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MATERIAL SCIENCE
Aim: At the end of the course the student will have an understanding of mechanics,
physical and chemical properties of materials including metals, ceramics, polymers
and composites and the reasons for these properties to exist.
Lecture Plan
Module Learning Units Hours Total
per topic Hours
1) Introduction 1. Historic perspective and Materials Science 1
2. Why study properties of materials. 1
Classification of materials 3
3. Advanced materials, Future materials and 1
Modern materials
2) Atomic Structure, 4. Atomic Structure and atomic bonding in 1
Interatomic Bonding solids
and Structure of 5. Crystal structures, Crystalline and non- 1
Crystalline Solids crystalline materials
6. Miller indices, Anisotropic elasticity and 1 5
elastic behavior of composites
7. Structure and properties of polymers 1
8. Structure and properties of Ceramics 1
3) Imperfections in 9. Pint defects, theoretical yield point, line 1
Solids defects and dislocations 2
10. Interfacial defects, bulk or volume defects 1
and atomic vibrations
4) Mechanical 11. Elastic deformation and plastic deformation 1
Properties of Metals 12. Interpretation of tensile stress-strain curves 1
13. Yielding under multiaxial stress, Yield 1 3
criteria and macroscopic aspects of plastic
deformation and property variability and
design factors
5) Diffusion 14. Diffusion Mechanisms and steady state and 1
non-steady state diffusion
15. Factors that influence diffusion and non- 1 2
equilibrium transformation and
microstructure
6) Dislocations and 16. Dislocation and plastic deformation and 1
Strengthening mechanisms of strengthening in metals
Mechanisms 17. Recovery, recrystallization and grain growth 1
18. Strengthening by second phase particles, 1 3
optimum distribution of particles and lattice
resistance to dislocation motion
7. Phase Diagrams 19. Equilibrium phase diagrams, Particle 1
strengthening by precipitation and
precipitation reactions
20. Kinetics of nucleation and growth 1 4
21. The iron-carbon system, phase 1
transformations
22. Transformation rate effects and TTT 1
diagrams, Microstructure and property
changes in iron-carbon system
8. Failure 23. Fracture, ductile and brittle fracture 1
24. Fracture mechanics 1
25. Impact fracture, ductile brittle transition 1
Introduction
Historical Perspective
Materials are so important in the development of civilization that we associate ages with
them. In the origin of human life on earth, the Stone Age, people used only natural
materials, like stone, clay, skins, and wood. When people found copper and how to make
it harder by alloying, the Bronze Age started about 3000 BC. The use of iron and steel, a
stronger material that gave advantage in wars started at about 1200 BC. The next big step
was the discovery of a cheap process to make steel around 1850, which enabled the
railroads and the building of the modern infrastructure of the industrial world.
Understanding of how materials behave like they do, and why they differ in properties
was only possible with the atomistic understanding allowed by quantum mechanics, that
first explained atoms and then solids starting in the 1930s. The combination of physics,
chemistry, and the focus on the relationship between the properties of a material and its
microstructure is the domain of Materials Science. The development of this science
allowed designing materials and provided a knowledge base for the engineering
applications (Materials Engineering).
• To be able to select a material for a given use based on considerations of cost and
performance.
• To understand the limits of materials and the change of their properties with use.
• To be able to create a new material that will have some desirable properties.
All engineering disciplines need to know about materials. Even the most "immaterial",
like software or system engineering depend on the development of new materials, which
in turn alter the economics, like software-hardware trade-offs. Increasing applications of
system engineering are in materials manufacturing (industrial engineering) and complex
environmental systems.
Classification of Materials
Like many other things, materials are classified in groups, so that our brain can handle
the complexity. One could classify them according to structure, or properties, or use. The
one that we will use is according to the way the atoms are bound together:
Metals: valence electrons are detached from atoms, and spread in an 'electron sea' that
"glues" the ions together. Metals are usually strong, conduct electricity and heat well and
are opaque to light (shiny if polished). Examples: aluminum, steel, brass, gold.
Semiconductors: the bonding is covalent (electrons are shared between atoms). Their
electrical properties depend extremely strongly on minute proportions of contaminants.
They are opaque to visible light but transparent to the infrared. Examples: Si, Ge, GaAs.
Ceramics: atoms behave mostly like either positive or negative ions, and are bound by
Coulomb forces between them. They are usually combinations of metals or
semiconductors with oxygen, nitrogen or carbon (oxides, nitrides, and carbides).
Examples: glass, porcelain, many minerals.
Polymers: are bound by covalent forces and also by weak van der Waals forces, and
usually based on H, C and other non-metallic elements. They decompose at moderate
temperatures (100 – 400 C), and are lightweight. Other properties vary greatly.
Examples: plastics (nylon, teflon, polyester) and rubber.
Advanced Materials
materials
materials’ needs
Structure
Performance
Properties Processing
Satish V. Kailas ME/MS 4
Properties Of Materials
¾ All solid engineering materials are characterized for their
properties.
¾ Engineering use of a material is reflection of its properties
under conditions of use.
¾ All important properties can be grouped into six categories:
Mechanical, Electrical, Thermal, Magnetic, Optical, and
Deteriorative.
¾ Each material possess a structure, relevant properties, which
dependent on processing and determines the performance.
Atomic Structure:
Atoms are composed of electrons, protons, and neutrons. Electron and protons are
negative and positive charges of the same magnitude, 1.6 × 10-19 Coulombs.
The mass of the electron is negligible with respect to those of the proton and the neutron,
which form the nucleus of the atom. The unit of mass is an atomic mass unit (amu) =
1.66 × 10-27 kg, and equals 1/12 the mass of a carbon atom. The Carbon nucleus has Z=6,
and A=6, where Z is the number of protons, and A the number of neutrons. Neutrons and
protons have very similar masses, roughly equal to 1 amu. A neutral atom has the same
number of electrons and protons, Z.
A mole is the amount of matter that has a mass in grams equal to the atomic mass in amu
of the atoms. Thus, a mole of carbon has a mass of 12 grams. The number of atoms in a
mole is called the Avogadro number, Nav = 6.023 × 1023. Note that Nav = 1 gram/1 amu.
Calculating n, the number of atoms per cm3 in a piece of material of density δ (g/cm3).
n = Nav × δ / M
where M is the atomic mass in amu (grams per mol). Thus, for graphite (carbon) with a
density δ = 1.8 g/cm3, M =12, we get 6 × 1023 atoms/mol × 1.8 g/cm3 / 12 g/mol) = 9 ×
1022 C/cm3.
For a molecular solid like ice, one uses the molecular mass, M(H2O) = 18. With a density
of 1 g/cm3, one obtains n = 3.3 × 1022 H2O/cm3. Note that since the water molecule
contains 3 atoms, this is equivalent to 9.9 × 1022 atoms/cm3.
Most solids have atomic densities around 6 × 1022 atoms/cm3. The cube root of that
number gives the number of atoms per centimeter, about 39 million. The mean distance
between atoms is the inverse of that, or 0.25 nm. This is an important number that gives
the scale of atomic structures in solids.
Ionic Bonding
This is the bond when one of the atoms is negative (has an extra electron) and another is
positive (has lost an electron). Then there is a strong, direct Coulomb attraction. An
example is NaCl. In the molecule, there are more electrons around Cl, forming Cl- and
less around Na, forming Na+. Ionic bonds are the strongest bonds. In real solids, ionic
bonding is usually combined with covalent bonding.
Covalent Bonding
In covalent bonding, electrons are shared between the molecules, to saturate the valency.
The simplest example is the H2 molecule, where the electrons spend more time in
between the nuclei than outside, thus producing bonding.
Metallic Bonding
In metals, the atoms are ionized, loosing some electrons from the valence band. Those
electrons form an electron sea, which binds the charged nuclei in place, in a similar way
that the electrons in between the H atoms in the H2 molecule bind the protons.
Since the electrons may be on one side of the atom or the other, a dipole is formed: the +
nucleus at the center, and the electron outside. Since the electron moves, the dipole
fluctuates. This fluctuation in atom A produces a fluctuating electric field that is felt by
the electrons of an adjacent atom, B. Atom B then polarizes so that its outer electrons are
on the side of the atom closest to the + side (or opposite to the – side) of the dipole in A.
This bond is called van der Waals bonding.
A polar molecule like H2O (Hs are partially +, O is partially – ), will induce a dipole in a
nearby atom, leading to bonding.
This is the case of the hydrogen bond in ice. The H end of the molecule is positively
charged and can bond to the negative side of another dipolar molecule, like the O side of
the H2O dipole
Crystal Structures:
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.
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
Single Crystals
Crystals can be single crystals where the whole solid is one crystal. Then it has a regular
geometric structure with flat faces.
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.
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 SiO2 (silica glass.)
Miller Indices:
Rules for Miller Indices:
• Determine the intercepts of the face along the crystallographic axes, in terms of
unit cell dimensions.
• Take the reciprocals
• Clear fractions
• Reduce to lowest terms
For example, if the x-, y-, and z- intercepts are 2, 1, and 3, the Miller indices are
calculated as:
Thus, the Miller indices are 3,6,2. If a plane is parallel to an axis, its intercept is at
infinity and its Miller index is zero. A generic Miller index is denoted by (hkl).
If a plane has negative intercept, the negative number is denoted by a bar above the
number. Never alter negative numbers. For example, do not divide -1, -1, -1 by -1 to get
1,1,1. This implies symmetry that the crystal may not have!
Anisotropy
Different directions in the crystal have 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.
The idea is that by combining two or more distinct materials one can engineer a new
material with the desired combination of properties (e.g., light, strong, corrosion
resistant). The idea that a better combination of properties can be achieved is called the
principle of combined action.
A type of composite that has been discussed is perlitic steel, which combines hard, brittle
cementite with soft, ductile ferrite to get a superior material.
• matrix (continuous)
• dispersed phase (particulates, fibers)
• Properties of phases
• Geometry of dispersed phase (particle size, distribution, orientation)
• Amount of phase
In many applications, like in aircraft parts, there is a need for high strength per unit
weight (specific strength). This can be achieved by composites consisting of a low-
density (and soft) matrix reinforced with stiff fibers.
The strength depends on the fiber length and its orientation with respect to the stress
direction.
The efficiency of load transfer between matrix and fiber depends on the interfacial bond.
Polymers are common in nature, in the form of wood, rubber, cotton, leather, wood, silk,
proteins, enzymes, starches, cellulose. Artificial polymers are made mostly from oil.
Their use has grown exponentially, especially after WW2. The key factor is the very low
production cost and useful properties (e.g., combination of transparency and flexibility,
long elongation).
Hydrocarbon Molecules
Most polymers are organic, and formed from hydrocarbon molecules. These molecules
can have single, double, or triple carbon bonds. A saturated hydrocarbon is one where
all bonds are single, that is, the number of atoms is maximum (or saturated). Among this
type are the paraffin compounds, CnH2n+2 (Table 15.1). In contrast, non-saturated
hydrocarbons contain some double and triple bonds.
Isomers are molecules that contain the same molecules but in a different arrangement.
An example is butane and isobutane.
Polymer molecules are huge, macromolecules that have internal covalent bonds. For most
polymers, these molecules form very long chains. The backbone is a string of carbon
atoms, often single bonded.
Polymers are composed of basic structures called mer units. A molecule with just one
mer is a monomer.
When all the mers are the same, the molecule is called a homopolymer. When there is
more than one type of mer present, the molecule is a copolymer.
Molecular Weight
The mass of a polymer is not fixed, but is distributed around a mean value, since polymer
molecules have different lengths. The average molecular weight can be obtained by
averaging the masses with the fraction of times they appear (number-average) or with the
mass fraction of the molecules (called, improperly, a weight fraction).
The degree of polymerization is the average number of mer units, and is obtained by
dividing the average mass of the polymer by the mass of a mer unit.
Polymers of low mass are liquid or gases, those of very high mass (called high-polymers,
are solid). Waxes, paraffins and resins have intermediate masses.
Molecular Shape
Polymers are usually not linear; bending and rotations can occur around single C-C bonds
(double and triple bonds are very rigid) (Fig. 15.5). Random kings and coils lead to
entanglement, like in the spaghetti structure shown in Fig. 15.6.
Molecular Structure
Molecular Configurations
The regularity and symmetry of the side-groups can affect strongly the properties of
polymers. Side groups are atoms or molecules with free bonds, called free-radicals, like
H, O, methyl, etc.
If the radicals are linked in the same order, the configuration is called isostatic
Copolymers
Copolymers, polymers with at least two different types of mers can differ in the way the
mers are arranged. Fig. 15.9 shows different arrangements: random, alternating, block,
and graft.
Polymer Crystallinity
Crystallinity in polymers is more complex than in metals (fig. 15.10). Polymer molecules
are often partially crystalline (semicrystalline), with crystalline regions dispersed within
amorphous material. .
Crystalline polymers are denser than amorphous polymers, so the degree of crystallinity
can be obtained from the measurement of density.
Polymer Crystals
Ceramics are inorganic and non-metallic materials that are commonly electrical and
thermal insulators, brittle and composed of more than one element (e.g., two in Al2O3)
Ceramic Structures
Ceramic bonds are mixed, ionic and covalent, with a proportion that depends on the
particular ceramics. The ionic character is given by the difference of electronegativity
between the cations (+) and anions (-). Covalent bonds involve sharing of valence
electrons. Very ionic crystals usually involve cations which are alkalis or alkaline-earths
(first two columns of the periodic table) and oxygen or halogens as anions.
• maintain neutrality
• charge balance dictates chemical formula
• achieve closest packing
the condition for minimum energy implies maximum attraction and minimum repulsion.
This leads to contact, configurations where anions have the highest number of cation
neighbors and viceversa.
Silicate Ceramics
Oxygen and Silicon are the most abundant elements in Earth’s crust. Their combination
(silicates) occur in rocks, soils, clays and sand. The bond is weekly ionic, with Si4+ as the
cation and O2- as the anion. rSi = 0.04 nm, rO.= 0.14 nm, so rC/rA = 0.286.
The tetrahedron is charged: Si4+ + 4 O2- ⇒ (Si O4)4-. Silicates differ on how the
tetrahedra are arranged. In silica, (SiO2), every oxygen atom is shared by adjacent
tetrahedra. Silica can be crystalline (e.g., quartz) or amorphous, as in glass.
Soda glasses melt at lower temperature than amorphous SiO2 because the addition of
Na2O (soda) breaks the tetrahedral network. A lower melting point makes it easy to form
glass to make, for instance, bottles.
Carbon
Carbon is not really a ceramic, but an allotropic form, diamond, may be thought as a type
of ceramic. Diamond has very interesting and even unusual properties:
Graphite has a layered structure with very strong hexagonal bonding within the planar
layers (using 3 of the 3 bonding electrons) and weak, van der Waals bonding between
layers using the fourth electron. This leads to easy interplanar cleavage and applications
as a lubricant and for writing (pencils). Graphite is a good electrical conductor and
chemically stable even at high temperatures. Applications include furnaces, rocket
nozzles, electrodes in batteries.
A recently (1985) discovered formed of carbon is the C60 molecule, also known as
fullerene or bucky-ball (after the architect Buckminster Fuller who designed the geodesic
structure that C60 resembles.) Fullerenes and related structures like bucky-onions amd
nanotubes are exceptionally strong. Future applications are as a structural material and
possibly in microelectronics, due to the unusual properties that result when fullerenes are
doped with other atoms.
Imperfections in Ceramics
Imperfections include point defects and impurities. Their formation is strongly affected
by the condition of charge neutrality (creation of unbalanced charges requires the
expenditure of a large amount of energy.
Charge neutral defects include the Frenkel and Schottky defects. A Frenkel-defect is a
vacancy- interstitial pair of cations (placing large anions in an interstitial position requires
a lot of energy in lattice distortion). A Schottky-defect is the a pair of nearby cation and
anion vacancies.
Introduction of impurity atoms in the lattice is likely in conditions where the charge is
maintained. This is the case of electronegative impurities that substitute a lattice anions
or electropositive substitutional impurities. This is more likely for similar ionic radii
since this minimizes the energy required for lattice distortion. Defects will appear if the
charge of the impurities is not balanced.
The brittle fracture of ceramics limits applications. It occurs due to the unavoidable
presence of microscopic flaws (micro-cracks, internal pores, and atmospheric
contaminants) that result during cooling from the melt. The flaws need to crack
formation, and crack propagation (perpendicular to the applied stress) is usually
transgranular, along cleavage planes. The flaws cannot be closely controlled in
manufacturing; this leads to a large variability (scatter) in the fracture strength of ceramic
materials.
The compressive strength is typically ten times the tensile strength. This makes ceramics
good structural materials under compression (e.g., bricks in houses, stone blocks in the
pyramids), but not in conditions of tensile stress, such as under flexure.
Non-crystalline ceramics, like common glass deform by viscous flow (like very high-
density liquids). Viscosity decreases strongly with increases temperature.
of Composites
Atomic bonding
Primary bonding
Secondary bonding
ionic covalent metallic
Fluctuating Polar
permanent
induced induced
Satish V. Kailas ME/MS 7
Primary Inter-Atomic Bonds
It is characterized by:
¾ Type of atom and their radii, R
¾ Cell dimensions, a and c (for hexagonal structures)
¾ Number of atoms per unit cell, n
¾ Coordination number (CN)– closest neighbors to an atom
¾ Atomic packing factor, APF
Most common unit cells – Face-centered cubic, Body-
centered cubic and Hexagonal.
oxygen/halogens.
Coordination
2 3 4 6 8 12
number
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.
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.
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.
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.
Other defects exist in all solid materials that are much larger than those heretofore
discussed. A typical volume defect is porosity, often introduced in the solid during
processing. A common example is snow, which is highly porous ice.
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 .In a sense, these atomic
vibrations may be thought of as imperfections or defects. At room temperature, a typical
vibrational frequency of atoms is of the order of 10^13 vibrations per second, whereas the
amplitude is a few thousandths of a nanometer.
Module-3
Imperfections in Solids
or Dislocations
vibrations
2Π x 2Π x Gx
τ = τ m sin τ ≈τm τ = Gγ =
b b a
(Hooke’s law)
G ≈ 20-150 GPa G b
τm =
Shear strength ≈ 3-30 GPa 2Π a
(ideal) If b≈a
G
Real strength values ≈ 0.5-10 MPa τm =
2Π
Satish V. Kailas ME/MS 4
Theoretical Yield Strength - 3
¾ Theoretical strength of solids shall possess an ideal value
in the range of 3-30 GPa.
¾ Real values observed in practice are 0.5-10 MPa.
¾ The assumption of perfectly arranged atoms in a solid
may not valid…..i.e. atomic order must have been
disturbed.
¾ Disordered atomic region is called defect or imperfection.
¾ Based on geometry, defects are: Point defects (zero-D),
Line defects (1-D) or Dislocations, Interfacial defects (2-
D) and Bulk or Volume defects (3-D).
Satish V. Kailas ME/MS 5
Point Defects - 1
¾ Point defects are of zero-dimensional i.e. atomic disorder
is restricted to point-like regions.
¾ Thermodynamically stable compared with other kind of
defects.
A negative
dislocation
Grain boundaries
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).
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:
σ=Eε
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 = dσ/dε
τ=Gγ
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.
grains. Before deformation the grains are equiaxed, or have approximately the same
dimension in all directions. For this particular deformation, the grains become elongated
along the directions. For this particular deformation, the grains become elongated along
the direction in which the specimen was extended.
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. Thus, a working value for
the tensile strength would be σW = σTS / N.
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
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.
Tensile strength. When stress continues in the plastic regime, the stress-strain passes
through a maximum, called the tensile strength (σTS) , and then falls as the material starts
to develop a neck and it finally breaks at the fracture point .
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 εmax or maximum area reduction.
These are measured after fracture (repositioning the two pieces back together).
Resilience. Capacity to absorb energy elastically. The energy per unit volume is the
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 .
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 σTS. 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.
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. Thus, a working value for
the tensile strength would be σW = σTS / N.
External load
Object
True strain:
L1 − L0 L2 − L1 L3 − L2 L
dL L
ε =∑ + + + ... ε=∫ = ln
L0 L1 L2 L0
L L0
True stress:
P P A0
σ= = = s (e + 1)
A A0 A
σ ∝ε σ = Eε
¾ Non-linear stress-strain relation is applicable for
materials. E.g.: rubber.
Secant module
represents the slope of
secant drawn from the
origin to some given
point of the σ-ε curve.
σ = σ o + Kε n
Yield strength – σ0
Satish V. Kailas ME/MS 14
Tensile Stress-Strain Curve - 1
s + su 2
U t ≈ su e f ≈ 0 ef area AEFI U t ≈ su e f (for brittle
2 3 materials)
Satish V. Kailas ME/MS 17
Yielding Under Multi-Axial Stress
With on-set of necking, uni-axial stress condition turns
into tri-axial stress as geometry changes tales place. Thus
flow curve need to be corrected from a point
corresponding to tensile strength. Correction has been
proposed by Bridgman.
(σ x ) avg
σ=
(1 + 2 R / a)[ln(1 + a / 2 R)]
where
(σx)avg measured stress in the axial direction,
a – smallest radius in the neck region,
R – radius of the curvature of neck
Satish V. Kailas ME/MS 18
Yield Criteria - 1
Von Mises or Distortion energy criterion:
yielding occurs once second invariant of stress deviator
(J2) reaches a critical value. In other terms, yield starts
once the distortion energy reaches a critical value.
J2 = k 2 J2 =
1
6
[
(σ 1 − σ 2 ) 2 + (σ 2 − σ 3 ) 2 + (σ 3 − σ 1 ) 2 ]
Under uni-axial tension, σ1 = σ0, and σ2= σ3= 0
1 2
(σ 0 + σ 02 ) = k 2 ⇒ σ 0 = 3k
6
⇒σ0 =
1
[
(σ 1 − σ 2 ) 2 + (σ 2 − σ 3 ) 2 + (σ 3 − σ 1 ) 2 ]
1
2
1
k= σ 0 = 0.577σ 0 where k – yield stress under shear
3
Satish V. Kailas ME/MS 19
Yield Criteria - 2
Tresca or Maximum shear stress criterion
yielding occurs once the maximum shear stress of the
stress system equals shear stress under uni-axial stress.
σ1 − σ 3
τ max =
2
σw = σy / N σd = N’σc
where σw – working stress
σy – yield strength
σd – design stress
σc – calculated stress
Satish V. Kailas ME/MS 24
Design Consideration - 2
¾ Values for N ranges around: 1.2 to 4.0.
¾ Higher the value of N, lesser will the design efficiency i.e.
either too much material or a material having a higher
than necessary strength will be used.
¾ Selection of N will depend on a number of factors:
Economics.
Previous experience
The accuracy with which mechanical forces
Material properties
The consequences of failure in terms of loss of life or
property damage.
Chapter 5. Diffusion
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.
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, Fick’s 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.
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).
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).
Non-equilibrium solidification
Non-equilibrium cooling
Diffusion
Contents
dc 1 dn
J x =− D = J x ≠ f ( x, t )
dx A dt
where D is the diffusion constant, dc/dx is the gradient of
the concentration c, dn/dt is the number atoms crossing per
unit time a cross-sectional plane of area A.
E.g.: Hydrogen gas purification using palladium metal
sheet.
Satish V. Kailas ME/MS 9
Non-Steady-State Diffusion 1
Most interesting industrial applications are non-steady-state
diffusion in nature.
Non-steady-state diffusion is characterized by Fick’s second
law, which can be expressed as
dc dJ d ⎛ dc ⎞ d 2c
=− = ⎜D ⎟ dc
=D 2
dt dx dx ⎝ dx ⎠ dt dx
where dc/dt is the time rate of change of concentration at a
particular position, x.
A meaningful solution can be obtained for the above
second-order partial equation if proper boundary conditions
can be defined.
⎛ Q ⎞
D = D0 exp⎜ − ⎟
⎝ RT ⎠
Dislocations can be edge dislocations, screw dislocations and exist in combination of the
two. Their motion (slip) occurs by sequential bond breaking and bond reforming . The
number of dislocations per unit volume is the dislocation density, in a plane they are
measured per unit area.
Characteristics of Dislocations
There is strain around a dislocation which influences how they interact with other
dislocations, impurities, etc. There is compression near the extra plane (higher atomic
density) and tension following the dislocation line.
Dislocations interact among themselves. When they are in the same plane, they repel if
they have the same sign and annihilate if they have opposite signs (leaving behind a
perfect crystal). In general, when dislocations are close and their strain fields add to a
larger value, they repel, because being close increases the potential energy (it takes
energy to strain a region of the material).
Plastic Deformation
Slip directions vary from crystal to crystal. When plastic deformation occurs in a grain, it
will be constrained by its neighbors, which may be less favorably oriented. As a result,
polycrystalline metals are stronger than single crystals (the exception is the perfect
single crystal, as in whiskers.)
This is based on the fact that it is difficult for a dislocation to pass into another grain,
especially if it is very misaligned. Atomic disorder at the boundary causes discontinuity
in slip planes. For high-angle grain boundaries, stress at end of slip plane may trigger
new dislocations in adjacent grains. Small angle grain boundaries are not effective in
blocking dislocations.
The finer the grains, the larger the area of grain boundaries that impedes dislocation
motion. Grain-size reduction usually improves toughness as well. Usually, the yield
strength varies with grain size d according to:
σy = σ0 + ky / d1/2
Grain size can be controlled by the rate of solidification and by plastic deformation.
Solid-Solution Strengthening
Adding another element that goes into interstitial or substitutional positions in a solution
increases strength. The impurity atoms cause lattice strain (Figs. 7.17 and 7.18) which
can "anchor" dislocations. This occurs when the strain caused by the alloying element
compensates that of the dislocation, thus achieving a state of low potential energy. It
costs strain energy for the dislocation to move away from this state (which is like a
potential well). The scarcity of energy at low temperatures is why slip is hindered.
Strain Hardening
Ductile metals become stronger when they are deformed plastically at temperatures well
below the melting point (cold working). (This is different from hot working is the
shaping of materials at high temperatures where large deformation is possible.) Strain
hardening (work hardening) is the reason for the elastic recovery discussed in Ch. 6.8.
The reason for strain hardening is that the dislocation density increases with plastic
deformation (cold work) due to multiplication. The average distance between dislocations
then decreases and dislocations start blocking the motion of each one.
The measure of strain hardening is the percent cold work (%CW), given by the relative
reduction of the original area, A0 to the final value Ad :
Plastic deformation causes 1) change in grain size, 2) strain hardening, 3) increase in the
dislocation density. Restoration to the state before cold-work is done by heating through
two processes: recovery and recrystallization. These may be followed by grain growth.
Recovery
Recrystallization
Strained grains of cold-worked metal are replaced, upon heating, by more regularly-
spaced grains. This occurs through short-range diffusion enabled by the high temperature.
Since recrystallization occurs by diffusion, the important parameters are both temperature
and time.
Grain Growth
The growth of grain size with temperature can occur in all polycrystalline
materials. It occurs by migration of atoms at grain boundaries by
diffusion, thus grain growth is faster at higher temperatures. The "driving
force" is the reduction of energy, which is proportional to the total area.
Big grains grow at the expense of the small ones.
P cos λ P
τR = = cos φ cos λ = σ cos φ cos λ
A cos φ A
⇒ m = cos φ cos λ
in multi-phase materials
- Precipitation strengthening
- Dispersion strengthening
- Fiber strengthening
- Martensite strengthening
Satish V. Kailas ME/MS 11
Strengthening By Grain Size Reduction
1
¾ It is based on the fact that dislocations will experience
hindrances while trying to move from a grain into the next
because of abrupt change in orientation of planes.
¾ Hindrances can be two types: forcible change of slip
direction, and discontinuous slip plane.
¾ Smaller the grain size, often a dislocation encounters a
hindrance. Yield strength of material will be increased.
¾ Yield strength is related to grain size (diameter, d) as Hall-
Petch relation:
σ y = σ i + kd −1 2
It characterizes that
material needs higher
stress to initiate plastic
flow than to continue it.
τ = Gb λ
4(1 − f )r
¾ Interspacing (λ) of spherical particles: λ=
where r - particle radius, f - volume fraction 3f
This very simple case is one complete liquid and solid solubility, an isomorphous
system. The example is the Cu-Ni alloy of Fig. 9.2a. The complete solubility
occurs because both Cu and Ni have the same crystal structure (FCC), near the
same radii, electronegativity and valence.
The liquidus line separates the liquid phase from solid or solid + liquid phases.
That is, the solution is liquid above the liquidus line.
The solidus line is that below which the solution is completely solid (does not
contain a liquid phase.)
a) Equilibrium cooling
Solidification in the solid + liquid phase occurs gradually upon cooling from the
liquidus line. The composition of the solid and the liquid change gradually during
cooling (as can be determined by the tie-line method.) Nuclei of the solid phase
form and they grow to consume all the liquid at the solidus line.
b) Non-equilibrium cooling
Solidification in the solid + liquid phase also occurs gradually. The composition
of the liquid phase evolves by diffusion, following the equilibrium values that can
be derived from the tie-line method. However, diffusion in the solid state is very
slow. Hence, the new layers that solidify on top of the grains have the equilibrium
composition at that temperature but once they are solid their composition does not
change. This lead to the formation of layered (cored) grains (Fig. 9.14) and to the
invalidity of the tie-line method to determine the composition of the solid phase
(it still works for the liquid phase, where diffusion is fast.)
Eutectic or invariant point. Liquid and two solid phases exist in equilibrium at the
eutectic composition and the eutectic temperature.
Note:
• the melting point of the eutectic alloy is lower than that of the
components (eutectic = easy to melt in Greek).
A terminal phase or terminal solution is one that exists in the extremes of concentration
(0 and 100%) of the phase diagram. One that exists in the middle, separated from the
extremes, is called an intermediate phase or solid solution.
The eutectoid (eutectic-like) reaction is similar to the eutectic reaction but occurs from
one solid phase to two new solid phases. It also shows as V on top of a horizontal line in
the phase diagram. There are associated eutectoid temperature (or temperature), eutectoid
phase, eutectoid and proeutectoid microstructures.
The peritectic reaction also involves three solid in equilibrium, the transition is from a
solid + liquid phase to a different solid phase when cooling. The inverse reaction occurs
when heating.
The strength and hardness of some metal and alloys may be enhanced by the formation of
extremely small uniformly dispersed particles of a second phase within the original phase
matrix; this must be accomplished by phase transformations that are induced by
appropriate heat treatments. The process is called precipitation hardening because the
small particles of the new phase are termed “precipitates”. Precipitation hardening and
the treating of steel to form tempered matrensite are totally different phenomena, even
though the heat treatment procedures are similar.
A precipitation reaction is a reaction in which soluble ions in separate solutions are mixed
together to form an insoluble compound that settles out of solution as a solid. That
insoluble compound is called a precipitate
From a micro structural standpoint, the first process to accompany a phase transformation
is nucleation- the formation of very small particles or nuclei, of the new phase which are
capable of growing. The second stage is growth, in which the nuclei increase in size;
during this process, some volume of the parent phase disappears. The transformation
reaches completion if growth of these new phase particles is allowed to proceed until the
equilibrium fraction is attained.
As would be expected, the time dependence of the transformations rate (which is often
termed the kinetics of a transformation) is an important consideration in the heat
treatment of materials. With many investigations, the fraction of reaction that has
occurred is measured as a function of time, while the temperature is maintained constant.
Transformation progress is usually ascertained by either microscopic examination or
measurement of some physical property. Data are plotted as the fraction of transformed
material versus the logarithm of time; an S-shaped curve, represents the typical kinetic
behavior for most solid state reactions.
This is one of the most important alloys for structural applications. The
diagram Fe—C is simplified at low carbon concentrations by assuming it
is the Fe—Fe3C diagram. Concentrations are usually given in weight
percent. The possible phases are:
For their role in mechanical properties of the alloy, it is important to note that:
Thus, combining these two phases in solution an alloy can be obtained with
intermediate properties. (Mechanical properties also depend on the
microstructure, that is, how ferrite and cementite are mixed.)
Since reactions below the eutectoid temperature are in the solid phase, the equilibrium is
not achieved by usual cooling from austenite. The new microstructures that form are
discussed in Ch. 10.
There are two main types of transformation diagram that are helpful in selecting the
optimum steel and processing route to achieve a given set of properties. These are time-
temperature transformation (TTT) and continuous cooling transformation (CCT)
diagrams. CCT diagrams are generally more appropriate for engineering applications as
components are cooled (air cooled, furnace cooled, quenched etc.) from a processing
temperature as this is more economic than transferring to a separate furnace for an
isothermal treatment.
Time-temperature transformation (TTT) diagrams measure the rate of transformation
at a constant temperature. In other words a sample is austenitised and then cooled rapidly
to a lower temperature and held at that temperature whilst the rate of transformation is
measured, for example by dilatometry. Obviously a large number of experiments is
required to build up a complete TTT diagram.
Continuous cooling transformation (CCT) diagrams measure the extent of
transformation as a function of time for a continuously decreasing temperature. In other
words a sample is austenitised and then cooled at a predetermined rate and the degree of
transformation is measured, for example by dilatometry. Obviously a large number of
experiments is required to build up a complete CCT diagram
• An increase in carbon content shifts the CCT and TTT curves to the right (this
corresponds to an increase in hardenability as it increases the ease of forming
martensite - i.e. the cooling rate required to attain martensite is less severe).
• An increase in carbon content decreases the martensite start temperature.
• An increase in Mo content shifts the CCT and TTT curves to the right and also
separates the ferrite + pearlite region from the bainite region making the attainment of
a bainitic structure more controllable.
We use as an example the cooling of an eutectoid alloy (0.76 wt% C) from the austenite
(γ- phase) to pearlite, that contains ferrite (α) plus cementite (Fe3C or iron carbide). When
cooling proceeds below the eutectoid temperature (727 oC) nucleation of pearlite starts.
The S-shaped curves (fraction of pearlite vs. log. time, fig. 10.3) are displaced to longer
times at higher temperatures showing that the transformation is dominated by nucleation
(the nucleation period is longer at higher temperatures) and not by diffusion (which
occurs faster at higher temperatures).
The family of S-shaped curves at different temperatures can be used to construct the TTT
(Time-Temperature-Transformation) diagrams (e.g., fig. 10.4.) For these diagrams to
apply, one needs to cool the material quickly to a given temperature To before the
transformation occurs, and keep it at that temperature over time. The horizontal line that
indicates constant temperature To intercepts the TTT curves on the left (beginning of the
transformation) and the right (end of the transformation); thus one can read from the
diagrams when the transformation occurs. The formation of pearlite shown in fig. 10.4
also indicates that the transformation occurs sooner at low temperatures, which is an
indication that it is controlled by the rate of nucleation. At low temperatures, nucleation
occurs fast and grain growth is reduced (since it occurs by diffusion, which is hindered at
low temperatures). This reduced grain growth leads to fine-grained microstructure (fine
pearlite). At higher temperatures, diffusion allows for larger grain growth, thus leading to
coarse pearlite.
At lower temperatures nucleation starts to become slower, and a new phase is formed,
bainite. Since diffusion is low at low temperatures, this phase has a very fine
(microscopic) microstructure.
A very important structure is martensite, which forms when cooling austenite very fast
(quenching) to below a maximum temperature that is required for the transformation. It
forms nearly instantaneously when the required low temperature is reached; since no
thermal activation is needed, this is called an athermal transformation. Martensite is a
different phase, a body-centered tetragonal (BCT) structure with interstitial C atoms.
Martensite is metastable and decomposes into ferrite and pearlite but this is extremely
slow (and not noticeable) at room temperature.
In the examples, we used an eutectoid composition. For hypo- and hypereutectoid alloys,
the analysis is the same, but the proeutectoid phase that forms before cooling through the
eutectoid temperature is also part of the final microstructure.
Phase Diagrams
Contents
P+F =C+2 P + F = C +1
cV Uc
CL = CS = CL + CS = 1
UV UV
Satish V. Kailas ME/MS 13
Eutectic Binary System
Many of the binary systems with limited solubility are of
eutectic type – eutectic alloy of eutectic composition
solidifies at the end of solidification at eutectic
temperature.
E.g.: Cu-Ag, Pb-Sn
∆H f ∆T
∆g
where Tm – freezing temperature (in K), ∆Hf – latent heat
of fusion, ∆T – amount of under-cooling at which nucleus
is formed.
γ αδ = γ αβ cos θ + γ βδ
Chapter 8. Failure
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.
• Track formation
• Track propagation
Ductile Brittle
Type of materials Most metals (not too cold) Ceramics, ice, cold metals
Necking Yes No
• Initial necking
• Small cavity formation (microvoids)
• Void growth (ellipsoid) by coalescence into a crack
• Fast crack propagation around neck. Shear strain at
45o
• Final shear fracture (cup and cone)
Brittle Fracture
Fracture occurs due to stress concentration at flaws, like surface scratches, voids, etc. If a
is the length of the void and ρ the radius of curvature, the enhanced stress near the flaw
is:
σm ≈ 2 σ0 (a/ρ)1/2
where σ0 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 = σm/σ0 ≈ 2 (a/ρ)1/2
Because of this enhancement, flaws with small radius of curvature are called stress
raisers.
Impact fractures can best be described as a flute or strip of material that was cleanly
sheared from a projectile point. The most common type of impact fracture starts at the tip
of a point and runs down one blade edge possibly reaching the shoulder of a point. Some
points were reworked into a useable point after having been damaged by an impact
fracture.
Normalized tests, like the Charpoy 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.
8.6 Fatigue:
Cyclic Stresses
These are characterized by maximum, minimum and mean stress, the stress amplitude,
and the stress ratio.
Stage I - propagation
• slow
• along crystallographic planes of high shear stress
• flat and featureless fatigue surface
Stage II - propagation
8.9 Creep
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:
Both temperature and the level of the applied stress influence the creep characteristics.
The results of creep rupture tests are most commonly presented as the logarithm of stress
versus the logarithm of rupture lifetime.
The behavior can be characterized by the following expression, where K, n and Qc are
constants for a given material:
dε/dt = K σn exp(-Qc/RT)
Failure
Contents
2. Fracture mechanics
σf ≈⎜ ⎟
⎝ 4c ⎠
Griffith’s criteria: a crack will propagate when the
decrease in elastic energy is at least equal to the energy
required to create the new crack surface. Thus for thin
12
plates: ⎛ 2 E γ ⎞
σ =⎜ ⎟
⎛ 2 Eγ ⎞
12
⎝ cπ ⎠
For thick plates: σ = ⎜⎜ ⎟⎟
⎝ (1 − ν )cπ ⎠
2
Extrusions &
Deformation feature Contour
Intrusions
Vacancy
Less Very high
concentration
Necessity of
Required Not necessary
diffusion
Satish V. Kailas ME/MS 24
Static Load Vs Cyclic Load - 2
Qc
−
ε& s = K 2σ n e RT
Ferrous alloys:
Ferrous alloys are those in which iron is the prime constituent. They are especially
important as engineering construction materials. The principal disadvantage of many
ferrous alloys is their susceptibility to corrosion. Different alloys of iron are given below:
Alloys of iron
• Steel (carbon)
o Stainless steel (chromium, nickel)
Surgical stainless steel (chromium, molybdenum, nickel)
o Silicon steel (silicon)
o Tool steel (tungsten or manganese)
• Cast iron (carbon)
• Spiegeleisen (manganese, carbon, silicon)
Nonferrous alloys:
Alloys of cobalt
Alloys of nickel
• Mu-metal (iron)
• Monel metal (copper, iron, manganese)
• Nichrome (chromium, iron)
Alloys of copper
• Brass (zinc)
• Prince's metal (zinc)
• Gilding metal (zinc)
• Bronze (tin, aluminium or any other element)
o Phosphor bronze (tin and phosphorus)
• Bell metal (tin)
• Beryllium copper (beryllium)
• Cupronickel (nickel)
Alloys of silver
Alloys of tin
Alloys of gold
Alloys of mercury
• Amalgam
Alloys of lead
• Solder
• Type metal
Alloys of bismuth
• Wood's metal
mill are available. Complete metallographic facilities to study the microstructure of the
materials processed are also located at the facility.
Forming operations
Forming operations are those in which the shape of a metal piece is changed by plastic
deformation; for example, forging, rolling, extrusion and drawing are common forming
techniques. When deformation is achived at a temperature above that at which
recrystallization occurs, the process is termed hot working, otherwise it is cold working.
Forging
Rolling
Rolling, the most widely used deformation process consists of passing a piece of metal
between two rolls, a reduction in thickness results from compressive stresses exerted by
the rolls.
Extrusion
For extrusion, a bar of metal piece through a die orifice by a compressive force that is
applied to a ram; the extruded piece that emerges has the desired shape and a reduced
cross sectional area.
Drawing
Drawing is the pulling of a metal pice through a die having a tapered bore by means of a
tensile force that is applied on the exit side. A reduction in cross section results, with a
corresponding increase in length.
Casting:
Casting is a fabrication process whereby a totally molten metal is poured into a mold
cavity having the desired shape; upon solidification, the metal assumes the shape of the
mold but experiences some shrinkages. Different types of casting techniques which are
commonly employed are: sand , die, investment and continuous casting.
Miscellaneous Techniques:
Powder Metallurgy
This is another fabrication technique which involoves the compaction of powdered metal,
followed by a heat treatment to produce a more dense piece. Diffusional processes during
the heat treatment are central to the development of these properties. This method is
especially suitable for metals having low ductilities, since only small plastic deformation
of the powder particles need occur.
Welding
In welding, two or more metal parts are joined to form a single piece when one part
fabrication is expensive or inconvenient. Both similar and non similar metals can be
joined by welding. The joining bond is metallurgical rather than juts mechanical. During
arc and gas welding, the work pieces to be joined and the filler material are heated to a
sufficiently high temperature to cause both to melt; upon solidification, the filler material
forms a fusion joint between the work pieces.
Annealing Processes
Annealing is a heat treatment where the material is taken to a high temperature, kept there
for some time and then cooled. High temperatures allow diffusion processes to occur
fast. The time at the high temperature (soaking time) is long enough to allow the desired
transformation to occur. Cooling is done slowly to avoid the distortion (warping) of the
metal piece, or even cracking, caused by stresses induced by differential contraction due
to thermal inhomogeneities. Benefits of annealing are:
• relieve stresses
• increase softness, ductility and toughness
• produce a specific microstructure
a) solution heat treatment where all the solute atoms are dissolved to form
a single-phase solution.
b) rapid cooling across the solvus line to exceed the solubility limit. This
leads to a supersaturated solid solution that remains stable (metastable)
due to the low temperatures, which prevent diffusion.
If the process is continued for a very long time, eventually the hardness decreases. This
is called overaging.
2. Fabrication of metals
Ceramics offer a high temperature range. However, ceramics are not very strong.
To compensate for their lack of strength ceramics are usually combined with
some other material to form a ceramic composite.
1) Glasses and glass ceramics- The glasses are a familiar group of ceramics;
containers, windows, lenses and fiberglass represent typical applications. The
properties of standard vitrified products are insufficient for architectural
applications and structural building components, insulation or other specialized
applications. Yet there is an effective way to improve these properties without
major alterations to the process itself - the introduction of a controlled
crystallization process through a subsequent heat treatment, i.e. by forming a
glass-ceramic.
Production of Glass-Ceramics
In the latter case, the powders are densified at relatively low temperatures by exploiting a
viscous flow sintering mechanism. After densification, the material is subjected to a
crystallisation heat-treatment to obtain the required glass-ceramic microstructure.
Alternatively, both densification and crystallisation may take place during a single
sintering step.
Along with the economic advantage of using relatively low processing temperatures, the
powder technology route is suitable for the production of a range of advanced materials,
including glass-ceramics with specified porosities and glass-ceramic matrix composites.
Using the petrurgic method, the slow cooling from the molten state causes nucleation and
growth of certain crystalline phases. Therefore, the final microstructure, and hence the
properties, depends mainly on the composition and the cooling rate.
The very high iron oxide content of coal ash, table 1, indicates the potential for
developing magnetic phases using appropriate processing - this was the aim of our work.
We calcined the as-received ash at 800°C for two hours to remove any volatile
compounds, including sulfur and carbon. The powder and petrurgic methods were
explored, and gave us products with different phases and microstructures. For the
sintering experiments, we mixed calcined ash powder with various amounts (10-50wt%)
of borosilicate (Pyrex) glass. The powder mixtures were uniaxial cold pressed to a
cylindrical shape and sintered in air at temperatures in the range of 1,000-1,500°C for
periods of up to 15 hours. Using the petrurgic method, coal ash was mixed with soda-
lime glass powder. The mixture was melted at 1,500°C and cooled to room temperature
at rates of between 1-10°C per minute.
Glass-Ceramic Composites
Work to date has largely concentrated on composites with a matrix of the slag-based
Silceram glass-ceramic (a glass-ceramic for floor and wall tiles and wear components).
We have investigated both particulate- (SiC and TiC) and fibre-reinforcement (SiC).
Properties measured include the fundamental mechanical properties but also more
complex properties such as thermal shock resistance and erosion resistance. As
mentioned previously, the thermal shock resistance of glass-ceramics is superior to the
parent glasses, and the shock resistance is further improved by particulate reinforcement.
For example, monolithic Silceram has a thermal shock critical temperature of 180°C,
whereas a 20wt%SiC composite has a value of 270°C. Erosion resistance may also be
improved by particulate reinforcement, e.g., for TiC reinforced Silceram - the larger the
reinforcement particle size and the greater the volume fraction, the lower the erosion rate.
Results indicate a way for transforming vitrified silicate residues into useful products
with broad application potential. The glass-ceramics obtained are candidate materials for
applications in floors of industrial buildings and in construction, and for outside and
inside facing walls. We are currently addressing issues associated with the effect of
environmental influences on the chemical durability and toxic potential of the materials,
which may be compromised by the presence of heavy metals incorporated in the glass or
crystalline phases. Public acceptance of the use and exploitation of glass-ceramic-based
materials in such applications will strongly depend on a satisfactory consideration of
these issues.
2) Refractories -Refractories are materials needed for handling high temperature liquids,
gases and solids, e.g., for industrial processing. Applications include solar furnaces,
casting molds for molten materials, heat exchangers, and aerobraking heat shields.
Industrial refractory needs can be satisfied by sintered calcia (CaO), silica (SiO2),
magnesia (MgO), alumina (Al2O3) and titania (TiO2), with the desired porosity. Of
course, these stable materials are commonly used on Earth for the same purposes, due to
their great resistance to heat, oxidation (they are already fully oxidized), corrosion and
abrasion. Minerals such as olivine [(MgFe)2SiO4] and anorthite (CaAl2Si2O8) are also
useful for making refractory bricks and ceramics. Some refractories and their ceramics
have low expansion due to heat and are attractive for space environments where a wide
range of temperatures are experienced.
Production of ceramics and refractories in space from lunar materials has been discussed
in a number of papers, including Poisl and Fabes, as well as Shirley et al., and Mackenzie
and Claridge, among others.
Aerobraking tiles are produced from amorphous silica fibers which are pressed and
sintered, with the resulting tile having as much as 93% porosity (i.e., very lightweight)
and low thermal expansion, low thermal conductivity, and good thermal shock properties.
This process can be readily performed in space when we can produce silica of the
required purity.
Cheaper materials besides silica fibers can be used. Silica fibers are used on the Space
Shuttle in order to keep its weight down, thereby increasing cargo weight capacity. For
resources already in space, we don't have this economic need. A number of other
materials can be used for heat shields, e.g., alumina (Al2O3) or anorthite (CaAl2Si2O8).
3) Abrasives- Abrasive cements are used to wear, grind or cut away other material, which
necessarily is softer. Therefor, the prime requisite for this group of materials is hardness
or wear resistancr; in addition, a hig degree of toughness is essential to ensure that the
abrasive particles do not easily fracture. Furthermore, high temperatures may be
produced from abrasive frictional forces, so some refractoriness is also desirable.
Diamonds, both natural and synthetic, are utilized as abrasives; however, they are
relatively expensive. The more common ceramic abrasives include silicon carbide,
tungsten carbide(WC), aluminium oxide and silica sand. Abrasives are used in several
forms-bonded to grinding wheels, as coated abrasives and as loose grains. Coated
abrasives are those in which an abrasive powder is coated on some type of paper or cloth
material; sandpaper is probably the mostly familiar example. Wood, metals, ceramics and
plastics are all frequently ground and polished using this form of abrasive.Grinding,
lapping and polishing wheels often employ loose abrasive grains that are delivered in
some type of oil or water based vehicle. Diamonds, corundum,silicon carbide and rouge
are used in loose form over a variety of grain size ranges.
4) Cements:
Portland Cement
The term "Portland" in Portland cement originated in 1824 when an English mason
obtained a patent for his product, which he named Portland Cement. This was because his
cement blend produced concrete that resembled the color of the natural limestone
quarried on the Isle of Portland in the English Channel.
Different types of Portland cement are manufactured to meet different physical and
chemical requirements for specific purposes. The American Society for Testing and
Materials (ASTM) Designation C 150 provides for eight types of Portland cement:
(reference).Portland Cement is a type of cement, not a brand name. Many cement
manufacturers make Portland Cement. Variuos types of Portland cements are:
Type 1
normal portland cement. Type 1 is a general use cement.
Type 2
is used for structures in water or soil containing moderate amounts of sulfate, or when
heat build-up is a concern.
Type 3
high early strength. Used when high strength are desired at very early periods.
Type 4
low heat portland cement. Used where the amount and rate of heat generation must be
kept to a minimum.
Type 5
Sulfate resistant portland cement. Used where the water or soil is high in alkali.
Types IA, IIA and IIIA are cements used to make air-entrained concrete. They have the
same properties as types I, II, and III, except that they have small quantities of air-
entrained materials combined with them.
These are very short descriptions of the basic types of cement. There are other types for
various purposes such as architectural concrete and masonry cements, just to name two
examples
5) Advanced Ceramics:
Advanced Cerametrics Inc. (ACI) has evolved over its 56 year history
from a small, family owned manufacturer of ceramic wear parts for the
textile industry, to a prominent, high-tech company developing and
manufacturing advanced materials. In recent years ACI has been the
recipient of numerous R & D grants from the Defense Department,
NASA and the Department of Energy.
Ceramic Fiber
Ceramic Synthesis: Our expertise and capabilities in synthesizing ceramics are based on
chemical solution techniques. Chemical solution or sol-gel approaches have been
developed to fabricate powders, films, and porous bodies. Materials of interest range
from silica to complex, multicomponent electronic ceramics. The complexity inherent in
fabricating materials with structured nanoporosity or complex chemistries requires a
fundamental understanding of these chemical solution approaches. Fabrication of unique
precursors for complex oxides is being done with novel metal alkoxide chemistry to
produce powders and thin-film materials with carefully controlled properties. Our ability
to synthesize materials with complex structures, chemistries, or both, is at the heart of
numerous research and development efforts at Sandia.
Ceramic Processing: Sandia's fabrication of ceramic components and devices is based
on a strong ceramic-processing capability. We recently have demonstrated the ability to
characterize and model the powder-compaction process in detail, and to address and
control density gradients in powder compacts that cause shape distortion and differential
shrinkage. Proprietary 3D, finite-element code packing and compaction models, and
process-control tools are now available to improve the production of ceramic
components. Sandia has capabilities in the areas of hydrostatic and triaxial compaction
testing to characterize materials properties, and x-ray radiography, ultrasound, and
computed tomography for density characterization. In addition, expertise in slurry
This requires creation of electron [e'] and hole [h⋅] pairs in ionic solid according to the
symbolic chemical reaction, which describes creation of carriers due to thermal activation
(this process results in intrinsic conductivity):
nil ⇔ e' + h⋅
K = [e'] + [h⋅ ] = n . p = exp (- ∆G0/RT) = exp (∆S0/R) exp (-Eg /RT)
The magnitude of the band gap Eg determines ability of a material to conduct. For Eg > 6
eV, materials are considered as insulators . This wide energy gap is typical for the
ionic oxides of metals having a single stable oxidation state: groups IA, IIA, IIIA. The
electrical resistivity of most stable insulators correlates with the ionic character of their
bond: the larger difference of electronegativity, the larger % of ionic bond, and the larger
energy gap Eg.
The band gap magnitude correlates also with the ionic bond energy, i.e. the most stable
ionic ceramic are also the best insulators. For example, the bond energy of alumina is
~6eV/equivalent (1/3 Al2O3) and Eg = ~7eV; the bond energy of one equivalent of
cadmium oxide (CdO) is ~4 eV/equivalent and Eg = ~2eV.
The oxides of metals able to have multiple oxidation states (such as transition elements,
with partially filled "d" orbitals) have narrower band gaps of the order of 2-5eV, resulting
in intrinsic semiconducting properties. The presence of point defects in ionic solids
(such as solutes, vacancies, interstistials) can dramatically decrease the energy required
for the creation of electron/hole pairs.
This is because these defects are typically located “within” the energy gap, either close to
the valence band (acceptors) or conduction band (donors). An example is KCl
containing VK', VCl•, CaK• , or MgO containing VMg'', VO•,VMg', VC0, AlMg•.
The point defects are the key feature of extrinsic semiconductors, the basic components
of modern electronics.
The variety of point defects present in ceramics gives frequently a mixed ionic and
electronic type of electrical conduction. To some extent, every ionic crystal is a mixed
conductor, but the share of electronic conductivity, expressed through the charge
transference number for electrons, can be negligible. If Ohm’s law is expressed in
terms of current density J [A/m2], material conductivity σ [A/Vm] and electric field Ee,
[V/m] following relationship results:
J = - σ.Ee
where, for mixed a conductor, σ = Σσi, the sum of conductvities due to the various
charge-carrying species, i.e. ions, holes and electrons. The transference number ti of a
given species is then defined as: tj = σj/Σσi
For ionic conductors, the aim is to maximize the charge transference due to the
movement of ions and minimize the transference due to electrons and holes movement.
That is, tion ≈ 1 , te,h ≈ 0 . This is principle behind the operation of solid
electrolytes. The sub-class of solid electrolytes useful for solid-state electrochemical
devices (batteries, sensors) can be defined as "fast ionic conductors" as long as:
1. The activation energy Ed for diffusion is LOW, less than ~0.1 eV/atom, or
2.5 kcal/mole, or 10 kJ/mole, or ~10% of the energy needed to form a point defect in a
close packed ionic solid.
If the above conditions are fulfilled, the diffusivity at room temperature will be D > 10-6
cm2/s, and room temperature ionic conductivity will be σ > 0.01 1/Ωcm, or resistivity ρ
= 100 Ωcm . This magnitude of conductivity allows the use of solid state ionic
conductors in devices like batteries, sensors and fuel cells.
The resistivity of ionic conductor is the primary factor that determines internal resistance
of the cell, and thus maximum current that can be drawn from the cell. As resistance R
= ρ L/A (L being electrolyte thickness, typically 0.1-1 cm, and A area, typically 10-1000
cm2), then the internal resistance of such battery is typically 1 Ω .
The description of stress-strain behavior is similar to that of metals, but a very important
consideration for polymers is that the mechanical properties depend on the strain rate,
temperature, and environmental conditions.
The stress-strain behavior can be brittle, plastic and highly elastic (elastomeric or rubber-
like). Tensile modulus (modulus) and tensile strengths are orders of magnitude smaller
than those of metals, but elongation can be up to 1000 % in some cases. The tensile
strength is defined at the fracture point and can be lower than the yield strength.
Mechanical properties change dramatically with temperature, going from glass-like brittle
behavior at low temperatures (like in the liquid-nitrogen demonstration) to a rubber-like
behavior at high temperatures .
In general, decreasing the strain rate has the same influence on the strain-strength
characteristics as increasing the temperature: the material becomes softer and more
ductile.
Many semicrystalline polymers have the spherulitic structure and deform in the following
steps :
The macroscopic deformation involves an upper and lower yield point and necking.
Unlike the case of metals, the neck gets stronger since the deformation aligns the chains
so increasing the tensile stress leads to the growth of the neck. (Fig. 16.5).
The tensile modulus decreases with increasing temperature or diminishing strain rate.
Obstacles to the steps mentioned in strengthen the polymer. Examples are cross-linking
(aligned chains have more van der Waals inter-chain bonds) and a large mass (longer
molecules have more inter-chain bonds). Crystallinity increases strength as the secondary
bonding is enhanced when the molecular chains are closely packed and parallel. Pre-
deformation by drawing, analogous to strain hardening in metals, increases strength by
orienting the molecular chains. For undrawn polymers, heating increases the tensile
modulus and yield strength, and reduces the ductility - opposite of what happens in
metals.
Crystallization rates are governed by the same type of S-curves we saw in the case of
metals (Fig. 16.7). Nucleation becomes slower at higher temperatures.
The melting temperature increases with the rate of heating, thickness of the lamellae, and
depends on the temperature at which the polymer was crystallized.
Melting involves breaking of the inter-chain bonds, so the glass and melting temperatures
depend on:
Polymerization
These are the cheapest and most widely used. They fall in two categories depending on
the size of the particles:
Properties are a combination of those of the components. The rule of mixtures predicts
that an upper limit of the elastic modulus of the composite is given in terms of the elastic
moduli of the matrix (Em) and the particulate (Ep) phases by:
Ec = EmVm + EpVp
where Vm and Vp are the volume fraction of the two phases. A lower bound is given by:
Concrete
The most common large-particle composite is concrete, made of a cement matrix that
bonds particles of different size (gravel and sand.) Cement was already known to the
Egyptians and the Greek. Romans made cement by mixing lime (CaO) with volcanic ice.
In its general from, cement is a fine mixture of lime, alumina, silica, and water. Portland
cement is a fine powder of chalk, clay and lime-bearing minerals fired to 1500o C
(calcinated). It forms a paste when dissolved in water. It sets into a solid in minutes and
hardens slowly (takes 4 months for full strength). Properties depend on how well it is
mixed, and the amount of water: too little - incomplete bonding, too much - excessive
porosity.
The advantage of cement is that it can be poured in place, it hardens at room temperature
and even under water, and it is very cheap. The disadvantages are that it is weak and
brittle, and that water in the pores can produce crack when it freezes in cold weather.
Concrete is cement strengthened by adding particulates. The use of different size (stone
and sand) allows better packing factor than when using particles of similar size.
Concrete is improved by making the pores smaller (using finer powder, adding polymeric
lubricants, and applying pressure during hardening.
Reinforced concrete is obtained by adding steel rods, wires, mesh. Steel has the
advantage of a similar thermal expansion coefficient, so there is reduced danger of
cracking due to thermal stresses. Pre-stressed concrete is obtained by applying tensile
stress to the steel rods while the cement is setting and hardening. When the tensile stress
is removed, the concrete is left under compressive stress, enabling it to sustain tensile
loads without fracturing. Pre-stressed concrete shapes are usually prefabricated. A
common use is in railroad or highway bridges.
Cermets
are composites of ceramic particles (strong, brittle) in a metal matrix (soft, ductile) that
enhances toughness. For instance, tungsten carbide or titanium carbide ceramics in Co or
Ni. They are used for cutting tools for hardened steels.
Reinforced rubber
Dispersion-Strengthened Composites
Use of very hard, small particles to strengthen metals and metal alloys. The effect is like
precipitation hardening but not so strong. Particles like oxides do not react so the
strengthening action is retained at high temperatures.
In many applications, like in aircraft parts, there is a need for high strength per unit
weight (specific strength). This can be achieved by composites consisting of a low-
density (and soft) matrix reinforced with stiff fibers.
The strength depends on the fiber length and its orientation with respect to the stress
direction.
The efficiency of load transfer between matrix and fiber depends on the interfacial bond.
Largest and most diverse use of composites due to ease of fabrication, low cost and good
properties.
Glass-fiber reinforced composites (GFRC) are strong, corrosion resistant and lightweight,
but not very stiff and cannot be used at high temperatures. Applications include auto and
boat bodies, aircraft components.
Carbon-fiber reinforced composites (CFRC) use carbon fibers, which have the highest
specific module (module divided by weight). CFRC are strong, inert, allow high
temperature use. Applications include fishing rods, golf clubs, aircraft components.
Kevlar, and aremid-fiber composite can be used as textile fibers. Applications include
bullet-proof vests, tires, brake and clutch linings.
Wood
This is one of the oldest and the most widely used structural material. It is a composite of
strong and flexible cellulose fibers (linear polymer) surrounded and held together by a
matrix of lignin and other polymers. The properties are anisotropic and vary widely
among types of wood. Wood is ten times stronger in the axial direction than in the radial
or tangential directions.
The corrosion resistance of metals and alloys is a basic property related to the easiness
with which these materials react with a given environment. Corrosion is a natural
process that seeks to reduce the binding energy in metals. The end result of corrosion
involves a metal atom being oxidized, whereby it loses one or more electrons and leaves
the bulk metal. The lost electrons are conducted through the bulk metal to another site
where they are reduced. In corrosion parlance, the site where metal atoms lose electrons
is called the anode, and the site where electrons are transferred to the reducing species is
called the cathode.
The following links will lead to interesting information concerning specific metals and
indexes to relevant pages of the Corrosion Doctors site:
Aluminum
Cadmium
Chromium
Cobalt
Copper
Gold
Iron
Lead
Magnesium
Molybdenum
Nickel
Silver
Tin
Titanium
Zinc
Pure metals are used in many applications. Copper, for example, is used to make the wire
which goes inside electrical cables. Copper was chosen because it can be drawn into long
thin wires very easily (it is ductile) and because it is a good conductor of electricity. Pure
aluminum can also be used in wiring. It is also used as a cladding material for aluminum
alloy substrates.
Currently there are 86 known metals. Before the 19th century only 24 of these metals had
been discovered and, of these 24 metals, 12 were discovered in the 18th century.
Therefore, from the discovery of the first metals, gold and copper, until the end of the
17th century, some 7700 years, only 12 metals were known. Four of these metals,
arsenic, antimony , zinc and bismuth , were discovered in the thirteenth and fourteenth
centuries, while platinum was discovered in the 16th century. The other seven metals,
known as the Metals of Antiquity, were the metals upon which civilization was based.
These seven metals are Gold, Copper, Silver, Lead, Tin, Iron,Mercury.
It is often said that one of the biggest advantages which ceramics have over other
materials is their corrosion resistance, that is, their chemical inertness in corrosive
environments. Is this always true?
Ceramics are indeed much more environmentally stable, as compared to any other group
of engineering materials, e.g. metals or plastics. Still, the potential for ceramics as
corrosion resistant engineering structural materials are far from being fully realized,
because of:
- Alumina in water, where preferential attack of the grain boundary glassy (silicate)
phases occurs.
- The preferential attack of free Si in reaction bonded SiC, by alkalis or molten metals.
- The oxide grain boundary phases in nonoxides (B2O3 in BN, silicates in Si3N4 and
SiC) are sensitive to water.
Severe corrosion takes place if the ceramic is in contact with a substance which can
combine with it and form low-melting liquids (i.e. with eutectic point below ambient
temperature).
The example of above situation is the system composed of metallurgical slag in contact
with refractories. If the reaction is thermodynamically possible, the corrosion will
proceed at a dramatic rate if the refractory is wetted by the slag.
Degradation of polymers:
While the plastics industry searches for solutions to the problem of plastics waste, there
is, surprisingly, a growing band of people trying to save plastics.Although the
manufacturers of early ‘plastics’ such as horn buttons, Bois Durci paperweights or
celluloid collars would be astonished to see how well many of their goods have survived,
many other plastics have begun to show disturbing signs of instability. Every collection
of plastics worldwide, from the Science Museum and Tate Gallery to the Comb &
Plastics Museum in Oyonnax, has already lost or is losing unique and beautiful pieces
through degradation.
The crucial fact is that plastics are organic and have been described as a time bomb
ticking away since cellulose nitrate based plastics were invented around 130 years ago. It
can of course be argued that manufacturers’ foremost intentions have never been to make
beautiful objects for museums. However, museums have a duty to preserve their
acquisitions.
It was not until the late 1980s that attention was paid to the fact that plastics artefacts had
been physically changing, showing signs of acid vapour, tackiness, warping,
embrittlement and crazing. Cellulose nitrate and cellulose acetate were particularly
affected. By 1991 John Morgan of the Plastics Historical Society had collected enough
data to write Conservation of Plastics -An Introduction, a joint PHS /Conservation Unit
publication, and the Conservation Unit launched a survey to identify objects at risk with
the aim of setting up a research programme. The survey included everything from radios
and cables to textiles and sculptures.
By 1992 acrylic based paintings worth millions of pounds by leading artists of the 1960s
including David Hockney and Jackson Pollock had begun to suffer discolouration,
cracking and greyness due to the absorption of dust and atmospheric pollutants. These
paints seemed particularly vulnerable. At room temperature they are relatively soft and
attract dirt which becomes embedded. However, to date no method has been found of
cleaning them.
The photographic film industry was also badly hit when irreplaceable archive nitrate
stock started to decompose. Today, the National Film Archive transfers cellulose nitrate
and cellulose triacetate onto more stable polyester at the rate of a million metres a year.
The PHS/CU survey unearthed some interesting facts. For example, 40% of museums
surveyed contain plastics objects manufactured and collected since 1980, and modem
plastics are also showing symptoms of decay. Polyurethane foam appears to be one of the
worst victims, and many early video and audio tapes on magnetic media are already
unplayable. The curator who has to supervise a collection of high-tech, mixed material
products such as space suits is confronted with a conservation dilemma: which material
deserves priority treatment when each separate plastic has different requirements?
The degradation of plastics can be said to begin as soon as the polymer is synthesised,
and is increased by residual stresses left by moulding processes. This can be followed by
exposure to light (especially UV), humidity, oxygen, heat, bacteria and stress. Plastics
can also be contaminated by other materials, including other plastics. A polystyrene
camera body, for example, can be attacked by plasticiser migrating from a PVC strap.
Ideally the conservator needs information about the history of an object before
prescribing treatment, but even before this, the plastics ‘doctor’ must jump another
hurdle. Specific conservation action cannot be taken until the polymer has been
identified, and this is a technical area full of pitfalls. A 1920s black brooch could be made
of at least six different plastics materials, or simply painted as was common practice in
the 19th century. Even a patent number, one of the few ‘hallmarks’ found on plastics and
an obvious aid to identification, may refer to a fixing mechanism and not to the
moulding.
Preserving Plastics
Derek Pullen, a conservator at the Tate Gallery, explains, ‘Plastics are giant molecules
held together by forces which can be broken by attacking energy forces such as light. All
the conservator can do is to keep mouldings in a very stable, low energy environment (the
burial chambers of the Pyramids were ideal)’.
There are two main types of plastics degradation being researched at present: physical
and chemical, and both are closely inter-connected. Physical degradation can involve
environmental stress cracking and plasticiser migration and loss. Chemical reactions
include oxidation and hydrolysis, and are a problem particularly affecting the cellulose
esters (cellulose nitrate and cellulose acetate), which emit acidic degradation products. If
not removed, these catalyse further reactions and eventually cause serious crazing and
total destruction of the object. If degrading cellulose esters are not isolated, the acidic
fumes will infect similar objects stored close by and initiate degradation there.
Conclusion
Compared to traditional materials with long established technologies such as metals and
glass, the complex chemical nature of plastics is providing conservators with possibly
their most formidable challenge yet.
Ohm’s Law
I = V/R
where R is the electrical resistance. R depends on the intrinsic resistivity ρ of the material
and on the geometry (length l and area A through which the current passes).
R = ρl/A
Electrical Conductivity
The electric field in the material is E=V/l, Ohm's law can then be expressed in terms of
the current density j = I/A as:
j=σE
The conductivity is one of the properties of materials that varies most widely, from 107
(Ω-m) typical of metals to 10-20 (Ω-m) for good electrical insulators. Semiconductors
have conductivities in the range 10-6 to 104 (Ω-m).
In metals, the current is carried by electrons, and hence the name electronic conduction.
In ionic crystals, the charge carriers are ions, thus the name ionic conduction.
When atoms come together to form a solid, their valence electrons interact due to
Coulomb forces, and they also feel the electric field produced by their own nucleus and
that of the other atoms. In addition, two specific quantum mechanical effects happen.
First, by Heisenberg's uncertainty principle, constraining the electrons to a small volume
raises their energy, this is called promotion. The second effect, due to the Pauli exclusion
principle, limits the number of electrons that can have the same property (which include
the energy). As a result of all these effects, the valence electrons of atoms form wide
valence bands when they form a solid. The bands are separated by gaps, where electrons
cannot exist. The precise location of the bands and band gaps depends on the type of
atom (e.g., Si vs. Al), the distance between atoms in the solid, and the atomic
arrangement (e.g., carbon vs. diamond).
In semiconductors and insulators, the valence band is filled, and no more electrons can be
added, following Pauli's principle. Electrical conduction requires that electrons be able to
gain energy in an electric field; this is not possible in these materials because that would
imply that the electrons are promoted into the forbidden band gap.
In metals, the electrons occupy states up to the Fermi level. Conduction occurs by
promoting electrons into the conduction band, that starts at the Fermi level, separated by
the valence band by an infinitesimal amount.
The resistivity then depends on collisions. Quantum mechanics tells us that electrons
behave like waves. One of the effects of this is that electrons do not scatter from a perfect
lattice. They scatter by defects, which can be:
One can express the total resistivity ρtot by the Matthiessen rule, as a sum of resistivities
due to thermal vibrations, impurities and dislocations. Fig. 19.8 illustrates how the
resistivity increases with temperature, with deformation, and with alloying..
14.2 Semiconductivity:
Intrinsic Semiconduction
Conduction is by electrons and holes. In an electric field, electrons and holes move in
opposite direction because they have opposite charges. The conductivity of an intrinsic
semiconductor is:
σ = n |e| µe + p |e| µh
where p is the hole concentration and µh the hole mobility. One finds that electrons move
much faster than holes:
µe > µh
n=p
Extrinsic Semiconduction
Excess electron carriers are produced by substitutional impurities that have more valence
electron per atom than the semiconductor matrix. For instance phosphorous, with 5
valence electrons, is an electron donor in Si since only 4 electrons are used to bond to the
Si lattice when it substitutes for a Si atom. Thus, elements in columns V and VI of the
periodic table are donors for semiconductors in the IV column, Si and Ge. The energy
level of the donor state is close to the conduction band, so that the electron is promoted
(ionized) easily at room temperature, leaving a hole (the ionized donor) behind. Since this
hole is unlike a hole in the matrix, it does not move easily by capturing electrons from
adjacent atoms. This means that the conduction occurs mainly by the donated electrons
(thus n-type).
Excess holes are produced by substitutional impurities that have fewer valence electrons
per atom than the matrix. This is the case of elements of group II and III in column IV
semiconductors, like B in Si. The bond with the neighbors is incomplete and so they can
capture or accept electrons from adjacent silicon atoms. They are called acceptors. The
energy level of the acceptor is close to the valence band, so that an electron may easily
hop from the valence band to complete the bond leaving a hole behind. This means that
conduction occurs mainly by the holes (thus p-type).
Temperature causes electrons to be promoted to the conduction band and from donor
levels, or holes to acceptor levels. The dependence of conductivity on temperature is like
other thermally activated processes:
σ = A exp(–Eg/2kT)
where A is a constant (the mobility varies much more slowly with temperature). Plotting
ln σ vs. 1/T produces a straight line of slope Eg/2k from which the band gap energy can
be determined. Extrinsic semiconductors have, in addition to this dependence, one due to
the thermal promotion of electrons from donor levels or holes from acceptor levels. The
dependence on temperature is also exponential but it eventually saturates at high
temperatures where all the donors are emptied or all the acceptors are filled.
This means that at low temperatures, extrinsic semiconductors have larger conductivity
than intrinsic semiconductors. At high temperatures, both the impurity levels and valence
electrons are ionized, but since the impurities are very low in number and they are
exhausted, eventually the behavior is dominated by the intrinsic type of conductivity.
Semiconductor Devices
A p-n-p junction transistor contains two diodes back-to-back. The central region is very
thin and is called the base. A small voltage applied to the base has a large effect on the
current passing through the transistor, and this can be used to amplify electrical signals
(Fig. 19.22). Another common device is the MOSFET transistor where a gate serves the
function of the base in a junction transistor. Control of the current through the transistor
is by means of the electric field induced by the gate, which is isolated electrically by an
oxide layer.
In ionic materials, the band gap is too large for thermal electron promotion. Cation
vacancies allow ionic motion in the direction of an applied electric field, this is referred
to as ionic conduction. High temperatures produce more vacancies and higher ionic
conductivity.
At low temperatures, electrical conduction in insulators is usually along the surface, due
to the deposition of moisture that contains impurity ions.
14.3 Superconductivity:
Scientists had been intrigued with the concept of superconductivity since its discovery in
the early 1900s, but the extreme low temperatures the phenomenon required was a barrier
to practical and low-cost applications. This all changed in 1986, when a new class of
ceramic superconductors was discovered that "superconducted" at higher temperatures.
The science of high-temperature superconductivity (HTS) was born, and along with it
came the prospect for an elegant technology that promises to "supercharge" the way
energy is generated, delivered, and used.
Capacitance
When two parallel plates of area A, separated by a small distance l, are charged by +Q, –
Q, an electric field develops between the plates
E = D/εε0
where D = Q/A. ε0 is called the vacuum permittivity and ε the relative permittivity, or
dielectric constant (ε = 1 for vacuum). In terms of the voltage between the plates, V = E
l,
V = Dl/εε0 = Q l/Aεε0 = Q / C
The dipole moment of a pair of positive and negative charges (+q and –q) separated at a
distance d is p = qd. If an electric field is applied, the dipole tends to align so that the
positive charge points in the field direction. Dipoles between the plates of a capacitor will
produce an electric field that opposes the applied field. For a given applied voltage V,
there will be an increase in the charge in the plates by an amount Q' so that the total
charge becomes Q = Q' + Q0, where Q0 is the charge of a vacuum capacitor with the
same V. With Q' = PA, the charge density becomes D = D0 E + P, where the polarization
P = ε0 (ε–1) E .
Types of Polarization
Electrons have much smaller mass than ions, so they respond more rapidly to a changing
electric field. For electric field that oscillates at very high frequencies (such as light) only
electronic polarization can occur. At smaller frequencies, the relative displacement of
positive and negative ions can occur. Orientation of permanent dipoles, which require the
rotation of a molecule can occur only if the oscillation is relatively slow (MHz range or
slower). The time needed by the specific polarization to occur is called the relaxation
time.
Dielectric Strength
Very high electric fields (>108 V/m) can free electrons from atoms, and accelerate them
to such high energies that they can, in turn, free other electrons, in an avalanche process
(or electrical discharge). This is called dielectric breakdown, and the field necessary to
start the is called the dielectric strength or breakdown strength.
Dielectric Materials
Capacitors require dielectrics of high ε that can function at high frequencies (small
relaxation times). Many of the ceramics have these properties, like mica, glass, and
porcelain). Polymers usually have lower ε.
14.6 Ferroelectricity
Ferroelectric materials are ceramics that exhibit permanent polarization in the absence of
an electric field. This is due to the asymmetric location of positive and negative charges
within the unit cell. Two possible arrangements of this asymmetry results in two distinct
polarizations, which can be used to code "0" and "1" in ferroelectric memories. A typical
ferroelectric is barium titanate, BaTiO3, where the Ti4+ is in the center of the unit cell and
four O2- in the central plane can be displaced to one side or the other of this central ion .
14.7 Piezoelectricity
Heat Capacity is a property that is indicative of a materials ability to absorb heat from
external surroundings; it represnts tha amount of energy required to produce a unit
temperature rise.In mathematical terms, the heat capacity C is expressed as follows:
C=dQ/dT
Where dQ is the energy required to produce a dT temperature change. Unit of heat
capacity is J/kg-K.
Over small temperature ranges, the linear nature of thermal expansion leads to expansion
relationships for length, area, and volume in terms of the linear expansion coefficient.
For metallic materials values in the range 10 x 10-6 to 30 x 10-6 K-1 are common, and the
thermal expansion of pure metals up to their melting points has been well characterised.
However data for engineering alloys at very high temperatures is often limited. This is
significant since there is generally a variation (usually an increase) in CTE with
temperature.
The thermal conductivity of a material is equivalent to the quantity of heat that passes in
unit time through unit area of a plate, when its opposite faces are subject to unit
temperature gradient (e.g. one degree temperature difference across a thickness of one
unit).
When a solid body is heated or cooled, the internal temperature distribution will depend
on its size and shape, the thermal conductivity pf the material and the rate of temperature
change. Thermal stresses may be established as a result of temperature gradients across a
body, which are frequently caused by rapid heating or cooling, in that the outside changes
temperature more rapidly than the interior.
Diamagnetism is a very weak form of magnetism that is nonpermanent and persists only
while an external field is being applied. It is induced by a change in the orbital motion of
electrons due to an applied magnetic field. The magnitude of the induced magnetic
moment is extremely small and in a direction opposite to that of the applied field.
paramagnetic material is one whose atoms do have permanent dipole moments, but the
magic of ferromagnetism is not active. If a magnetic field is applied to such a material,
the dipole moments try to line up with the magnetic field, but are prevented from
becoming perfectly aligned by their random thermal motion. Because the dipoles try to
line up with the applied field, the susceptibilities of such materials are positive, but in the
absence of the strong ferromagnetic effect, the susceptibilities are rather small, say in the
range to . When a paramagnetic material is placed in a strong magnetic field, it
becomes a magnet, and as long as the strong magnetic field is present, it will attract and
repel other magnets in the usual way. But when the strong magnetic field is removed, the
net magnetic alignment is lost as the dipoles relax back to their normal random motion.
16.2 Ferromagnetism:
Certain metallic materials possess a permanent magnetic moment in the absence of an
external field, and manifest very large and permanent magnetizations. These are the
characteristics of ferromagnetism, and they are displayed by the transition metals iron,
cobalt, nickel, and some of the rare earth metals. Permanent magnetic moments in
ferromagnetic materials result from atomic magnetic moments due to electron spin-
uncancelled electron spins as a consequence of the electron structure. There is also an
orbital magnetic moments contribution that is small in comparison to the spin moment.
Furthermore, in a ferromagnetic material, coupling interactions cause net spin magnetic
moments of adjacent atoms to align with one another, even in the absence of an external
field. The maximum possible magnetization or saturation magnetization Ms of a
ferromagnetic material represents the magnetization that results when all the magnetic
diploes in a solid piece are mutually aligned with the external field; there is also a
corresponding saturation flux density Bs.
16.3 Antiferromagnetism:
This phenomenon of magnetic moment coupling between adjacent atoms or ions occurs
in materials other than those that are ferromagnetic. In one such group, this coupling
results in an antiparallel alignment; the alignment of the spin moments of neighbouring
atoms or ions in exactly opposite directions is termed antiferromagentism. Manganese
oxide(MnO) is one such material that displays this behavior. Manganese oxide is a
ceramic material that is ionic in character, having both Mn and O ions.No net magnetic
moment is associated with O ions, since there is a total cancellation of both spin and
orbital moments. However, the Mn ions possesses s nrt magnetic moment that is
predominantly of spin origin.These Mn ions are arrayed in the crystal structure such that
the moments of adjacent ions are antiparallel. Obvioulsy, the opposing magnetic
moments cancel one another and as a consequence, the solid as a whole possesses no net
magnetic moment.
Ferrimagnetism
Some ceramics also exhibit a permanent magnetizations termed ferrimagentism. The
macroscopic magnetic characteristics of ferromagnets and ferrimagents are similar; the
distinction lies in the source of the net magnetic moments. The net ferrimagentic moment
arises from the incomplete cancellation of spin moments.
All electromagnetic radiation traverses a vacuum at the same velocity, that of light.
This velocity,c, is related to the electric permittivity of a vacuum and the magnetic
permeability of a vacuum through . Thus there is an association between the
electromagnetic constant c and these electrical and magnetic constants. Furthermore, the
frequency ν and wavelength λ of the electromagnetic radiation are a function of velocity
according to:
C= ν/λ
Frequency is expressed in terms of hertz(Hz), and 1 Hz=1 cycle per second. Ranges of
frequency for the various forms of electromagnetic radiation are also included in the
spectrum.
The electromagnetic spectrum covers a wide range of wavelengths and photon energies.
Light used to "see" an object must have a wavelength about the same size as or smaller
than the object. The ALS generates light in the far ultraviolet and soft x-ray regions,
which span the wavelengths suited to studying molecules and atoms.
the energy associated with light photons having short wavelengths is not reemitted as
visible light.
Refraction:
Light that is transmitted into the interior of transparent materials experiences decrease in
velocity and as result is bent at the interface; this phenomenon is termed refraction. The
index of refraction n of a material is defined as the ratio of the velocity in vacuum c to the
velocity in the medium ν , or
n=c/ν
The magnitude of n will depend on the wavelength of the light. This effect is graphically
demonstrated by the familiar dispersion or separation of a beam of white light into its
component colors by a class prism. Each color is deflected by a different amount as it
passes into and out of the glass, which results in the separation of colors. Not only does
the index of refraction affect the optical path of light, but also it influences the fraction of
incident light that is reflected at the surface. The phenomenon of refraction is related to
electronic polarization at the relatively high frequencies for visible light; thus the
electronic component of the dielectric constant may be determined from index of
refraction measurements.
Since the retardation of electromagnetic radiation in a medium results from electronic
polarization, the size of the constituent atoms or ions has a considerable influence on the
magnitude of this effect-generally, the larger an atom or ion, the greater will be the
electronic polarization, the slower the velocity and greater the index of refraction.
Reflection:
When light radiation passes from one medium into another having a different index of
refraction, some of the light is scattered at the interface between the two media even if
both are transparent. The reflectivity R represents the fraction of the incident light that is
reflected at the interface.
R=Ir/Io
Where Io and Ir are the intensities of the incident and reflected beams, respectively.Just
as the index of refraction of a solid depends on the wavelength of the incident light, so
does the reflectivity vary with wavelength.
Absorption:
Nonmetallic materials may be opaque or transparent to visible light; and, if transparent,
they often appear colored. In principle, light radiation is absorbed in this group of
materials by two basic mechanisms, which also influence the transmission characteristics
of these nonmetals. Absorption by electronic polarization is important only at light
frequencies in the vicinity of the relaxation frequency of the constituent atoms. The other
mechanism involves valence band-conduction band electron transitions, which depends
on the electron energy band structure of the material.
Transmission:
The phenomena of absorption, reflection and transmission may be applied to the passage
of light through a transparent solid. The fraction of incident light that is transmitted
through a transparent material depends on the losses that are incurred by absorption and
reflection. The sum of reflectivity R, absorptivity A and transmittivity T, is unity. Also,
each of of the variables R, A and T depends on light wavelength.
Luminescence
Some materials are capable of absorbing energy and then reemitting visible light in a
phenomenon called luminescence. Photons of emitted light are generated from electron
transitions in the solid. Energy is absorbed when an electron is promoted to an excited
energy; visible light is emitted when it false back to a lower energy state. The absorbed
energy may be applied as higher energy electrons or by heat, mechanical or chemical
energy. Furthermore, luminescence is classified according to the magnitude of the delay
time between absorption and reemission events.
Luminescence is "cold light", light from other sources of energy, which can take place at
normal and lower temperatures. In luminescence, some energy source kicks an electron
of an atom out of its "ground" (lowest-energy) state into an "excited" (higher-energy)
state; then the electron gives back the energy in the form of light so it can fall back to its
"ground" state.
There are several varieties of luminescence, each named according to what the source of
energy is, or what the trigger for the luminescence is.
electric lights, in which the electricity is used to produce heat, and it is the heat that in
turn produces light.
Photoconductivity
Lasers
All the radioactive electron transitions are spontaneous; that is, an electron falls from a
high energy state to a lower one without any external provocation. These transition events
occur independently of one another and at random times, producing radiation that is
incoherent; that is, the light waves are out of phase with one another. With
lasers,however,coherent light is generated by electron transitions initiated by an external
stimulus;in fact,”laser” is just the acronym for light amplification by stimulated emission
of radiation.
Applications of Lasers
The light beam produced by most lasers is pencil-sized, and maintains its size and
direction over very large distances; this sharply focused beam of coherent light is
suitable for a wide variety of applications. Lasers have been used in industry for cutting
and boring metals and other materials, and for inspecting optical equipment. In medicine,
they have been used in surgical operations. Lasers have been used in several kinds of
scientific research. The field of holography is based on the fact that actual wave-front
patterns, captured in a photographic image of an object illuminated with laser light, can
be reconstructed to produce a three-dimensional image of the object.
Lasers have opened a new field of scientific research, nonlinear optics, which is
concerned with the study of such phenomena as the frequency doubling of coherent light
by certain crystals. One important result of laser research is the development of lasers
that can be tuned to emit light over a range of frequencies, instead of producing light of
only a single frequency. Work is being done to develop lasers for communication; in a
manner similar to radio transmission, the transmitted light beam is modulated with a
signal and is received and demodulated some distance away. Lasers have also been used
in plasma physics and chemistry.
For years after its invention, the laser was spoken of as a solution without a problem.
That reputation soon disappeared as lasers found uses in a variety of industries. But now
several new lasers, particularly solid state instruments that operate at ultraviolet
wavelengths and those based on nonlinear materials, are finding uses in emerging areas.
Computing, telecommunications, and, in particular, medicine, stand to benefit from the
unique qualities of these new or improved systems.
Our current "age of technology" is the result of many brilliant inventions and discoveries,
but it is our ability to transmit information, and the media we use to do it, that is perhaps
most responsible for its evolution . Progressing from the copper wire of a century ago to
today’s fiber optic cable, our increasing ability to transmit more information, more
quickly and over longer distances has expanded the boundaries of our technological
development in all areas. Today’s low-loss glass fiber optic cable offers almost unlimited
bandwidth and unique advantages over all previously developed transmission media. The
basic point-to-point fiber optic transmission system consists of three basic elements: the
optical transmitter, the fiber optic cable and the optical receiver.
The Optical Transmitter: The transmitter converts an electrical analog or digital signal
into a corresponding optical signal. The source of the optical signal can be either a light
emitting diode, or a solid state laser diode. The most popular wavelengths of operation
for optical transmitters are 850, 1300, or 1550 nanometers.
The Fiber Optic Cable: The cable consists of one or more glass fibers, which act as
waveguides for the optical signal. Fiber optic cable is similar to electrical cable in its
construction, but provides special protection for the optical fiber within. For systems
requiring transmission over distances of many kilometers, or where two or more fiber
optic cables must be joined together, an optical splice is commonly used.
The Optical Receiver: The receiver converts the optical signal back into a replica of the
original electrical signal. The detector of the optical signal is either a PIN-type
photodiode or avalanche-type photodiode.
1. The ability to carry much more information and deliver it with greater fidelity than
either copper wire or coaxial cable.
2. Fiber optic cable can support much higher data rates, and at greater distances, than
coaxial cable, making it ideal for transmission of serial digital data.
3. The fiber is totally immune to virtually all kinds of interference, including lightning,
and will not conduct electricity. It can therefore come in direct contact with high voltage
electrical equipment and power lines. It will also not create ground loops of any kind.
4. As the basic fiber is made of glass, it will not corrode and is unaffected by most
chemicals. It can be buried directly in most kinds of soil or exposed to most corrosive
atmospheres in chemical plants without significant concern.
5. Since the only carrier in the fiber is light, there is no possibility of a spark from a
broken fiber. Even in the most explosive of atmospheres, there is no fire hazard, and no
danger of electrical shock to personnel repairing broken fibers.
6. Fiber optic cables are virtually unaffected by outdoor atmospheric conditions, allowing
them to be lashed directly to telephone poles or existing electrical cables without concern
for extraneous signal pickup.
7. A fiber optic cable, even one that contains many fibers, is usually much smaller and
lighter in weight than a wire or coaxial cable with similar information carrying capacity.
It is easier to handle and install, and uses less duct space. (It can frequently be installed
without ducts.)
8. Fiber optic cable is ideal for secure communications systems because it is very difficult
to tap but very easy to monitor. In addition, there is absolutely no electrical radiation
from a fiber.
How are fiber optic cables able to provide all of these advantages? This guide will
provide an overview of fiber optic technology – with sections devoted to each of the three
system components – transmitters, receivers, and the fiber cable itself. An appreciation of
the underlying technology will provide a useful framework for understanding the reasons
behind its many benefits.
The growing awareness of environmental issues has increased the attention focused on
the materials industry. There is a danger that this could give a negative picture,
highlighting examples where materials production and use has led to environmental
problems. In many of these cases, materials, additives and production methods were used
for very good materials engineering reasons before environmental concerns were
established. The more positive image of materials engineering that can be portrayed is
one where the industry is at the forefront of technical advances - not only to 'deal with
past mistakes', but also to drive sustainable and safe use of materials for the future.
The topic of 'Environmental Materials' is broad and can touch on some relatively in-depth
aspects of materials structure, chemical and physical properties, processing and design as
well as more general areas such as legislative, economic and social aspects. Interesting
topics within this area can be presented at a range of levels: for instance the sustainable
use of materials in the IT sector can be discussed by 11 year olds with as much
enthusiasm as by post-graduate students - although the latter would be expected to grasp
the chemical details of identifying brominated flame-retardants, whereas the former
would consider much simpler aspects, that are nonetheless important.
It could easily be argued that steel is a very sustainable material; it is abundant, takes
relatively little energy to extract and is easy to recycle, however people living near a
steelworks would argue against this. It is probably sensible to define such materials as
those that have distinct differences that achieve environmental benefit compared to
conventional materials. With this definition, the list would include:
The most exciting developments in Materials Science are in the realm of functional
materials, and many of these serve an environmentally-beneficial purpose, particularly in
the production of green energy.
These include:
o Solar-cell materials
o Fuel-cell technology
o Catalytic pollution control
The figure below schematically shows how the disparate areas under the heading of
'environmental materials' can be linked via a life cycle analysis approach.