Crystal Structures

3.2 Fundamental Concepts

Atoms self-organize in crystals, most of the time. The crystalline lattice, is a periodic
array of the atoms. When the solid is not crystalline, it is called amorphous. Examples
of crystalline solids are metals, diamond and other precious stones, ice, graphite.
Examples of amorphous solids are glass, amorphous carbon (a-C), amorphous Si,
most plastics

To discuss crystalline structures it is useful to consider atoms as being hard spheres,

with well-defined radii. In this scheme, the shortest distance between two like atoms
is one diameter.

3.3 Unit Cells

The unit cell is the smallest structure that repeats itself by translation through the
crystal. We construct these symmetrical units with the hard spheres. The most
common types of unit cells are the faced-centered cubic (FCC), the body-centered
cubic (FCC) and the hexagonal close-packed (HCP). Other types exist, particularly
among minerals. The simple cube (SC) is often used for didactical purpose, no
material has this structure.

3.4 Metallic Crystal Structures

Important properties of the unit cells are

The type of atoms and their radii R.

cell dimensions (side a in cubic cells, side of base a and height c in HCP) in
terms of R.
n, number of atoms per unit cell. For an atom that is shared with m adjacent
unit cells, we only count a fraction of the atom, 1/m.
CN, the coordination number, which is the number of closest neighbors to
which an atom is bonded.
APF, the atomic packing factor, which is the fraction of the volume of the cell
actually occupied by the hard spheres. APF = Sum of atomic volumes/Volume of cell.
 Unit Cell
n CN a/R APF

SC
1 6 2 0.52

BCC
2 8 4 3 0.68

FCC
4 12 2 2 0.74

HCP
6 12 0.74

The closest packed direction in a BCC cell is along the diagonal of the cube; in a FCC
cell is along the diagonal of a face of the cube.

3.5 Density Computations

The density of a solid is that of the unit cell, obtained by dividing the mass of the
atoms (n atoms x Matom) and dividing by Vc the volume of the cell (a3in the case of a
cube). If the mass of the atom is given in amu (A), then we have to divide it by the
Avogadro number to get Matom. Thus, the formula for the density is:

3.6 Polymorphism and Allotropy

Some materials may exist in more than one crystal structure, this is called
polymorphism. If the material is an elemental solid, it is called allotropy. An example
of allotropy is carbon, which can exist as diamond, graphite, and amorphous carbon.

3.7 3.10 Crystallography Not Covered

3.11 Close-Packed Crystal Structures

The FCC and HCP are related, and have the same APF. They are built by packing
spheres on top of each other, in the hollow sites (Fig. 3.12 of book). The packing is
alternate between two types of sites, ABABAB.. in the HCP structure, and alternates
between three types of positions, ABCABC in the FCC crystals.

Crystalline and Non-Crystalline Materials

3.12 Single Crystals

Crystals can be single crystals where the whole solid is one crystal. Then it has a
regular geometric structure with flat faces.

3.13 Polycrystalline Materials

A solid can be composed of many crystalline grains, not aligned with each other. It is
called polycrystalline. The grains can be more or less aligned with respect to each
other. Where they meet is called a grain boundary.

3.14 Anisotropy

Different directions in the crystal have a different packing. For instance, atoms along
the edge FCC crystals are more separated than along the face diagonal. This
causes anisotropy in the properties of crystals; for instance, the deformation depends
on the direction in which a stress is applied.

3.15 X-Ray Diffraction Determination of Crystalline Structure not covered

3.16 Non-Crystalline Solids

In amorphous solids, there is no long-range order. But amorphous does not mean
random, since the distance between atoms cannot be smaller than the size of the hard
spheres. Also, in many cases there is some form of short-range order. For instance, the
tetragonal order of crystalline SiO2 (quartz) is still apparent in amorphous SiO 2 (silica
glass.)

Terms:

Allotropy
Amorphous
Anisotropy
Atomic packing factor (APF)
 Body-centered cubic (BCC)
Coordination number
Crystal structure
Crystalline
Face-centered cubic (FCC)
Grain
Grain boundary
Hexagonal close-packed (HCP)
Isotropic
Lattice parameter
Non-crystalline
Polycrystalline
Polymorphism
Single crystal
Unit cell

Imperfections in Solids
4.1 Introduction

Materials are often stronger when they have defects. The study of defects is divided
according to their dimension:

0D (zero dimension) point defects: vacancies and interstitials. Impurities.

1D linear defects: dislocations (edge, screw, mixed)

2D grain boundaries, surfaces.

3D extended defects: pores, cracks.

 Point Defects
4.2 Vacancies and Self-Interstitials

A vacancy is a lattice position that is vacant because the atom is missing. It is created
when the solid is formed. There are other ways of making a vacancy, but they also
occur naturally as a result of thermal vibrations.

An interstitial is an atom that occupies a place outside the normal lattice position. It
may be the same type of atom as the others (self interstitial) or an impurity atom.

In the case of vacancies and interstitials, there is a change in the coordination of atoms
around the defect. This means that the forces are not balanced in the same way as for
other atoms in the solid, which results in lattice distortion around the defect.

The number of vacancies formed by thermal agitation follows the law:

NV = NA exp(-QV/kT)

where NA is the total number of atoms in the solid, QV is the energy required to form a
vacancy, k is Boltzmann constant, and T the temperature in Kelvin (note, not in oC
or oF).

When QV is given in joules, k = 1.38 10-23 J/atom-K. When using eV as the unit of
energy, k = 8.62 10-5 eV/atom-K.

Note that kT(300 K) = 0.025 eV (room temperature) is much smaller than typical
vacancy formation energies. For instance, QV(Cu) = 0.9 eV/atom. This means that
NV/NA at room temperature is exp(-36) = 2.3 10 -16, an insignificant number. Thus, a
high temperature is needed to have a high thermal concentration of vacancies. Even
so, NV/NA is typically only about 0.0001 at the melting point.

4.3 Impurities in Solids

All real solids are impure. A very high purity material, say 99.9999% pure (called 6N
six nines) contains ~ 6 1016 impurities per cm3.

Impurities are often added to materials to improve the properties. For instance, carbon
added in small amounts to iron makes steel, which is stronger than iron. Boron
impurities added to silicon drastically change its electrical properties.
Solid solutions are made of a host, the solvent or matrix) which dissolves the solute
(minor component). The ability to dissolve is called solubility. Solid solutions are:

homogeneous
maintain crystal structure
contain randomly dispersed impurities (substitutional or interstitial)

Factors for high solubility

Similar atomic size (to within 15%)

Similar crystal structure
Similar electronegativity (otherwise a compound is formed)
Similar valence

Composition can be expressed in weight percent, useful when making the solution,
and in atomic percent, useful when trying to understand the material at the atomic
level.

Miscellaneous Imperfections
4.4 DislocationsLinear Defects

Dislocations are abrupt changes in the regular ordering of atoms, along a line
(dislocation line) in the solid. They occur in high density and are very important in
mechanical properties of material. They are characterized by the Burgers vector, found
by doing a loop around the dislocation line and noticing the extra interatomic spacing
needed to close the loop. The Burgers vector in metals points in a close packed
direction.

Edge dislocations occur when an extra plane is inserted. The dislocation line is at the
end of the plane. In an edge dislocation, the Burgers vector is perpendicular to the
dislocation line.

Screw dislocations result when displacing planes relative to each other through shear.
In this case, the Burgers vector is parallel to the dislocation line.

4.5 Interfacial Defects

The environment of an atom at a surface differs from that of an atom in the bulk, in
that the number of neighbors (coordination) decreases. This introduces unbalanced
forces which result in relaxation (the lattice spacing is decreased)
or reconstruction (the crystal structure changes).

The density of atoms in the region including the grain boundary is smaller than the
bulk value, since void space occurs in the interface.

Surfaces and interfaces are very reactive and it is usual that impurities segregate there.
Since energy is required to form a surface, grains tend to grow in size at the expense
of smaller grains to minimize energy. This occurs by diffusion, which is accelerated at
high temperatures.

Twin boundaries: not covered

4.6 Bulk or Volume Defects

A typical volume defect is porosity, often introduced in the solid during processing. A
common example is snow, which is highly porous ice.

4.7 Atomic Vibrations

Atomic vibrations occur, even at zero temperature (a quantum mechanical effect) and
increase in amplitude with temperature. Vibrations displace transiently atoms from
their regular lattice site, which destroys the perfect periodicity we discussed in
Chapter 3.

Macroscopic Examination
Sections 4.8 to 4-10 were not covered.

Terms:

Alloy
Atom percent
Atomic vibration
Boltzmanns constant
Burgers vector
Composition
Dislocation line
Edge dislocation
Grain size
 Imperfection
Interstitial solid solution
Microstructure
Point defect
Screw dislocation
Self-Interstitial
Solid solution
Solute
Solvent
Substitutional solid solution
Vacancy
Weight percent

5.1 Introduction

Many important reactions and processes in materials occur by the motion of atoms in
the solid (transport), which happens by diffusion.

Inhomogeneous materials can become homogeneous by diffusion, if the temperature

is high enough (temperature is needed to overcome energy barriers to atomic motion.

5.2 Diffusion Mechanisms

Atom diffusion can occur by the motion of vacancies (vacancy diffusion) or

impurities (impurity diffusion). The energy barrier is that due to nearby atoms which
need to move to let the atoms go by. This is more easily achieved when the atoms
vibrate strongly, that is, at high temperatures.

There is a difference between diffusion and net diffusion. In a homogeneous material,

atoms also diffuse but this motion is hard to detect. This is because atoms move
randomly and there will be an equal number of atoms moving in one direction than in
another. In inhomogeneous materials, the effect of diffusion is readily seen by a
change in concentration with time. In this case there is a net diffusion. Net diffusion
occurs because, although all atoms are moving randomly, there are more atoms
moving in regions where their concentration is higher.

5.3 Steady-State Diffusion

The flux of diffusing atoms, J, is expressed either in number of atoms per unit area
and per unit time (e.g., atoms/m2-second) or in terms of mass flux (e.g., kg/m2-
second).
Steady state diffusion means that J does not depend on time. In this case, Ficks first
law holds that the flux along direction x is:

J = D dC/dx

Where dC/dx is the gradient of the concentration C, and D is the diffusion constant.
The concentration gradient is often called the driving force in diffusion (but it is not a
force in the mechanistic sense). The minus sign in the equation means that diffusion is
down the concentration gradient.

5.4 Nonsteady-State Diffusion

This is the case when the diffusion flux depends on time, which means that a type of
atoms accumulates in a region or that it is depleted from a region (which may cause
them to accumulate in another region).

5.5 Factors That Influence Diffusion

As stated above, there is a barrier to diffusion created by neighboring atoms that need
to move to let the diffusing atom pass. Thus, atomic vibrations created by temperature
assist diffusion. Also, smaller atoms diffuse more readily than big ones, and diffusion
is faster in open lattices or in open directions. Similar to the case of vacancy
formation, the effect of temperature in diffusion is given by a Boltzmann factor: D =
D0 exp(Qd/kT).

5.6 Other Diffusion Paths

Diffusion occurs more easily along surfaces, and voids in the material (short circuits
like dislocations and grain boundaries) because less atoms need to move to let the
diffusing atom pass. Short circuits are often unimportant because they constitute a
negligible part of the total area of the material normal to the diffusion flux. .

Terms:

Activation energy
Concentration gradient
Diffusion
Diffusion coefficient
Diffusion flux
Driving force
 Ficks first and second laws
Interdiffusion
Interstitial diffusion
Self-diffusion
Steady-state diffusion
Vacancy diffusion

Mechanical Properties of Metals

1. Introduction

Often materials are subject to forces (loads) when they are used.
Mechanical engineers calculate those forces and material scientists how
materials deform (elongate, compress, twist) or break as a function of
applied load, time, temperature, and other conditions.

Materials scientists learn about these mechanical properties by testing

materials. Results from the tests depend on the size and shape of material
to be tested (specimen), how it is held, and the way of performing the
test. That is why we use common procedures, or standards, which are
published by the ASTM.

2. Concepts of Stress and Strain

To compare specimens of different sizes, the load is calculated per unit

area, also called normalization to the area. Force divided by area is
called stress. In tension and compression tests, the relevant area is that
perpendicular to the force. In shear or torsion tests, the area is
perpendicular to the axis of rotation.

= F/A0 tensile or compressive stress

= F/A0 shear stress

The unit is the Megapascal = 106 Newtons/m2.

There is a change in dimensions, or deformation elongation, L as a

result of a tensile or compressive stress. To enable comparison with
specimens of different length, the elongation is also normalized, this
time to the length L. This is called strain, .

= L/L
 The change in dimensions is the reason we use A0 to indicate the initial
area since it changes during deformation. One could divide force by the
actual area, this is called true stress (see Sec. 6.7).

For torsional or shear stresses, the deformation is the angle of

twist, Fig. 6.1) and the shear strain is given by:

= tg

3. StressStrain Behavior

Elastic deformation. When the stress is removed, the material returns to

the dimension it had before the load was applied. Valid for small strains
(except the case of rubbers).

Deformation is reversible, non permanent

Plastic deformation. When the stress is removed, the material does not
return to its previous dimension but there is a permanent, irreversible
deformation.

In tensile tests, if the deformation is elastic, the stress-strain relationship

is called Hooke's law:

= E

That is, E is the slope of the stress-strain curve. E is Young's

modulus or modulus of elasticity. In some cases, the relationship is not
linear so that E can be defined alternatively as the local slope:

E = d/d

Shear stresses produce strains according to:

= G

where G is the shear modulus.

Elastic moduli measure the stiffness of the material. They are related to
the second derivative of the interatomic potential, or the first derivative
of the force vs. internuclear distance (Fig. 6.6). By examining these
curves we can tell which material has a higher modulus. Due to thermal
 vibrations the elastic modulus decreases with temperature. E is large for
ceramics (stronger ionic bond) and small for polymers (weak covalent
bond). Since the interatomic distances depend on direction in the
crystal, E depends on direction (i.e., it is anisotropic) for single crystals.
For randomly oriented policrystals, E is isotropic.

4. Anelasticity

Here the behavior is elastic but not the stress-strain curve is not
immediately reversible. It takes a while for the strain to return to zero.
The effect is normally small for metals but can be significant for
polymers.

5. Elastic Properties of Materials

Materials subject to tension shrink laterally. Those subject to

compression, bulge. The ratio of lateral and axial strains is called
the Poisson's ratio .

= lateral/ axial

The elastic modulus, shear modulus and Poisson's ratio are related
by E = 2G(1+)

6. Tensile Properties

Yield point. If the stress is too large, the strain deviates from being
proportional to the stress. The point at which this happens is the yield
point because there the material yields, deforming permanently
(plastically).

Yield stress. Hooke's law is not valid beyond the yield point. The stress
at the yield point is called yield stress, and is an important measure of the
mechanical properties of materials. In practice, the yield stress is chosen
as that causing a permanent strain of 0.002 (strain offset, Fig. 6.9.)

The yield stress measures the resistance to plastic deformation.

The reason for plastic deformation, in normal materials, is not that the
atomic bond is stretched beyond repair, but the motion of dislocations,
which involves breaking and reforming bonds.
 Plastic deformation is caused by the motion of dislocations.

Tensile strength. When stress continues in the plastic regime, the stress-
strain passes through a maximum, called the tensile strength (TS) , and
then falls as the material starts to develop a neck and it finally breaks at
the fracture point (Fig. 6.10).

Note that it is called strength, not stress, but the units are the same, MPa.

For structural applications, the yield stress is usually a more important

property than the tensile strength, since once the it is passed, the
structure has deformed beyond acceptable limits.

Ductility. The ability to deform before braking. It is the opposite

of brittleness. Ductility can be given either as percent maximum
elongation max or maximum area reduction.

%EL = max x 100 %

%AR = (A0 - Af)/A0

These are measured after fracture (repositioning the two pieces back
together).

Resilience. Capacity to absorb energy elastically. The energy per unit

volume is the

area under the strain-stress curve in the elastic region.

Toughness. Ability to absorb energy up to fracture. The energy per unit

volume is the total area under the strain-stress curve. It is measured by
an impact test (Ch. 8).

7. True Stress and Strain

When one applies a constant tensile force the material will break after
reaching the tensile strength. The material starts necking (the transverse
area decreases) but the stress cannot increase beyond TS. The ratio of
the force to the initial area, what we normally do, is called the
engineering stress. If the ratio is to the actual area (that changes with
stress) one obtains the true stress.
8. Elastic Recovery During Plastic Deformation

If a material is taken beyond the yield point (it is deformed plastically)

and the stress is then released, the material ends up with a permanent
strain. If the stress is reapplied, the material again responds elastically at
the beginning up to a new yield point that is higher than the original
yield point (strain hardening, Ch. 7.10). The amount of elastic strain that
it will take before reaching the yield point is called elastic strain
recovery (Fig. 6. 16).

9. Compressive, Shear, and Torsional Deformation

Compressive and shear stresses give similar behavior to tensile stresses,

but in the case of compressive stresses there is no maximum in
the curve, since no necking occurs.

10.Hardness

Hardness is the resistance to plastic deformation (e.g., a local dent or

scratch). Thus, it is a measure of plastic deformation, as is the tensile
strength, so they are well correlated. Historically, it was measured on an
empirically scale, determined by the ability of a material to scratch
another, diamond being the hardest and talc the softer. Now we use
standard tests, where a ball, or point is pressed into a material and the
size of the dent is measured. There are a few different hardness tests:
Rockwell, Brinell, Vickers, etc. They are popular because they are easy
and non-destructive (except for the small dent).

11. Variability of Material Properties

Tests do not produce exactly the same result because of variations in the
test equipment, procedures, operator bias, specimen fabrication, etc. But,
even if all those parameters are controlled within strict limits, a variation
remains in the materials, due to uncontrolled variations during
fabrication, non homogenous composition and structure, etc. The
measured mechanical properties will show scatter, which is often
distributed in a Gaussian curve (bell-shaped), that is characterized by the
mean value and the standard deviation (width).

12.Design/Safety Factors
 To take into account variability of properties, designers use, instead of an
average value of, say, the tensile strength, the probability that the yield
strength is above the minimum value tolerable. This leads to the use of
a safety factor N > 1 (typ. 1.2 - 4). Thus, a working value for the tensile
strength would be W =TS / N.

Important Terms:

Anelasticity
Ductility
Elastic deformation
Elastic recovery
Engineering strain
Engineering stress
Hardness
Modulus of elasticity
Plastic deformation
Poissons ratio
Proportional limit
Shear
Tensile strength
Toughness
Yielding
Yield strength

Chapter 8. Failure

1. Introduction

Failure of materials may have huge costs. Causes included improper

materials selection or processing, the improper design of components,
and improper use.

2. Fundamentals of Fracture

Fracture is a form of failure where the material separates in pieces due to stress, at
temperatures below the melting point. The fracture is termed ductile or brittle
depending on whether the elongation is large or small.

Steps in fracture (response to stress):

 track formation
track propagation

Ductile vs. brittle fracture

Ductile Brittle

deformation extensive little

track propagation slow, needs stress fast

type of materials most metals (not too cold) ceramics, ice, cold metals

warning permanent elongation none

strain energy higher lower

fractured surface rough smoother

necking yes no

Ductile Fracture

Stages of ductile fracture

Initial necking

small cavity formation (microvoids)

void growth (elipsoid) by coalescence into a crack

fast crack propagation around neck. Shear strain at 45 o

final shear fracture (cup and cone)

The interior surface is fibrous, irregular, which signify plastic deformation.

Brittle Fracture

There is no appreciable deformation, and crack propagation is very fast. In most

brittle materials, crack propagation (by bond breaking) is along specific
crystallographic planes (cleavage planes). This type of fracture is transgranular
(through grains) producing grainy texture (or faceted texture) when cleavage direction
changes from grain to grain. In some materials, fracture is intergranular.
 5. Principles of Fracture Mechanics

Fracture occurs due to stress concentration at flaws, like surface

scratches, voids, etc. If a is the length of the void and the radius of
curvature, the enhanced stress near the flaw is:

m 2 0 (a/ )1/2

where 0 is the applied macroscopic stress. Note that a is 1/2 the length
of the flaw, not the full length for an internal flaw, but the full length for
a surface flaw. The stress concentration factor is:

Kt = m/0 2 (a/)1/2

Because of this enhancement, flaws with small radius of curvature are

called stress raisers.

6. Impact Fracture Testing

Normalized tests, like the Charpy and Izod tests measure the impact energy required
to fracture a notched specimen with a hammer mounted on a pendulum. The energy is
measured by the change in potential energy (height) of the pendulum. This energy is
called notch toughness.

Ductile to brittle transition occurs in materials when the temperature is dropped

below a transition temperature. Alloying usually increases the ductile-brittle
transition temperature (Fig. 8.19.) For ceramics, this type of transition occurs at much
higher temperatures than for metals.

Fatigue

Fatigue is the catastrophic failure due to dynamic (fluctuating) stresses. It can happen
in bridges, airplanes, machine components, etc. The characteristics are:

long period of cyclic strain

the most usual (90%) of metallic failures (happens also in
ceramics and polymers)
is brittle-like even in ductile metals, with little plastic deformation
 it occurs in stages involving the initiation and propagation of
cracks.

Cyclic Stresses

These are characterized by maximum, minimum and mean stress, the

stress amplitude, and the stress ratio (Fig. 8.20).

The SN Curve

SN curves (stress-number of cycles to failure) are obtained using

apparatus like the one shown in Fig. 8.21. Different types of SN curves
are shown in Fig. 8.22.

Fatigue limit (endurance limit) occurs for some materials (like some
ferrous and Ti allows). In this case, the SN curve becomes horizontal at
large N . This means that there is a maximum stress amplitude (the
fatigue limit) below which the material never fails, no matter how large
the number of cycles is.

For other materials (e.g., non-ferrous) the SN curve continues to fall

with N.

Failure by fatigue shows substantial variability (Fig. 8.23).

Failure at low loads is in the elastic strain regime, requires a large

number of cycles (typ. 104 to 105). At high loads (plastic regime), one
has low-cycle fatigue (N < 104 - 105 cycles).

Crack Initiation and Propagation

Stages is fatigue failure:

I. crack initiation at high stress points (stress raisers)

II. propagation (incremental in each cycle)

III. final failure by fracture

Nfinal = Ninitiation + Npropagation

Stage I - propagation
 slow
along crystallographic planes of high shear stress
flat and featureless fatigue surface

Stage II - propagation

crack propagates by repetive plastic blunting and sharpening of the crack tip. (Fig.
8.25.)

. Crack Propagation Rate (not covered)

. Factors That Affect Fatigue Life

Mean stress (lower fatigue life with increasing mean).

Surface defects (scratches, sharp transitions and edges). Solution:

polish to remove machining flaws

add residual compressive stress (e.g., by shot peening.)
case harden, by carburizing, nitriding (exposing to appropriate gas at
high temperature)

. Environmental Effects

Thermal cycling causes expansion and contraction, hence thermal stress,

if component is restrained. Solution:

o eliminate restraint by design

o use materials with low thermal expansion coefficients.

Corrosion fatigue. Chemical reactions induced pits which act as stress

raisers. Corrosion also enhances crack propagation. Solutions:

o decrease corrosiveness of medium, if possible.

o add protective surface coating.
o add residual compressive stresses.
 Creep

Creep is the time-varying plastic deformation of a material stressed at high

temperatures. Examples: turbine blades, steam generators. Keys are the time
dependence of the strain and the high temperature.

. Generalized Creep Behavior

At a constant stress, the strain increases initially fast with time (primary or transient
deformation), then increases more slowly in the secondary region at a steady rate
(creep rate). Finally the strain increases fast and leads to failure in the tertiary region.
Characteristics:

Creep rate: d/dt

Time to failure.

. Stress and Temperature Effects

Creep becomes more pronounced at higher temperatures (Fig. 8.37).

There is essentially no creep at temperatures below 40% of the melting
point.

Creep increases at higher applied stresses.

The behavior can be characterized by the following expression, where K,

n and Qc are constants for a given material:

d/dt = K n exp(-Qc/RT)

. Data Extrapolation Methods (not covered.)

. Alloys for High-Temperature Use

These are needed for turbines in jet engines, hypersonic airplanes, nuclear reactors,
etc. The important factors are a high melting temperature, a high elastic modulus and
large grain size (the latter is opposite to what is desirable in low-temperature
materials).

Some creep resistant materials are stainless steels, refractory metal alloys (containing
elements of high melting point, like Nb, Mo, W, Ta), and superalloys (based on Co,
Ni, Fe.)
Terms:

Brittle fracture
Charpy test
Corrosion fatigue
Creep
Ductile fracture
Ductile-to-brittle transition
Fatigue
Fatigue life
Fatigue limit
Fatigue strength
Fracture mechanics
Fracture toughness
Impact energy
Intergranular fracture
Izod test
Stress intensity factor
Stress raiser
Thermal fatigue
Transgranular fracture