CHAPTER 1

INTRODUCTION OF MATERIAL SCIENCE & ENGINEERING

Materials are probably more deep-seated in our culture than most of us realize.
Transportation, housing, clothing, communication, recreation and food production–virtually every
segment of our daily lives is influenced to one degree or another by materials. Historically, the
development and advancement of societies have been intimately tied to the member’s ability to
produce and manipulate materials to fill their needs.

Definition of Materials Science & Engineering

MATERIALS SCIENCE – involves investigating the relationships that exists between the structures and
properties of materials.

MATERIALS ENGINEERING – designing or engineering the structure to produce a predetermined set

of properties.

From a functional perspective, the role of a materials scientist is to develop or synthesize new
materials whereas a materials engineer creates new products or systems using existing materials and
to develop techniques for processing materials.

Most graduates in materials programs are trained to be both materials scientists and materials
engineer.

Components that are Involved in the Design, Production, and Utilization of Materials

Processing

 Major determinant of the structure of a material.

 The structure and properties of a material depend on how it is processed
Structure

 Arrangement of the internal components of a material

 Sub-atomic/Atomic – deals with atoms of a material and how they are arranged to give
molecules, crystals, etc.
 Microscopic/Microstructure – large groups of atom or molecules agglomerated together; can
strongly influence physical properties
 Macroscopic/Macrostructure – structural elements that may be viewed with the naked eye
Properties

 Material trait in terms of the kind and magnitude of response to a specific impose stimulus.
The properties of a material determine its usability and its engineering application.

Performance

 A material’s performance will be a function of its properties.

PROCESSING STRUCTURE PROPERTIES PERFORMANCE

 Properties of Solid Materials

Mechanical Properties

› Relate deformation to an applied load or force. Examples include stiffness, strength,

toughness, etc.

Electrical Properties

 For electrical properties such as conductivity & dielectric constant, the stimulus is an electric
field.

Thermal Properties

 The thermal behavior of solids can be represented in terms of heat capacity and thermal
conductivity.

Magnetic Properties

 Demonstrate the response of a material to the application of magnetic field.

Optical Properties

 The stimulus electromagnetic or light radiation

Deteriorative Properties

 Relate to the chemical reactivity of materials

Criteria on Material Selection

1. In-service conditions
 The properties required of the material
 Conditions to which the materials will be subjected
 On only rare occasions does a material possess the maximum or ideal combinations of
properties thus, it may be necessary to trade one characteristic for another. Ex: strength and
ductility.

2. Deterioration of material properties during operation

Ex: significant reduction in mechanical strength may result from exposure to elevated
temperatures or corrosive environments

3. Economic cost
 Finished product cost
 Expense incurred during fabrication to produce the desired shape

Classification of Materials

Metals

 Materials in this group are composed of one or more metallic elements (e.g., iron aluminum,
copper, titanium and nickel)
 Denser than ceramics and polymers
 Have large numbers of nonlocalized electrons; that is, these electrons are not bound to
particular atoms.
 These materials are relatively stiff and strong, yet ductile and are resistant to fracture.
Ceramics

 Compounds between metallic and nonmetallic elements (oxides, nitrites & carbides)
 Relatively strong and stiff – stiffness and strength are comparable to those of the metals but
highly susceptible to fracture
 More resistant to high temperatures and harsh environments than metals and polymers
 With regard to optical characteristics, ceramics may be transparent, translucent or opaque and
some oxide exhibit magnetic behavior

Polymers

 Many of them are organic compounds that are chemically based on carbon, hydrogen and
other nonmetallic elements
 Low density and extremely ductile and pliable
 Have the tendency to soften/decompose at modest temperatures. Low conductivity and are
nonmagnetic
 Have very large molecular structures, that often have the backbone of carbon atoms

Composites

 composed of two or more materials from the 3 categories

 Incorporate the best characteristics of each of the component materials

Ex.: fiber glass, carbon fiber-reinforced polymer

Advanced materials

Materials that are utilized in high-technology applications (e.g., electronic equipment, computers,
fiber-optic systems, spacecraft, aircraft and military rocketry) are termed advanced materials. These
advanced materials are typically traditional materials whose properties have been enhanced and also
newly developed, high performance materials.

• Semiconductors

• Biomaterials

• Smart materials

• Nano materials
 CHAPTER 2
ATOMIC STRUCTURE AND INTERATOMIC BONDING

ATOMIC STRUCTURE

PROTONS
Mass – 1.67 x 10^-27 kg
Charge – 1.602 x 10^ -19 C
ELECTRONS
Mass – 9.11 x 10^ -31 kg
Charge – (-) 1.602 x 10^ -19 C
NEUTRONS
Mass – 1.67 x 10^ -27 kg
Electrically neutral

A=Z+N

Atomic number (Z)

- number of protons and electrons
Atomic mass (A)
- sum of the masses of protons and neutrons(N)(variable)
Isotopes
- elements that have two or more different atomic masses
Atomic Weight
- weighted average of the atomic masses
- amu per atom or mass per mole
1 mole = 6.022 x 10^23

BOHR MODEL WAVE MECHANICAL MODEL

QUANTUM NUMBER
Principal quantum number (n)
n= 1,2,3,4 or K,L,M,N,O

Angular quantum number (l)

l= 0,1,2..(n-1) – describes the shape of the orbital (s,p,d,f )
l=0 ( s orbital) l=2 ( d orbital)
l=1 (p orbital) l=3 (f orbital)

Magnetic quantum number (m’s of l)

= -l..l
- determines the number of energy states for each subshell.

Spin quantum number (m’s of s)

= ½ or -½
Pauli Exclusion Principle
- every electron in an atom has a unique set of quantum numbers. NO two electrons in an atom can
have precisely the same four quantum numbers.

Electron Configurations

• When all the electrons occupy the lowest possible energies in accord with the foregoing
restrictions, an atom is said to be on its ground state.
• The electronic configuration or structure of an atom represents the manner in which these
states are occupied.
• Valence electrons are those that occupy the outermost shell (valence shell).
• These electrons participate in the bonding between atoms to form atomic and molecular
aggregates.
• Most of the chemical and physical properties of solids are usually based on their valence
electrons.
• Stable electronic configuration- the states within the outermost or valence electronic shell
are completely filled.
Examples: Neon, Argon, Krypton
• These elements are considered as inert, or noble gases which are virtually unreactive.

The Periodic Table

• In the periodic table the elements are arranged and situated with increasing atomic number,
in seven horizontal rows called period.
• Arranged in groups in such all the members of the group having the same valence electron,
as well as their physical and chemical properties.
• Group 0 – inert gases, which have filled electron shells and stable electronic configurations
• Group VIIA and VIA elements are one and two electrons deficient respectively.
• The group VIIA are sometimes termed as halogens.
• Group IA – alkali earth metals
• Group IIA – alkaline earth metals
• Group IIIB and IIB – termed as transition metals.
• Group IIIA, IVA and VA – display characteristics that are intermediate between the metals and
non-metals by virtue of their valence electron structures.
• Electropositive- elements indicating that they are capable of giving up their few valence
electrons.
• Electronegative- readily to accept electrons to form negatively charged ions, or sometimes
they share electrons with other atoms.
• Electronegativity increases left to right and bottom to top.
• Atoms are more likely to accept electrons if their outer shells are almost full and if they’re
less shielded from the nucleus.

Primary Interatomic Bonds

• Ionic bonding- always found in compounds that are composed of both metallic and
nonmetallic elements. Example: NaCl
• Covalent Bonding- type of bonding in which stable electronic configurations are assumed by
sharing of electrons between adjacent atoms. (Bonding between non-metals) Example: CH4,
H2
• Metallic Bonding- found in metals and their alloys. Metallic elements have one, two at most
three valence electrons.
-Formation of Electron Cloud
-Ion Cores
 Secondary Bonding or Vander waals Bonding

• weak in comparison to the primary or chemical ones

• exists between virtually all atoms or molecules. -evidenced for the inert gases(stable electron
structures and molecules that are covalently bonded Secondary bonding forces
• arise from atomic or molecular dipoles. Electric dipole
• exists when there is dome separation of positive and negative portions of an atom. Hydrogen
bonding
• a special type of secondary bonding that exists between some molecules that have hydrogen
as one of the constituents.

Fluctuating Induced Dipole Bonds

• maybe created or induced in an atom or molecule that is normally electrically symmetric.

• All atoms are experiencing constant vibrational motion that can cause
• instantaneous and short-lived distortions of this electrical symmetry for some of the atoms.
• the creation of small electric dipoles.

Polar Molecule-Induced Dipole Bonds

• molecules termed when permanent dipole moments exist in some molecules by virtue of an
asymmetrical arrangement of positively and negatively charged regions.
• can also induce dipoles in adjacent non-polar molecules
• a bond will form as a result of attractive forces b/w two molecules.
 CHAPTER 3
THE STRUCTURE OF CRYSTALLINE SOLIDS

Crystal Structure

• A crystalline material is one in which the atoms are situated in a repeating or periodic array
over large atomic distances; that is, long-range order exists, such that upon solidification, the
atoms will position themselves in a repetitive three-dimensional pattern, in which each atom
is bonded to its nearest-neighbor atoms.
• Those that do not crystallize, this long-range atomic order is absent these is called non-
crystalline or amorphous materials.
• Some of the properties of crystalline solids depend on the crystal structure of the material,
the manner in which atoms, ions, or molecules are spatially arranged.
• Crystalline structures, atoms (or ions) are thought of as being solid spheres having well-
defined diameters. This is termed the atomic hard-sphere model in which spheres
representing nearest-neighbor atoms touch one another.
• Lattice is used in the context of crystal structures; in this sense lattice means a three-
dimensional array of points coinciding with atom positions (or sphere centers).

Unit Cells
• Atomic order in crystalline solids indicates that small groups of atoms form a repetitive
pattern.
• Crystal Structures is often convenient to subdivide the structure into small repeat entities
called unit cells.
• Unit cells for most crystal structures are parallelepipeds or prisms having three sets of parallel
faces.
• Chosen to represent the symmetry of the crystal structure, wherein all the atom positions in
the crystal may be generated by translations of the unit cell integral distances along each of
its edges.
• Basic structural unit or building block of the crystal structure and defines the crystal structure
by virtue of its geometry and the atom positions within.

Metallic Crystal Structures

• The atomic bonding in this group of materials is metallic and thus non-directional in nature.
• There are minimal restrictions as to the number and position of nearest-neighbor atoms; this
leads to relatively large numbers of nearest neighbors and dense atomic packing for most
metallic crystal structures.
• For metals, using the hard-sphere model for the crystal structure, each sphere represents an
ion core.
• Three relatively simple crystal structures are found for most of the common metals: face
centered cubic, body-centered cubic, and hexagonal close-packed.

The Face-Centered Cubic Crystal Structure (FCC)

Face-centered cubic (FCC) crystal structure

• Crystal structure that is found for many metals has a unit cell of cubic geometry, with atoms
located at each of the corners and the centers of all the cube faces.
• The spheres or ion cores touch one another across a face diagonal; the cube edge length a
and the atomic radius R are related through a= 2R
• Each corner atom is shared among eight unit cells, whereas a face-centered atom belongs to
only two.
• Two other important characteristics of a crystal structure are the coordination number and
the atomic packing factor (APF).
• The APF is the sum of the sphere volumes of all atoms within a unit cell (assuming the atomic
hard-sphere model) divided by the unit cell volume.

• For the FCC structure, the atomic packing factor is 0.74, which is the maximum packing
possible for spheres all having the same diameter.

• Metals typically have relatively large atomic packing factors to maximize the shielding
provided by the free electron cloud.

The Body-Centered Cubic Crystal Structure (BCC)

• Another common metallic crystal structure has a cubic unit cell with atoms located at all eight
corners and a single atom at the cube center.

• Center and corner atoms touch one another along cube diagonals, and unit cell
length a and atomic radius R are related through

• Two atoms are associated with each BCC unit cell: the equivalent of one atom from the eight
corners, each of which is shared among eight unit cells and the single center atom, which is
wholly contained within its cell. Corner and center atom positions are equivalent.

• The coordination number is less for BCC than FCC, the atomic packing factor for BCC lower—
0.68 versus 0.74.

The Hexagonal Close-Packed Crystal Structure (HCP)

• The top and bottom faces of the unit cell consist of six atoms that form regular hexagons and
surround a single atom in the center.

• The equivalent of six atoms is contained in each unit cell; one-sixth of each of the 12 top and
bottom face corner atoms, one-half of each of the 2 center face atoms, and all 3 mid plane
interior atoms.

Polymorphism and Allotropy

• Polymorphism is when a material that can have more than one crystal structure.
• Allotropy is polymorphism for elemental solids.
• Prevailing crystal structure depends on both the temperature and the external pressure.
• Modification of the density and other physical properties accompanies a polymorphic
transformation.
Crystal Systems
• The concept of crystal system is used to classify crystal structures on the basis of unit cell
geometry—that is, unit cell edge lengths and inter axial angles.
• There are seven crystal systems: cubic, tetragonal, hexagonal, orthorhombic, rhombohedral
(trigonal), monoclinic, and triclinic.

Crystallographic Points, Directions, and Planes

• It is necessary to specify a particular point within a unit cell, a crystallographic direction, or
some crystallographic plane of atoms.
• The basis for determining index values is the unit cell, with a right-handed coordinate system
consisting of three (x, y, and z) axes situated at one of the corners and coinciding with the unit
cell edges.

Point Coordinates
• The position of any point located within a unit cell may be specified in terms of its coordinates
as fractional multiples of the unit cell edge lengths (i.e., in terms of a, b, and c).
• We specify the position of P in terms of the generalized coordinates q, r, and s where q is some
fractional length of an along the x axis, r is some fractional length of b along the y axis, and
similarly for s.

Crystallographic Directions

• A line between two points, or a vector.

• The following steps are used to determine the three directional indices:
1. A vector of convenient length is positioned such that it passes through the origin of the
coordinate system. Any vector may be translated throughout the crystal lattice without
alteration, if parallelism is maintained.

2. The length of the vector projection on each of the three axes is determined; these are
measured in terms of the unit cell dimensions a, b, and c.

3. These three numbers are multiplied or divided by a common factor to reduce them to the
smallest integer values.

4. The three indices, not separated by commas, are enclosed in square brackets, thus: [uvw].
The u, v, and w integers correspond to the reduced projections along the x, y, and z axes,
respectively.

Hexagonal Crystals

• Directional indices, which are obtained as described earlier, will be denoted by four indices, as
[uv tw]; by convention, the first three indices pertain to projections along the respective a1,
a2, and a3 axes in the basal plane.

Crystallographic Planes

• The orientations of planes for a crystal structure are represented in a similar manner.
• Hexagonal crystal system, crystallographic planes are specified by three Miller indices as (hkl).
• Any two planes parallel to each other are equivalent and have identical indices. The procedure
used to determine the h, k, and l index numbers is as follows:
1. If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be
established at the corner of another unit cell.
2. At this point the crystallographic plane either intersects or parallels each of the three axes; the
length of the planar intercept for each axis is determined in terms of the lattice parameters a,
b, and c.
3. The reciprocals of these numbers are taken. A plane that parallels an axis may be considered
to have an infinite intercept, and, therefore, a zero index.
4. If necessary, these three numbers are changed to the set of smallest integers by multiplication
or division by a common factor.
5. The integer indices, not separated by commas, are enclosed within parentheses, thus: (h k l).

Atomic Arrangements
• The atomic arrangement for a crystallographic plane, which is often of interest, depends on
the crystal structure.
• A “family” of planes contains all planes that are crystallographically equivalent— that is,
having the same atomic packing; a family is designated by indices that are enclosed in braces—
such as {100}.

Hexagonal Crystals
• Equivalent planes have the same indices; as with directions, this is accomplished by the Miller–
Bravais system.
• This convention leads to the four-index (hkil) scheme, which is favored in most instances
because it more clearly identifies the orientation of a plane in a hexagonal crystal.
• There is some redundancy in that i is determined by the sum of h and k through
i= - (h + k)
• The three h, k, and l indices are identical for both indexing systems.
•
Linear and Planar Densities
• Directional equivalency is related to linear density, for a particular material, equivalent
directions have identical linear densities.
• The corresponding parameter for crystallographic planes is planar density, and planes having
the same planar density values are also equivalent.

Close-Packed Crystal Structures

• Both face centered cubic and hexagonal close-packed crystal structures have atomic packing
factors of 0.74, which is the most efficient packing of equal-sized spheres or atoms.
• Both crystal structures may be generated by the stacking of these close-packed planes on top
of one another; the difference between the two structures lies in the stacking sequence.
A - centers of all the atoms in one close-packed plane
B - triangle vertex pointing up
C - remaining depressions with the down vertices
A second close-packed plane may be positioned with the centers of its atoms over either B or
C sites; at this point both are equivalent. Suppose that the B positions are arbitrarily chosen;
the stacking sequence is termed AB.
• The real distinction between FCC and HCP lies in where the third close-packed layer is
positioned.
• It is more difficult to correlate the stacking of close-packed planes to the FCC unit cell.
• Crystallographic planes and directions can specify in terms of directional and Miller indices.
• It is important to ascertain the atomic and ionic arrangements of particular crystallographic
planes.
• The crystal structures of a number of ceramic materials may be generated by the stacking of
close-packed planes of ions
Crystalline and Noncrystalline Materials

Single Crystals
• When the periodic and repeated arrangement of atoms is perfect or extends throughout the
entirety of the specimen without interruption, the result is a single crystal.
• Single crystals produced artificially and they are difficult to grow, because the environment
must be carefully controlled.
• Single crystals have become extremely important in many of our modern technologies, in
particular electronic microcircuits, which employ single crystals of silicon and other
semiconductors.
• Most crystalline solids are composed of a collection of many small crystals or grains; such
materials are termed polycrystalline.
• There exists some atomic mismatch within the region where two grains meet; this area, called
a grain boundary.

Anisotropy
• The physical properties of single crystals of some substances depend on the crystallographic
direction in which measurements are taken.
• This directionality of properties is termed anisotropy, and it is associated with the variance of
atomic or ionic spacing with crystallographic direction.
• Substances in which measured properties are independent of the direction of measurement
are isotropic.
• The modulus of elasticity values at [100], [110], and [111] orientations for several materials are
presented in Table.
• Sometimes the grains in polycrystalline materials have a preferential crystallographic
orientation, in which case the material is said to have a “texture.”
• The magnetic properties of some iron alloys used in transformer cores are anisotropic—that
is, grains (or single crystals) magnetize in a <100>-type direction easier than any other
crystallographic direction.
• Energy losses in transformer cores are minimized by utilizing polycrystalline sheets of these
alloys into which have been introduced a “magnetic texture”.
• Most of the grains in each sheet have a <100>-type crystallographic direction that is aligned
(or almost aligned) in the same direction, which is oriented parallel to the direction of the
applied magnetic field.

X-Ray Diffraction: Determination of Crystal Structures

• The atomic and molecular arrangements in solids has resulted from x-ray diffraction
investigations.
• X-rays are very important in developing new materials.

The Diffraction Phenomenon

• Diffraction occurs when a wave encounters a series of regularly spaced obstacles that
(1) are capable of scattering the wave,
(2) have spacings that are comparable in magnitude to the wavelength.
• Diffraction is a consequence of specific phase relationships established between two or more
waves that have been scattered by the obstacles.
• Diffraction is a diffracted beam as one composed of a large number of scattered waves that
mutually reinforce one another.
• X-ray diffractometry is used for crystal structure and interplanar spacing determinations.
• A beam of x-rays directed on a crystalline material may experience diffraction (constructive
interference) as a result of its interaction with a series of parallel atomic planes.

X-Ray Diffraction
• X-rays are a form of electromagnetic radiation that have high energies and short wavelength
on the order of the atomic spacings for solids.
• When a beam of x-rays impinges on a solid material, a portion of this beam will be scattered
in all directions by the electrons associated with each atom or ion that lies within the beam’s
path.

Diffraction Techniques
• Employs a powdered or polycrystalline specimen consisting of many fine and randomly
oriented particles that are exposed to monochromatic x-radiation.
• The diffractometer is an apparatus used to determine the angles at which diffraction occurs
for powdered specimens.

Noncrystalline Solids
• Non-crystalline solids lack a systematic and regular arrangement of atoms over relatively large
atomic distances.
• Amorphous (meaning literally “without form”), or super cooled liquids, inasmuch as their
atomic structure resembles that of a liquid.
• A crystalline or amorphous solid form depends on the ease with which a random atomic
structure in the liquid can transform to an ordered state during solidification.
• Amorphous materials are characterized by atomic or molecular structures that are relatively
complex and become ordered only with some difficulty.
• Polymers may be completely non-crystalline and semi crystalline consisting of varying degrees
of crystallinity.
 CHAPTER 4
IMPERFECTIONS IN SOLIDS

 Real crystals are never perfect: they always contain a considerable density of defects and
imperfections that affect their physical, chemical, mechanical and electronic properties.
 The existence of defects also plays an important role in various technological processes and
phenomena such as annealing, precipitation, diffusion, sintering, oxidation and others.
 All defects and imperfections can be conveniently considered under four main divisions: point
defects, line defects or dislocations, planar defects or interfacial defects, and volume defects.

Point Defects
 If the deviation occurs because of missing atoms, displaced atoms or extra atoms, the
imperfection is named as a point defect. Point defects are defects that occur only at or around
a single lattice point.

Stoichiometric Defects
 also called intrinsic or thermodynamic defects. Due to these defects the stoichiometry (i.e.,
the ratio of cations and anions as per the chemical formula) of the solid is not disturbed.
 Non-ionic solids show following defects:

(A) Vacancy Defects: This defect arises due to a vacancy created in the lattice Generally, this
defect arises on heating of a substance.
(B) Self-Interstitial Defect: Extra atom occupies a place outside the normal lattice position.
(C) Schottky Defect: Basically, it is a vacancy defect but in this case number of missing cations
and anions are equal so that electrical neutrality of the substance is maintained. This
defect is shown by the ionic compounds having cations and anions of almost similar size.
For example—NaCl.
(D) Frenkel Defect: Also called dislocation defect because in this defect cation (smaller ion)
is dislocated from its normal site to an interstitial site. Thus, vacancy defect arises at the
original site while interstitial defect at the new location. This defect is shown by the ionic
compounds having large difference in the size of ions.

Non-stoichiometric Defects

 when the stoichiometry of a substance is disturbed, this type of defects arises.

(A) Metal Excess Defect: This defect may arise due to either anionic vacancies or presence of extra
cations at interstitial sites.

F-Centres (Color Centres): These are the anionic sites occupied by the unpaired electrons. F-centres
impart the colours to the crystals as a result of excitation of electrons when they absorb energy from
the visible light falling on the crystals. For example:

—Yellow colours of NaCl crystals due to excess of Na.

—Pink colour of LiCl crystals due to excess of Li.

—Violet colour of KCl crystals due to excess of K.

(B) Metal Deficiency Defect: This defect arises due to the missing of a cation from its lattice site and
the presence of another cation having higher charge in the adjacent lattice site.

Impurities

Impurities (extrinsic point defects) - atoms which are different from the host.
Even the purest materials contain some impurities and the concentration of the impurities is, in most
real materials, comparable to or exceeds the concentration of the equilibrium intrinsic point defects.
May be intentional or unintentional
Examples: Carbon added in small amounts to iron makes steel, which is stronger than pure iron
Boron added to silicon change its electrical properties

Solid solutions are made of a host (the solvent or matrix) which dissolves the minor component
(solute). The ability to dissolve is called solubility.

Solvent: in an alloy, the element or compound present in greater amount

Solute: in an alloy, the element or compound present in lesser amount
Solid Solution:
• Homogeneous
• maintains crystal structure
• contains randomly dispersed impurities (substitutional or interstitial)

Substitutional Impurity- Substitutional impurities result from replacing the particle that should occupy
a lattice site with a different particle, such as substituting a K+ ion for a Na+ ion in NaCl.

Interstitial Impurity- When a particle forces its way into a hole between lattice sites, we get an
interstitial impurity.

Bulk or Volume Defects

Pores (Voids) – affects optical, thermal, electrical, and mechanical properties.
• As the porosity increases the thermal conductivity and electrical conductivity decreases.
• It reduces the strength of certain materials like ceramics.
Cracks (Fractures) – affects mechanical properties.

Types of Fractures

Ductile Fracture - is characterized by tearing of metal and significant plastic deformation. The ductile
fracture may have a gray, fibrous appearance. Ductile fractures are associated with overload of the
structure or large discontinuities.

Brittle Fracture - is characterized by rapid crack propagation with low energy release and without
significant plastic deformation. Brittle metals experience little or no plastic deformation prior to
fracture. The fracture may have a bright granular appearance.

Factors Affecting the Fracture of a Material

Stress concentration - is a location in an object where stress is concentrated.

Speed of loading - a sudden blow to the material may lead to fracture where the same stress applied
more slowly would not.
Temperature – many metals which are ductile at high temperatures are brittle at low temperatures.
Thermal shock - when hot water is poured into a cold glass it causes the glass to crack.
Foreign inclusions – affects electrical, mechanical, and optical properties.

• Inclusions are present in any steel to a greater or lesser extent according to the mixture and
conditions of production.
• Non-metallic inclusions in steel are foreign substances. They disrupt the homogeneity of structure,
so their influence on the mechanical and other properties can be considerable.
 Atomic Vibrations
• Every atom in a solid material vibrates rapidly about its lattice position. In a sense, these may be
thought as an imperfection or defect.
• Not all atoms vibrate at the same frequency and amplitude, nor with the same energy.
• At room temperature, a typical vibrational frequency is on the order of 1013 vibrations per second,
whereas the amplitude is a few thousandths of a nanometer.

Basic Concepts of Microscopy

• On occasion it is necessary or desirable to examine the structural elements and defects that
influence the properties of materials.
• Grain size and shape are only two features of what is termed the microstructure.
• Optical, electron, and scanning probe microscopes are commonly used in microscopy. These
instruments aid in investigations of the microstructural features of all material types.
• The photograph on which the image is recorded is called a photomicrograph.
• Several important applications of microstructural examinations are as follows: to ensure that the
associations between the properties and structure (and defects) are properly understood, to
predict the properties of materials once these relationships have been established, to design alloys
with new property combinations, to determine whether a material has been correctly heat-treated,
and to ascertain the mode of mechanical fracture.

Microscopic Techniques
Optical Microscopy - is a techniquee employed to closely view a sample through the magnification of
a lens with visible light.

Electron Microscopy - The electron microscope is a type of microscope that uses a beam of electrons
to create an image of the specimen. It is capable of much higher magnifications and has a greater
resolving power than a light microscope, allowing it to see much smaller objects in finer detail.

Transmission Electron Microscopy - is a microscopy technique in which a beam of electrons is

transmitted through a specimen to form an image. The specimen is most often an ultrathin section
less than 100 nm thick or a suspension on a grid.

Scanning Electron Microscopy - uses a focused beam of high-energy electrons to generate a variety
of signals at the surface of solid specimens. The signals that derive from electron-sample
interactions reveal information about the sample including external morphology (texture), chemical
composition, and crystalline structure and orientation of materials making up the sample.

Scanning Probe Microscopy - is a branch of microscopy that forms images of surfaces using a
physical probe that scans the specimen.
 CHAPTER 5
DIFFUSION

DIFFUSION - migration of solute molecules from higher concentration to lower concentration to

achieve equilibrium.
Diffusion Mechanism
The atoms in solid materials are in constant motion, rapidly changing position. 2 Conditions must meet:
1. Empty adjacent space.
2. Enough energy to break bond with its neighbour atom.

Factors Affecting Diffusion Diffusion Coating

Types of Diffusion Coating

Aluminizing

DIFFUSION
COATING Boronizing

Chormnizing

Diffusion Coating
ALUMINIZING
 high temperature chemical process whereby aluminium diffuses into the surface of the base
metal to form a metallurgical aluminide surface layer.
Aluminum Diffusion Coating Protects Against:
1. Metal Dusting
2. Sulfidation
3. Hot Corrosion
4. Oxidation

Properties of
Aluminium

Corrosive
Reflectivity Strength Machining Formability Zero toxicity
Resistance
 Materials suitable for Aluminizing

Mild steels

Cast
Nickel Iron
stainless
alloys
steels
Materials
suitable for
aluminizing

Nickel base Low alloy

alloy steels

BORONIZING
 sometimes referred to as boriding, is a diffusion coating that has a low co-efficient of friction
that is capable of retaining its high hardness at elevated temperatures.
Applications
 Boronised Glass bottle moulds to wear resistance
 Oil & gas field tubing (OCTG)

CHORMINIZING
 surface treatment carried out at elevated temperatures in which an alloy is formed by the
inward diffusion of chromium into the base metal.
Applications
 The swaged tube ends or "bottles" are chromized with a proprietary process that prevents
chromium diffusion to the portion to be rolled into the drum wall. We can supply either the
chromized bottles or the services to chromize the user's parts

Diffusion bonding
 solid-state welding technique used in metalworking, capable of joining similar and dissimilar
metals. It operates on the principle of solid-state diffusion, wherein the atoms of two solid,
metallic surfaces intersperse themselves over time.

Simplified Stages of Diffusion Bonding

Before the surfaces completely contact, asperities (very small
surface defects) on the two surfaces contact and plastically
deform. As these asperities deform, they interlink, forming
interfaces between the two surfaces.

Elevated temperature and pressure causes

accelerated creep in the materials; grain boundaries and
raw material migrate and gaps between the two
surfaces are reduced to isolated pores

Material begins to diffuse across the boundary of the

abutting surfaces, blending this material boundary and
creating a bond
 Diffusion Hardening
 Case hardening, or surface hardening, is the process of hardening the surface of a metal object
while allowing the metal deeper underneath to remain soft, thus forming a thin layer of harder
metal at the surface.

CARBURIZING
Case Hardening - diffuse carbon atoms into the host iron atoms at the surface.

Result:
 the presence of carbon(C) atoms makes iron(steel) harder.

NITRIDING
 a heat-treating process that diffuses nitrogen into the surface of a metal to create a case-
hardened surface.

Semiconductor Diffusion
P-N JUNCTION
The electrons from the n type material will diffuse into the p type material (and vice versa for holes).
After crossing the junction, the electrons in the p type (holes in n type) material are minority carriers
with a recombination lifetime

ELECTRONIC STRUCTURES AND PROCESSES

The distribution of electrons among the orbitals of an atom is called the electronic structure
or electronic configuration.

Electron Configuration - arrangement of electrons within their respective sublevels.

2p6
2 – principal energy level
p – type of orbital
6 - number of electrons in sublevel orbitals

Mnemonic Device - used to find the electronic configuration.

Orbitals

Energy Levels of Electron

 According to Bohr, the energies of electrons in an atom are quantized.
 The wave-mechanical model of the atom also predicts discrete principal energy levels within
the atom.

The Principal Quantum Number n

 The first four principal energy levels of the hydrogen atom.
 Each level is assigned a principal quantum number n.
 As n increases, the energy of the electron increases.
 Each principal energy level is subdivided into sublevels.
 An atomic orbital can hold a maximum of two electrons.
  The two electrons that occupy an atomic orbital must have opposite spins.
 An electron can spin in one of two possible directions represented by ↑ or ↓.
S Sublevel

 An s orbital is spherical in shape.

 The spherical surface encloses a space where there is a 90% probability that the electron may
be found.
P Sublevel

 Each p orbital has two lobes.

 Each p orbital can hold a maximum of two electrons.
 A p sublevel can hold a maximum of 6 electrons.

D Sublevel

 The five d orbitals all point in different directions.

 Each d orbital can hold a maximum of two electrons.
 A d sublevel can hold a maximum of 10 electrons.

Atomic Structure of the First 18 Elements

To Determine the Electronic Structures of Atoms, the following guidelines are used:

1. No more than two electrons can occupy one orbital.

2. Electrons occupy the lowest energy orbitals available. They enter a higher energy orbital
only after the lower orbitals are filled.
3. For the atoms beyond hydrogen, orbital energies vary as s<p<d<f for a given value of n.
4. Each orbital in a sublevel is occupied by a single electron before a second electron enters.
For example, all three p orbitals must contain one electron before a second electron enters a
p orbital.

AUFBAU Principle
 AUFBAU is a German term that means "building up." As protons are added one by one to the
nucleus to build up the elements, electrons are likewise added to the orbital.
Hund’s Rule of Maximum Multiplicity
 Every orbital in a subshell is singly occupied with one electron before any orbitals is doubly
occupied and all electrons in singly occupied orbitals have the same spin.
 Applications of Electronic Structures and Processes
ORGANIC CHEMISTRY - generally the second course sequence for students majoring in chemistry or
chemical engineering.
FUNDAMENTALS OF STRUCTURE-REACTIVITY RELATIONSHIPS - from their first courses in chemistry,
all students have at least a rudimentary knowledge of acids as proton donors.
PHYSICAL CHEMISTRY - the physical chemistry curriculum can be divided into the following major
segments: thermodynamics and thermochemistry, chemical kinetics, and quantum chemistry.
THERMO CHEMISTRY - an important topic in physical chemistry is the ability to obtain
thermochemical information on unstable species or reaction intermediates and transition state
structures.
CHROMATOGRAPHY - describe how electronic structure computations can be used effectively in
developing a student’s understanding of chromatographic separations

Electrical Conductivity
 Property that is used to describe how well materials allow electrons to flow.
Conductor is a material that has a high electrical conductivity.
Insulator is a material that has a low electrical conductivity.
Rank Metal
1 Silver
2 Copper
3 Gold
4 Aluminum
5 Zinc
6 Nickel
7 Brass
8 Bronze
9 Iron
10 Platinum
11 Carbon Steel
12 Lead
13 Stainless Steel

Factors Affecting Electrical Conductivity

TEMPERATURE – increasing the temperature causes thermal excitation of the atoms and decreases
conductivity (increases resistivity).
IMPURITIES – Adding an impurity to a conductor decreases its conductivity.
CRYSTAL STRUCTURE AND PHASES – if there are different phases of a material, conductivity will
slow slightly at the interface and may be different from one structure than another.
ELECTROMAGNETIC FIELDS – Conductors can generate their own electromagnetic fields when
electricity run to them. External electromagnetic fields can produce magnetoresistance, which can
slow the flow of current.
 CHAPTER 6
MECHANICAL PROPERTIES OF METALS

Metals can be processed into various shapes by deforming them plastically under the application
of external forces. The effects of these forces on material behavior are described in this chapter,
including:

 Types of tests for determining the mechanical behavior of materials.

 Elastic and plastic features of stress-strain curves and their significance.
 Relationships between stress and strain and their significance, as influenced by temperature
and deformation rate.
 Characteristics of hardness, fatigue, creep, impact, and residual stresses, and their role in
materials processing.
 Effects of inclusions and defects in the brittle and ductile behavior of metals.
 Why and how materials fail when subjected to external forces.

Tension Test

 Strength
 Ductility
 Toughness
 Elastic Modulus
 Strain-hardening capability

Test Specimen

 Usually solid and round

 Original Gauge length lo
 Cross-sectional area Ao
TENSION

 Stress-strain curves

Linear elastic: elongation in the specimen that is proportional to the applied load.

Engineering stress: the ratio of the applied load P, to the original cross-sectional area, Ao, of the
specimen.

- Engineering stress equation: σ = P/Ao

- Engineering strain equation: e = (l-lo)/lo

Yield Stress - the stress at which permanent (plastic) deformation occurs.

Permanent (plastic) deformation - stress and strain are no longer proportional.

Ultimate tensile strength (UTS) - the maximum engineering stress.

 If the specimen is loaded beyond its UTS it begins to “neck.”

 Fracture stress: the engineering stress at fracture.
 Modulus of elasticity: ration of stress to strain in the elastic region.
 Modulus of elasticity equation: E = σ/e
 This linear relationship is known as Hooke’s Law.
 Poisons Ratio: the ratio of the lateral strain to the longitudinal strain.

DUCTILITY

 extent of plastic deformation that the material undergoes before fracture.

Two measures of ductility:

- Total elongation: (lf-lo)/lo x 100%

- Reduction of Area: (Ao-Af)/Ao x 100%

True Stress and True Strain

True-stress - ratio of the load, P, to the instantaneous cross-sectional area, A, of the specimen.

True-strain - the sum of all the instantaneous engineering strains.

- True-stress equation: σ = P/A

- True-strain equation: e = ln(l/lo)

Strain at Necking in a Tension Test

 True-strain at necking is equal numerically to the strain-

hardening exponent, n, of the material.

Temperature Effects

 As temperature increases:
- Ductility and toughness increase.
- Yield stress and the modulus of elasticity decrease.
 Temperature also affects the strain-hardening exponent of most metals, in that n decreases
as temperature increases.

Rate of Deformation Effects

 Some machines form materials at low speeds.

- Hydraulic Presses
 Some Machines form materials at high speeds.
- Mechanical Presses
 Deformation rate: the speed at which a tension test is being carried out, in units of m/s or
ft/min.
 Strain rate: a function of the specimen length.
 Short specimens stretch more during the same time period than a long specimen would.

Effects of Temperature and Strain

 Sensitivity of strength-to-strain rate increases with temperature.
 Increasing the strain rate increases the strength of the material (strain-rate hardening).
 The slope of these curves is called the strain-rate sensitivity exponent.
 The relationship between strength and strain is represented by: σ= Cem
 C is the strength coefficient and e is the true strain rate. m is the slope of the graph.

Superplasticity
 Refers to the capability of some materials to undergo large, uniform elongation prior to
necking and fracture.
 This elongation can be as long as 200% to 2000% of the original length.
 Common items that demonstrate this: bubble gum, glass (at high temp) and thermo plastics.

- Because of this capability, some materials can be formed into complex shapes such as beverage
bottles and even neon advertisement signs.

Other Deformation Effects

 Hydrostatic Pressure: pressure due to weight of a fluid.

 Exposing some types of metals to high radiation is known to increase yield stress, tensile
strength, and hardness. However, it decreases ductility and toughness.
  Increasing hydrostatic pressure can increase the strain at fracture of materials.

- Billet: A semi-finished form of steel that is used for long products such as bars and channels.

- Creating hydrostatic pressure on a billet can turn 1 m of billet into 14 km of wire.

Compression

 Many operations in manufacturing, especially with forging, rolling, and extrusion, are
performed with the material being subjected to compressive forces.

COMPRESSION TEST

 A specimen is subjected to a compressive load.

 Carried out by compressing a solid cylindrical specimen between two well-lubricated flat dies.
 The cylindrical specimen’s surface begins to bulge, known as barreling.

DISK TEST

 Compression test developed for brittle materials such as ceramics and glass.
 A disk-shaped specimen is loaded between to solid platens. Tensile stresses build up
perpendicular to the centerline along the disk, fracture begins, and the disk will split vertically.
 Tensile stress from this test can be calculated with the following equation: σ = 2P/dt; P is load
at fracture, d is diameter of disk, t is thickness.

TORSION TEST

 In addition to tension and compression, a work-piece may be subjected to shear strains.

- Punching holes in sheet metal.
- Metal cutting.
 Torsion test used for determination of properties in “shear.” Usually performed on a thin
tubular specimen.
 Shear stress can be calculated with formula: T/2  r2t
- T is torque, r is average radius of tube, t is thickness of tube.
 Shear strain is calculated with formula: rФ/l
- r is radius of tube, Ф is angle of twist in radians, and l is length of tube.
 The ratio of the shear stress to the shear strain in the elastic range is known as the shear
modulus or modulus of rigidity.
 The angle of twist, Ф, to fracture in the torsion of solid round bars and elevated temp can help
estimate forge-ability of metals.

BENDING

 Preparing specimens from brittle materials, such as ceramics and carbides, is difficult because
of problems in shaping and machining them to certain dimensions.
 The most common test for brittle materials is the bend or flexure test.

BEND / FLEXURE TEST

 Rectangular specimen supported at its ends.

 Load is applied vertically at 1 or 2 pts.
 The stress at fracture in bending is known as the modulus of rupture, flexural strength, or
transverse rupture strength.

HARDNESS

 Commonly used property which gives indication of the strength and resistance to scratch and
wear of a material/specimen.

- Resistance to permanent indentation.

- Hardness is not a fundamental property because indentation depends on shape of indenter and load
applied.

BRINELL TEST

 J. A. Brinell 1900
 Involves pressing a steel or carbide ball of 10mm against a surface with various loads. - 500,
1500, or 3000 kg
 Measures diameter of indentation.
 Harder surfaces have small indentation while softer surfaces have larger indentation.

ROCKWELL TEST

 S. P. Rockwell 1922
 Test measures depth rather than diameter of indentation.
 Diamond indenter presses against surface with minor load and then major load.

- The difference in depths of penetration is a measure of the hardness of material.

VICKERS TEST

 Developed in 1922.
 Comparable to Brinell Test except using a pyramid shaped diamond to make indentation.
 Lighter loads than Brinell Test - From 1 to 120 kg

KNOOP TEST

 Developed in 1939.
 Comparable to Brinell and Vickers test.
 Uses an elongated pyramid shaped diamond to make indentations.
 Uses very light loads.

- From 25 g to 5 kg.

 Known as a micro-hardness test because of the lights loads.

- Suitable for very small or very thin specimens.

 Test also used for measuring the hardness of individual grains and components in a metal alloy.

MOHS HARDNESS TEST

 Developed by F. Mohs in 1822.

 Test based on capability of one material to scratch another.
 Each material can scratch all materials below it with a lesser hardness.
 Based on a scale of 1 to 10.

SCLEROSCOPE

 Instrument with diamond-tipped hammer.

 Hammer is dropped from a certain height.
 Hardness is related to the rebound of the indenter.
 Small and portable.

DUROMETER

 Used to test hardness of plastics, rubbers, and other soft materials.

 An indenter is pressed against the surface and then a constant load is applied rapidly.
 Hardness is measured based on depth of indent after 1 second.
 CHAPTER 12
STRUCTURES AND PROPERTIES OF CERAMICS

CERAMICS

 The word ceramic is originated from Greek word “keromikos”, which means ‘burnt stuff’.
 compounds of metallic and non-metallic elements.
 Are wide-ranging group of materials whose ingredients are clays, sand and feldspar.
 Are Inorganic non-metallic materials obtained by the action of heat and subsequent cooling.
 Always composed of more than one element (e.g., Al2O3, NaCl, SiC, SiO2)
 Bonds are partially or totally ionic, and can have combination of ionic and covalent bonding
 Generally hard and brittle
 Generally electrical and thermal insulators
 Can be optically opaque, semi-transparent, or Transparent

Crystal Structures
 contains at least 2 and often 3 or more atoms
 usually compounds between metallic ions (e.g. Fe, NI, Al) -called cations - and non-metallic ions
(e.g. O, N, Cl) -called anions
 Bonding will usually have some covalent character but is usually mostly ionic
Stable ceramic crystal structures: anions surrounding a cation and are all in contact with that
cation.

For a specific coordination number there is a critical or

minimum cation anion radius ratio rC/rA for which this
contact can be maintained.

Examples of crystal structures in ceramics: Rock Salt Structure, Cesium Chloride Structure

Silicate Ceramics
 Silicates are materials composed primarily of silicon and oxygen.
Carbon
 Carbon is an element that exists in various polymorphic forms, as well as in the amorphous
state.

Diffusion in Ionic Materials

 Diffusion in ionic materials normally occurs by a vacancy mechanism; localized charge
neutrality is maintained by the coupled diffusive motion of a charged vacancy and some
other charged entity.

Ceramic Phase Diagrams

 The general characteristics of ceramic phase diagrams are similar to those for
metallic systems.
 These diagrams are especially useful in assessing the high-temperature performance of
ceramic materials.

Mechanical Properties of Ceramics

BRITTLE FRACTURE OF CERAMICS

 At room temperature, both crystalline and noncrystalline ceramics almost always fracture
before any plastic deformation can occur in response to an applied tensile load.
 It consists of the formation and propagation of cracks through the cross section of material in
a direction perpendicular to the applied load.
 Crack growth in crystalline ceramics may be either transgranular (through the grains) or
intergranular (along grain boundaries).
 The measure of a ceramic material’s ability to resist fracture when a crack is
present is specified in terms of fracture toughness.
Stress raisers

 Very small and omnipresent flaws in the material. May be minute surface or interior cracks
(microcracks), internal pores, and grain corners, which are virtually impossible to eliminate or
control.

Fractography of Ceramics

 A fractographic study involves examining the path of crack propagation as well as microscopic
features of the fracture surface.
 Materials that can be used are inexpensive materials such as magnifying glass or low power
stereo binocular optical microscope.

For brittle ceramic materials, schematic representations of crack origins and configurations that result
from (a) impact (point contact) loading, (b) bending, (c) torsional loading, and (d) internal pressure.

During propagation, a crack accelerates until a critical velocity is achieved; Upon reaching this critical
velocity, a crack may branch, a process that may be successively repeated until a family of cracks is
produced.

Mirror Region - The crack surface that formed during the initial acceleration stage of propagation

Stress–Strain Behavior

Elastic Behavior
 The elastic stress–strain behavior for ceramic materials using these flexure tests is similar to
the tensile test results for metals: a linear relationship exists between stress and strain.

Mechanisms of Plastic Deformation

Crystalline Ceramics
 Plastic deformation occurs, as with metals, by the motion of dislocations. One reason for the
hardness and brittleness of these materials is the difficulty of slip (or dislocation motion).

Noncrystalline Ceramics
 These materials deform by viscous flow, the same manner in which liquids deform; the rate of
deformation is proportional to the applied stress.

Viscosity is the measure of a noncrystalline material’s resistance to deformation.

Miscellaneous Mechanical Considerations

Influence
 Porosity can be generated through the appropriate selection of raw materials, the
manufacturing process, and in some cases through the use of additives.
 This allows closed and open pores to be created with sizes from a few nm up to a few µm.

Hardness
 One beneficial mechanical property of ceramics is their hardness, which is often utilized when
an abrasive or grinding action is required; in fact, the hardest known materials are ceramics.

Creep
 Often ceramic materials experience creep deformation as a result of exposure to stresses
(usually compressive) at elevated temperatures.
 In general, the time–deformation creep behavior of ceramics is similar to that of metals;
 However, creep occurs at higher temperatures in ceramics.
 High-temperature compressive creep tests are conducted on ceramic materials to ascertain
creep deformation as a function of temperature and stress level.
 CHAPTER 13
APPLICATIONS AND PROCESSING OF CERAMICS

TYPES AND APPLICATION OF CERAMICS

Glasses

 They are non-crystalline silicates containing other oxides, notably CaO, Na2O, K2O and Al2O2,
which influence the glass properties.
 The two prime assets of this materials are their optical transparency and the relative ease with
which they may be fabricated.

Glass Ceramics

 Glass ceramics are fine-grained polycrystalline materials formed from inorganic glasses by the
proper high-temperature heat treatment.

Characteristics of glass ceramics:

 Relatively high mechanical strengths

 Low coefficients of thermal expansion
 Relatively high temperature capabilities
 Good dielectric properties
 Good biological compatibility
 Some glass ceramics may be made optically transparent, others are opaque.

Applications of glass ceramics:

 Conventional glass forming techniques may be used conveniently in the mass production of
nearly pore-free ware.
 The most common uses for these materials are as ovenware, tableware, oven windows, and
range tops –primarily because of their strengths and excellent resistance to thermal shock.
 Also serve as an electrical insulator and as substrates for printed circuit boards and for heat
exchangers and regenerators.
 Clay Products

Structural clay products

• Building bricks
• Tiles
• Sewer pipes
• Structural integrity is important

Whitewares
• Porcelain
• Pottery
• Tableware
• China
• Sanitary ware

Many of this clay products also contain nonplastic ingredients, which influence the changes that
take place during the drying and firing processes.

Refractories

Properties
 The capacity to withstand high temperatures without melting or decomposing
 The capacity to remain inactive and inert when exposed to severe environments
 The ability to provide thermal insulations

Applications:
 Furnace linings for metal refining
 Glass manufacturing
 Metallurgical heat treatment
 Power generation

1. Fireclay Refractories
 The primary ingredients for the fireclay refractories are high purity fireclays, alumina and silica
mixtures usually containing between 25 and 45wt% alumina.
 Fireclay bricks are used primarily in furnace construction to confine hot atmospheres, and to
thermally insulate structural members from excessive temperature.

2. Silica Refractories
• Also called acid refractories
• Prime ingredient –silica
• Well known for their high-temperature load-bearing capacity
• Commonly used in the arched roofs of steel and glass making furnaces
• Also resistant to slags that are rich in silica (acid slags) and are often used as containment
vessels for them.
3. Basic Refractories
• The refractories that are rich in periclase, or magnesia, are termed basic; they may also contain
calcium, chromium and iron compounds.
• Find extensive use in some steel-making open hearth furnaces.

4. Special Refractories
• Relatively expensive
Abrasives
 Used to wear, grind or cut away other material, which is softer.
 Diamonds both natural and synthetic, are utilized as abrasives; however, they are relatively
expensive.

More common ceramic abrasives:

 Silicon carbide
 Tungsten carbide
 Aluminum oxide
 Silica sand

Abrasives are used in several forms –bonded to grinding wheels, as coated abrasives, and as
loose grains.

Cements

 These materials when mixed with water, form a paste that sets and hardens.
 One important difference from other materials is that the cementitious bond develops at room
temperature.
 Portland cement- consumed in most cases
- produced by grinding and intimately mixing clay and lime-bearing minerals in the proper
proportions and then heating the mixture in a rotary kiln –” calcination”.
- termed hydraulic cement because its hardness develops by chemical reactions with
water.

Advanced Ceramics

1. Microelectromechanical System (MEMS)

 Are miniature “smart” systems consisting of a multitude of mechanical devices that are
integrated with large numbers of electrical elements on a substrate of silicon.
 There are some limitations to the use of silicon in MEMS. Silicon has a low fracture
toughness and a relatively low softening temperature and is highly active to the presense
of water and oxygen.

Practical MEMS application –accelerometer (accelerator/decelerator sensor)

Potential MEMS application –electronic displays, data storage units, energy conversion
devices, chemical detectors and microsystems for DNA amplification and identification

2. Optical Fibers

 made of extremely high-purity silica

 advanced ceramic materials that is a critical component in our modern optical
communications systems

3. Ceramic Ball Bearings

 silicon nitride (Si3N4) balls have begun replacing steel balls in a number of applications
 “Hybrid bearing” – the combination of ceramics balls and steel races
 Some applications with the use of hybrid bearing:

 Inline skates
 Bicycle
 Electric motors
 Machine tool spindles
 Medical hand tool
 Chemical equipment

Fabrication and Processing of Ceramics

Several specific points that are important in the fabrication of glasses:

1. The melting point corresponds to the temperature at which the viscosity is 10 Pa•s (100 P);
the glass is fluid enough to be considered liquid.
2. The working point represents the temperature at which the viscosity is 103 Pa•s (104 P); the
glass is easily deformed at this viscosity.
3. The softening point, the temperature at which the viscosity is 4×106 Pa•s (4×107 P), is the
maximum temperature at which a glass piece is may be handled without causing significant
dimensional alterations.
4. 4. The annealing point is the temperature at which the viscosity is 1012 Pa•s (1013P); at this
temperature, atomic diffusion is sufficiently rapid that any residue stresses may be removed
within about 15 mins.
5. 5. The strain point corresponds to the temperature at which the viscosity becomes 3×1013
Pa•s (3×1014 P); for temperatures below the strain point, fractures will occur before the
onset of plastic deformation. The glass transition temperature will be above the strain point.

Glass Forming

Methods to fabricate glass products:

1. Pressing- fabrication of relatively thick-walled pieces (plates and dishes). The glass piece is
formed by pressure application in a graphite-coated cast iron most having the desired shape; the
mold is ordinary heated to ensure an even surface.

2. Blowing- some glass blowing is done by hand, especially for art objects, the process has been
completely automated for the production of glass jars, bottles, and light bulbs.
3. Drawing- used to form long glass pieces such as sheet, rod, tubing, and fibers which have a
constant cross section

4. Fiber Forming- fibers are formed by drawing the molten glass through many small orifices at
the chamber base

Heat-treating Glasses

1. Annealing

- When a ceramic material is cooled from an elevated temperature, internal stresses (thermal
stress) may occur as a result of the difference in cooling rate and thermal contraction
between the surface and interior regions. Elimination/reduction in the stress magnitude is
possible by annealing heat treatment in which the glass ware is heated to the annealing
point, then slowly cooled to room temperature.

2. Glass Tempering

 Thermal tempering- the glassware is heated to a temperature above the glass transition
region yet below the softening point
 Tempered glass is used for applications in which high strength is important; these include
large doors and eyeglass lenses.

Fabrication and Processing of Clay Products

The characteristics of clay:

 Hydroplasticity- when water is added to clay mineral, they become very plastic
 Clay fuses or melts over a range of temperature; thus a dense and strong ceramic piece may
be produced during firing without complete melting such that the desired shape is
maintained.
 Clays are aluminosilicates.
 Crystal structures for the clay minerals are relatively complicated; however, one prevailing
characteristics is a layered structure.

Composition of Clay Products

 Some of the clay products also contain some nonplastic ingredient: the nonclay minerals
include flint or finely ground quartz, and a flux such as feldspar.
 Quartz- used as a filler material, being inexpensive, relatively hard and chemically unreactive
 Feldspar- fluxing agents
 A typical porcelain might contain approximately 50% clay, 25% quartz and 25% feldspar
 Fabrication Techniques

1. Hydroplastic Forming

 Extrusion
 a stiff plastic ceramic mass is forced through. A die orifice having the desired cross-sectional
geometry
 Similar to the extrusion of metals
 Brick, pipe, ceramic blocks and tiles

2. Slip Casting - a slip (suspension of clay and other minerals in water) is poured into a porous
mold. As water is absorbed into the mold, a solid layer is deposited on the inside of the mold
wall.

Drying and Firing

 After forming a clay based body must be first dried and then fired at an elevated
temperature to reduce porosity and enhance strength.

Powder Pressing

 Powder pressing is used to fabricate both clay and nonclay compositions, including electronic
and magnetic ceramics as well as some refractory brick products.
 Basic powder-pressing procedures:
1. Uniaxial pressing- the powder is compacted in a metal die by pressure that is applied in a
single direction
2. Isostatic pressing- the powdered material is contained in a rubber envelope and the pressure
is applied by a fluid, isostatically
3. Hot pressing
Tape Casting

With tape casting, a thin sheet of ceramic of uniform thickness is formed from a slip that is
spread onto a flat surface using a doctor blade. This tape is then subjected to drying and firing
operations.
 CHAPTER 17
CORROSION AND DEGRADATION OF MATERIALS

Corrosion
Deterioration and loss of a material and its critical properties due to chemical, electrochemical and
other reactions of the exposed material surface with the surrounding environment.

Electrochemical Considerations
For metallic materials, corrosion process is normally electrochemical.
 There is a transfer of electrons from one chemical species to another. Known as Redox
Reactions.
e-

X Y

Redox Reactions

OXIDATION is LOSS (OIL) of electrons

REDUCTION is GAIN (RIG) of electrons

Oxidation Reaction

Oxidation reaction for Metal (M)

M → Mn+ + ne-
Examples in which metals oxidize are:
Fe → Fe2+ + 2e-
Al → Al3+ + 3e-

• An overall electrochemical reaction must consist of at least one oxidation and one reduction
reaction.
• The individual oxidation and reduction reactions are termed HALF-REACTIONS.
• If no other oxidation or reduction reactions occur, the total electrochemical reaction is just the
sum of the two reactions.

Electrode Potentials
• In an electrochemical cell, an electric potential is created between two dissimilar metals.
• This potential is a measure of the energy per unit charge which is available from the
oxidation/reduction reactions to drive the reaction.

Electrochemical Cell
• an apparatus that is used to generate electricity from a spontaneous redox reaction or,
conversely, that uses electricity to drive a nonspontaneous redox reaction

Standard EMF Series

• An electromotive force series (EMF series) is a metal's ranking in respect to inherent reactivity.
• This series is helpful in determining the tendency of a metal to release energy and corrode.

Galvanic Series
• The galvanic series plays a vital role in determining and preventing corrosion.
• Also known as the "electropotential series"
• This series identifies semi-metal and metal nobility.
• A more realistic and practical ranking
 Environmental Effects
• The variables in the corrosion environment can have decided influence on the corrosion
properties of the materials that are in contact with it. These variables include:
- fluid velocity
- temperature
- composition

Forms of Corrosion
• It is convenient to classify corrosion according to the manner in which it is manifest Metallic
corrosion is sometimes classified into eight forms.

UNIFORM ATTACK
• form of corrosion that is more or less uniformly distributed over the entire exposed surface of
a metal
Examples: rusting of steel and iron and the tarnishing of silverware.

Prevention:
 Use thicker materials for corrosion allowance
 Use paints or metallic coatings such as plating, galvanizing or anodizing
 Use Corrosion inhibitors or modifying the environment

GALVANIC CORROSION
• occurs when two metals or alloys having different compositions are electrically coupled while
exposed to an electrolyte
Example: steel screws corrode when in contact with brass in a marine environment

Prevention:
• Select metals/alloys as close together as possible in the galvanic series.
• Insulate dissimilar metals wherever practical
• Apply coatings with caution. Paint the cathode (or both) and keep the coatings in good
repair on the anode.

PITTING
• also a type of very localized corrosion attack in which small pits or holes form the top of
horizontal surfaces.

Prevention:
• Proper selection of materials with known resistance to the service environment
• Control pH, chloride concentration and temperature

INTERGRANULAR CORROSION
• occurs preferentially along grain boundaries for specific metals/alloys (e.g., some stainless
steels) and in specific environments.

Prevention:
• subjecting the sensitized material to a high-temperature heat treatment in which all the
chromium carbide particles are redissolved,

Example: welding of stainless steels, when it is often termed weld decay

SELECTIVE LEACHING
• found in solid solution and occurs when one element/constituent of an alloy is removed
selectively by corrosive action.
Example: dezincification of brass, in which zinc is selectively leached from a copper–zinc brass
alloy.

Prevention:
• Select metals/alloys that are more resistant to dealloying.
• Control the environment to minimize the selective leaching
• Use sacrificial anode cathodic protection or impressed current cathodic protection

EROSION – CORROSION
• The combined action of chemical attack and mechanical wear as a consequence of fluid
motion

Examples: Propellers, turbine blades, valves, and pumps are also susceptible to this form of
corrosion

Prevention:
• changing the design to eliminate fluid turbulence and impingement effects
• removal of particulates and bubbles from the solution will lessen its ability to erode

STRESS CORROSION
• the formation and propagation of cracks (and possible failure) resulting from the combined
effects of corrosion and the application of a tensile stress.

Prevention:
• lower the magnitude of the stress:
(a) reducing the external load
(b) increasing the cross-sectional area perpendicular to the applied stress
• appropriate heat treatment may be used to anneal out any residual thermal stresses.
HYDROGEN EMBRITTLEMENT
• in a strict sense, a type of failure rather than a form of corrosion; however, it is often
produced by hydrogen that is generated from corrosion reactions.

Example: cracking of weldments or hardened steels when exposed to conditions which inject
hydrogen into the component.

Prevention:
• reducing the tensile strength of the alloy via a heat treatment
• removal of the source of hydrogen,
• substitution of a more embrittlement-resistant alloy.

Corrosion Environments

Corrosive environments include:

ATMOSPHERE → On a tonnage basis, atmospheric corrosion accounts for the greatest losses.
AQUEOUS SOLUTIONS → Water environments can also have a variety of compositions and
corrosion characteristics.
(1) Freshwater normally contains dissolved oxygen as well as minerals, several of which account
for hardness.
(2) Seawater contains approx. 3.5% salt as well as some minerals and organic matter.
SOILS → have a wide range of compositions and susceptibilities to corrosion.
MOLTEN SALT → Since molten salts are ionic
and good conductors of electricity, oxidation reactions (corrosion) will occur readily
LIQUID METAL → The destruction of solid metal or alloy due to chemical action of flowing liquid
metal at high temperatures.
HUMAN BODY → current used orthopaedic implants have the tendencies to fail after long period
of usage, due to the corrosion issue of implant in the human body

Corrosion Prevention

Material Selection
 Be judicious on selecting materials
Environmental Alteration
 Changing the character of environment
1. Temperature - Lowering the temperature of fluid
2. Velocity - Decreasing the velocity produces
 Increase or decrease in the concentration of some species in the solution
The use of Inhibitors
 Substances that decreases the corrosiveness when it is added at relatively low
concentration to its environment.
Design changes
 Design should allow for complete drainage in case of a shutdown and easy washing.
 If possible, design should include provision for the exclusion of air.
Application of Coatings
 Must maintain a high degree of surface adhesion; requires preapplication surface
treatments.
 Should be resistant to mechanical damage that exposes bare metal to the corrosive
environment

Material types that can be used as coatings for metals:

• Metals
• Ceramics
• Polymers

Cathodic Protection
Cathodic protection involves supplying, from an external source, electrons to the metal to be
protected. It is especially useful in preventing corrosion of water heaters, underground tanks and
pipes and marine equipment.

1st Cathodic Protection Technique

The metal to be protected is electrically connected to
another metal that is more reactive in the particular
environment. The latter experiences oxidation that
protects the first metal from corrosion, the oxidized
metal is called SACRIFICIAL ANODE.

2nd Cathodic Protection Technique

The source of electrons is an impressed current from an
external DC power source.

The process of Galvanizing

 This process is simply one in which a layer of zinc
is applied to the surface of steel by hot dipping. In the atmosphere and most aqueous
environments, zinc is anodic to and will thus cathodically protect the steel if there is any
surface damage. Any corrosion of the zinc coating will proceed at an extremely slow rate
because the ratio of the anode-to-cathode surface area is quite large.
 Corrosion of Ceramic Materials
Ceramic materials are compounds between metallic and non-metallic elements that are
exceedingly immune to corrosion by almost all environments especially at room temperature,
which generally involves simple chemical dissolution. These materials are frequently used because
of its resistivity to corrosion.

To resist the corrosion in refractory ceramics, it must:

• withstand high temperatures
• provides thermal insulation
• resistive to high temperature attack by molten metals, salts, slags and glasses

Degradation of Polymers
Polymeric materials experience deterioration by means of environmental actions. It may
deteriorate by swelling and dissolution.

Swelling and Dissolution

• Swelling and dissolution takes place when polymers are exposed to liquids

SWELLING → A partial dissolution process where the liquid or solute diffuses into and is absorbed
within the polymer, when they are forced apart, it causes up expansion.
Effects on Polymer:
• becomes softer
• becomes more ductile
• becomes weak
• becomes rubbery

DISSOLUTION → It occurs when the polymer is completely soluble, just a continuation of swelling.

Bond Rupture
SCISSION is the rupture of molecular chain bonds that causes separation of chain segments at its
point and a reduction in the molecular weight. It may result from exposure to radiation or to heat,
and from chemical reaction.
**Stabilizers may be added to protect polymers from radiation and oxidation**

CHEMICAL REACTION EFFECTS

 Accelerate scission
 Rupture of material
THERMAL EFFECTS
 Gaseous species are produced
 Accelerates decomposition

Weathering
• involves outdoor conditions
• any deterioration is primarily caused by oxidation
EFFECTS:
• Reduces hardness
• Decrease in stiffness
 CHAPTER 21
MATERIAL SELECTION AND DESIGN CONSIDERATIONS USING OPTICAL PROPERTIES

Why Study the Optical Properties of Materials?

• When materials are exposed to electromagnetic radiation, it is sometimes important to be able

to predict and alter their responses. This is possible when we are familiar with their optical
properties and understand the mechanisms responsible for their optical behaviors

• Optical property refers to a material’s response to exposure to electromagnetic radiation and,

in particular, to visible light.

Electromagnetic Radiation

 Electromagnetic radiation is considered to be wavelike, consisting of electric and magnetic

field components that are perpendicular to each other and also to the direction of
propagation. An electromagnetic wave showing electric field (Violet) and magnetic field
(Orange) components, and the wavelength λ.

• All electromagnetic radiation traverses a vacuum at the same velocity, that of light—namely,
3 x 108 m/s (186,000 miles/s).
Interaction with Solids

Light Interactions with Solids

• When light proceeds from one medium into another (e.g., from air into a solid substance),
several things happen. Some of the light radiation may be transmitted through the medium,
some will be absorbed, and some will be reflected at the interface between the two media.
• The intensity I0 of the beam incident to the surface of the solid medium must equal the sum of
the intensities of the transmitted, absorbed, and reflected beams, denoted as IT, IA, and IR,
respectively, or
• Intensity of incident beam at an interface is equal to the sum of the intensities of transmitted,
absorbed, and reflected beams
• The color of the objects we see in the natural world is a result of the way objects interact with
light. When a light wave strikes an object, it can be absorbed, reflected, or refracted by the
object. All objects have a degree of reflection and absorption.
• In the natural world, light can also be transmitted by an object. That is, light can pass through
an object with no effect (an x-ray, for example). These types of light, however, are not
represented in because they have no visual effect.
Transparent Materials - Materials that are capable of transmitting light with relatively little absorption
and reflection one can see through them.

Translucent Materials - Are those through which light is transmitted diffusely; that is, light is scattered
within the interior, to the degree that objects are not clearly distinguishable when viewed through a
specimen of the material

Opaque - Materials that are impervious to the transmission of visible light

OPTICAL PROPERTIES OF METALS

 Metals are opaque because the incident radiation having frequencies within the visible range
excites electrons into unoccupied energy states above the Fermi energy, as demonstrated in
the figure.
 All frequencies of visible light are absorbed by metals because of the continuously available
empty electron states, which permit electron transitions
 In fact, metals are opaque to all electromagnetic radiation on the low end of the frequency
spectrum, from radio waves, through infrared and the visible, and into about the middle of the
ultraviolet radiation. Metals are transparent to high frequency (x- and -ray) radiation
  Most of the absorbed radiation is reemitted from the surface in the form of visible light of the
same wavelength, which appears as reflected light
 The reflectivity for most metals is between 0.90 and 0.95; some small fraction of the energy
from electron decay processes is dissipated as heat
 A bright silvery appearance when exposed to white light indicates that the metal is highly
reflective
 Aluminum and silver are two metals that exhibit this reflective behavior
 Copper and gold appear red-orange and yellow, respectively, because some of the energy
associated with light photons having short wavelengths is not reemitted as visible light

OPTICAL PROPERTIES OF NONMETALS

REFRACTION - Light that is transmitted into the interior of transparent materials experiences a
decrease in velocity, and, as a result, is bent at the interface; this phenomenon is termed refraction.

Definition of index of refraction

 the ratio of light velocities in a vacuum and in the medium of interest

 The index of refraction n of a material is defined as the ratio of the velocity in a vacuum c to
the velocity in the medium.
 The magnitude of n (or the degree of bending) 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 glass prism
 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.
 Thus, the higher the index of refraction of the solid, the greater the reflectivity.
 Reflection losses for lenses and other optical instruments are minimized significantly by
coating the reflecting surface with very thin layers of dielectric materials such as magnesium
fluoride (MgF2).

TRANSMISSION

 Ability of an object to let light pass through

 Object with clear surfaces have higher transmission

ABSORPTION

 Light stops at the object and does not reflect or refract. Objects appear dark or opaque.
 Absorption is when light heat the surfaces and is converted into another form of energy. Heat
generally.
 Objects that are solid or compact has more absorption rate

COLOR

 Transparent materials appear colored as a consequence of specific wavelength ranges of light

that are selectively absorbed.
 The color discerned is a result of the combination of wavelengths that are transmitted.
 If absorption is uniform for all visible wavelengths, the material appears colorless; examples
include high-purity inorganic glasses and high-purity and single-crystal diamonds and sapphire
 Transmission of light radiation as a function of wavelength for sapphire (single-crystal
aluminum oxide) and ruby (aluminum oxide containing some chromium oxide). The sapphire
appears colorless, whereas the ruby has a red tint due to selective absorption over specific
wavelength ranges
 Opacity and Translucency In Insulators

 The extent of translucency and opacity for inherently transparent dielectric materials depends
to a great degree on their internal reflectance and transmittance characteristics
 Many dielectric materials that are intrinsically transparent may be made translucent or even
opaque because of interior reflection and refraction
 Opacity results when the scattering is so extensive that virtually none of the incident beam is
transmitted, undeflected, to the back surface
 Scattering of light also occurs in two-phase materials in which one phase is finely dispersed
within the other
 As a consequence of fabrication or processing, many ceramic pieces contain some residual
porosity in the form of finely dispersed pores. These pores also effectively scatter light
radiation

Applications of Optical Phenomena

LUMINESCENCE

 Some materials are capable of absorbing energy and then reemitting visible light in a
phenomenon called luminescence
 Some of luminous thing we can see are: Bulb, watches, paints and even your detergents.
 Luminescence is classified according to the magnitude of the delay time between absorption
and reemission events. If reemission occurs for times much less than one second, the
phenomenon is termed fluorescence
 for longer times, it is called phosphorescence

Other Types of Luminescence

Bioluminescence - made by living creatures such as fireflies, glow-worms, and many marine creatures.
Chemoluminescence - made by a chemical reaction. Glow sticks work this way.
Electroluminescence - made by passing electricity through something like a gas.
Photoluminescence - made by shining light at "luminous" (phosphorescent) paints.
Röntgenoluminescence - made by shining X-rays at things. (The curious name comes from Wilhelm
Röntgen (1845–1923), the discoverer of X-rays.)
Sonoluminescence - made by passing energetic sound waves through liquids.
Thermoluminescence - made when photons are emitted from hot materials.
Triboluminescence - made by rubbing, scratching, or physically deforming crystals.

Commercial Application of Luminescence

 Watches
 UV Light – Used for forensic investigation, Medical Tests, and archeological research
 Fluorescent Lamps
 Construction Vests
 Detergents

PHOTOCONDUCTIVITY
• Photoconductivity the increase in the electrical conductivity of certain materials when they are
exposed to light of sufficient energy.
• Most semiconductor materials have this property Photoconductive materials are used in the
manufacture of photoelectric devices. Typical photoconductive substances consist of
germanium, gallium, selenium, or silicon with impurities, also known as dopants, added. Other
common materials include metal oxides and sulfides

LASERS (Light Amplification by Stimulated Emission of Radiation)

• Coherent and high-intensity light beams are produced in lasers by stimulated electron
transitions.
 • A laser is effectively a machine that makes billions of atoms pump out trillions of photons (light
particles) all at once so they line up to form a really concentrated light beam.
What Are Lasers Used For?

• It is used extensively for range-finding and missile-tracking.

• Over half a century later, applications like this precision tools, digital communication, and
defense remain among the most important uses of lasers.

LASERS (Other Applications)

 Laser Printer
 Cutting tools
 Medicine
 Communications (Barcode Scanner)
 DVD’s or CD’s
 Defense (Laser Guided Weapons)

Optical Fibers in Communications

• Use of fiber-optic technology in our modern telecommunications provides for the transmission
of information that is interference free, rapid, and intense.
• An optical fiber is composed of the following elements: A core through which the pulses of
light propagate. The cladding, which provides for total internal reflection and containment of
the light beam within the core. The coating, which protects the core and cladding from
damage.

OPTICAL FIBERS (How do they Work?)

• Fiber optics transmit data in the form of light particles or photons that pulse through a fiber
optic cable. The glass fiber core and the cladding each have a different refractive index that
bends incoming light at a certain angle.
• When light signals are sent through the fiber optic cable, they reflect off the core and cladding
in a series of zigzag bounces, adhering to a process called total internal reflection.
The light signals do not travel at the speed of light because of the denser glass layers, instead
traveling about 30% slower than the speed of light.

OPTICAL FIBERS vs. Copper wires

• Most telephone company long-distance lines are now made of fiber optic cables. Optical fiber
carries more information than conventional copper wire, due to its higher bandwidth and
faster speeds
• Because glass does not conduct electricity. Fiber optic cables can be submerged in water and
are used in more at-risk environments like undersea cable
• Fiber optic cables are also stronger, thinner and lighter than copper wire cables and do not
need to be maintained or replaced as frequently