
rolling direction, while the curves
for samples cut at 45 and 90 to
the rolling direction are lower and
almost identical.
The anisotropy of the elongation
to failure very pronounced, with
the 45 sample having an
elongation nearly 25% (in relative
terms) greater than the
longitudinal (0) sample.
Uniaxial stress-strain curve for recrystallised alloy 5754-O.
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C. POLYMORPHIC AND ALLOTROPIC MATERIALS
Some materials have different crystal structures at lower temperatures than at higher
temperatures. (The inherent energy of a crystal structure is temperature-dependent.)
Materials that undergo a transformation from one crystal structure to another are
called polymorphic or, when referring to elements, allotropic. A well-known example
is the allotropic transformation of room temperature, ductile, tetragonal, white, -tin to
its low-temperature, brittle, diamond cubic, gray, modification. The transformation
occurs slowly at 286.2 K and causes a 27% expansion and thus a disintegration into
powder (tin plague, tin pest or tin leprosy). As a consequence of this transformation,
old organ pipes made of tin (or tin alloys) may disintegrate in severe winter
temperatures. A similar breakdown has been reported for the tin-based coat buttons
of Napoleons army in a harsh Russian winter. Another example is the temperature-
dependent FCC to BCC allotropic transformation of pure iron at 912C. The prevailing
crystal structure also may depend on the external pressure. As an example, graphite
is stable at ambient conditions whereas diamond is the high pressure modification of
carbon.
Diamond and graphite are
two allotropes of carbon:
pure forms of the same
element that differ in
structure.
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Some allotropes of carbon:
a) diamond;
b) graphite;
c) lonsdaleite;
d) f) fullerenes (C60, C540, C70);
g) amorphous carbon;
h) carbon nanotube.
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EXAMPLES OF ALLOTROPES
elements Allotropes
Carbon
diamond - an extremely hard, transparent crystal, with
the carbon atoms arranged in a tetrahedral lattice. A
poor electrical conductor. An excellent thermal
conductor.
lonsdaleite - also called hexagonal diamond.
graphite - a soft, black, flaky solid, a moderate
electrical conductor. The C atoms are bonded in flat
hexagonal lattices (graphene), which are then layered
in sheets.
amorphous carbon
fullerenes, including "buckyballs", such as C60.
carbon nanotubes - allotropes of carbon with a
cylindrical nanostructure.
Phosphorus
White phosphorus - crystalline solid P4
Red phosphorus - polymeric solid
Scarlet phosphorus
Violet phosphorus
Black phosphorus - semiconductor, analogous to
graphite
Diphosphorus
Oxygen
dioxygen, O2 - colorless
ozone, O3 - blue
tetraoxygen, O4 - metastable
octaoxygen, O8 - red
Nitrogen
dinitrogen
tetranitrogen
trinitrogen
two solid forms: one hexagonal close-packed and the
other alpha cubic
elements Allotropes
Sulfur
Plastic (amorphous) sulfur - polymeric solid
Rhombic sulfur - large crystals composed of S8
molecules
Monoclinic sulfur - fine needle-like crystals
Other ring molecules such as S7 and S12
Selenium
Red selenium," cyclo-Se8
Gray selenium, polymeric Se
Black selenium
Boron
amorphous boron - brown powder
crystalline boron - black, hard (9.3 on Mohs'scale),
and a weak conductor at room temperature.
Germanium
-germanium -
-germanium - at high pressures
Silicon
amorphous silicon - brown powder
crystalline silicon - has a metallic luster and a
grayish color. Single crystals of crystalline silicon
can be grown with a process known as the
Czochralski process
Arsenic
Yellow arsenic - molecular non-metallic As4
Gray arsenic, polymeric As (metalloid)
Black arsenic (metalloid) and several similar other
ones.
Antimony
blue-white antimony - the stable form (metalloid)
yellow antimony (non-metallic)
black antimony (non-metallic)
(a fourth one too)
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EXAMPLES OF METALS WITH ALLOTROPIC PROPERTIES
425
912
885
865
450