ENGINEERING MATERIALS GET 226

INTRODUCTION

Materials science and engineering (MSE) is an interdisciplinary field of science and engineering
that studies and manipulates the composition and structure of materials across length scales to
control materials properties through synthesis and processing. The term composition means the
chemical make-up of a material. The term structure means a description of the arrangement of
atoms, as seen at different levels of detail. Materials scientists and engineers not only deal with
the development of materials, but also with the synthesis and processing of materials and
manufacturing processes related to the production of components. The term “synthesis” refers
to how materials are made from naturally occurring or man-made chemicals. The term
“processing” means how materials are shaped into useful components to cause changes in the
properties of different materials.

In materials science, the emphasis is on the underlying relationships between the synthesis and
processing, structure, and properties of materials. In materials engineering, the focus is on
how to translate or transform materials into useful devices or structures

One of the most fascinating aspects of materials science involves the investigation of a
material’s structure. The structure of materials has a profound influence on many properties of
materials, even if the overall composition does not change! For example, if you take a pure
copper wire and bend it repeatedly, the wire not only becomes harder but also becomes
increasingly brittle! Eventually, the pure copper wire becomes so hard and brittle that it will
break! The electrical resistivity of the wire will also increase as we bend it repeatedly. In this
simple example, take note that we did not change the material’s composition (i.e., its chemical
make-up). The changes in the material’s properties are due to a change in its internal structure. If
you look at the wire after bending, it will look the same as before; however, its structure has been
changed at the microscopic scale. The structure at the microscopic scale is known as the
microstructure. If we can understand what has changed microscopically, we can begin to
discover ways to control the material’s properties.
 Figure 1.0: Application of the tetrahedron of materials science and engineering to sheet
steels for automotive chassis. Note that the composition, microstructure, and synthesis-
processing are all interconnected and affect the performance-to-cost ratio

What are the Responsibilities of Materials Engineer?

1. Design of the process
Drawing the basic design.
Selection of Proper Materials, i.e. section of material according to many parameters e.g.

 Mechanical loads,
 Wear,
 Electrical insulation,
 Thermal properties
  Availability and cost.
2. Proper choice (selecting) of substitute (alternative) materials when needed,
3. Contributing and Evaluating Materials tests results,
4. Studying and Composing Materials Data sheets before placing an order
5. Doing Research Activities to enhance materials performance.

GENERAL CLASSFICATION OF ENGINEERING MATERIALS

Solid materials have been conveniently grouped into three basic classifications: metals, ceramics,
and polymers. This scheme is based primarily on chemical makeup and atomic structure, and
most materials fall into one distinct grouping or another, although there are some intermediates.
In addition, there are three other groups of important engineering materials—composites,
semiconductors, and biomaterials. Composites consist of combinations of two or more different
materials, whereas semiconductors are utilized because of their unusual electrical characteristics;
biomaterials are implanted into the human body. A brief explanation of the material. Types and
representative characteristics is offered next.

1. Metals and Alloys

Metals and alloys include steels, aluminum, magnesium, zinc, cast iron, titanium, copper, and
nickel. An alloy is a metal that contains additions of one or more metals or non-metals. In
general, metals have good electrical and thermal conductivity. Metals and alloys have relatively
high strength, high stiffness, ductility or formability, and shock resistance. They are particularly
useful for structural or load-bearing applications. Although pure metals are occasionally used,
alloys provide improvement in a particular desirable property or permit better combinations of
properties

Ceramics:

Ceramics are compounds between metallic and nonmetallic elements. They can be defined as
inorganic crystalline materials. They are most frequently oxides, nitrides, and carbides. Beach
sand and rocks are examples of naturally occurring ceramics. The wide range of materials that
falls within this classification includes ceramics that are composed of clay minerals, cement, and
glass. Some ceramics are used as barrier coatings to protect metallic substrates in turbine
engines. Ceramics are also used in such consumer products as paints, plastics, and tires, and for
industrial applications such as the tiles for the space shuttle, a catalyst support, and the oxygen
sensors used in cars. Traditional ceramics are used to make bricks, tableware, toilets, bathroom
sinks, refractories (heat-resistant material), and abrasives. In general, due to the presence of
porosity (small holes), ceramics do not conduct heat well; they must be heated to very high
temperatures before melting. Ceramics are strong and hard, but also very brittle. We normally
prepare fine powders of ceramics and convert these into different shapes. New processing
techniques make ceramics sufficiently resistant to fracture that they can be used in load-bearing
applications, such as impellers in turbine engines. Ceramics have exceptional strength under
compression. Can you believe that an entire fire truck can be supported using four ceramic coffee
cups?

These materials are

 Typically, insulative to the passage of electricity and heat, and are more resistant to high
temperatures and harsh environments than metals and polymers
 Brittle and less tough under tensile loading
 Much stronger under compression loading
 With regard to mechanical behavior, ceramics are hard but very brittle.

Polymers:

Polymers include the familiar plastic and rubber materials. Many of them are organic
compounds that are chemically based on carbon, hydrogen, and other nonmetallic elements;
furthermore, they have very large molecular structures. These materials typically have low
densities and may be extremely flexible.

Composites:

A number of composite materials have been engineered that consist of more than one material
type. Fiberglass is a familiar example, in which glass fibers are embedded within a polymeric
material. A composite is designed to display a combination of the best characteristics of each of
the component materials. Fiberglass acquires strength from the glass and flexibility from the
polymer. Sports equipment such as bicycles, golf clubs, tennis rackets, and the like also make
use of different kinds of composite materials that are light and stiff. Many of the recent material
developments have involved composite materials (combination of two or more materials with
distinct characteristics).

Semiconductors: these are electric current carrying materials. They are weak for mechanical
loading.

Biomaterials:

Biomaterials are employed in components implanted into the human body for replacement of
diseased or damaged body parts. These materials must not produce toxic substances and must be
compatible with body tissues (i.e., must not cause adverse biological reactions). All of the above
materials—metals, ceramics, polymers, composites, and semiconductors—may be used as
biomaterials.

Advanced materials: Materials that are utilized in high-technology applications are sometimes
termed advanced materials. High technology device or product are those that operates or
functions using relatively intricate and sophisticated principles; eg, electronic equipment (VCRs,
CD players, etc.), computers, fiber optic systems, spacecraft, aircraft, marine vessels and military
rocketry. These advanced materials are typically either traditional materials whose properties
have been enhanced or newly developed, high-performance materials.

All the above materials are prone to environmental attacks which include: chemical attacks,
degradation due to temperature changes.
Figure 1.2: Representative strengths of various categories of materials.
Figure 1.3: Representative examples, applications, and properties for each category
of materials

Assignment
For each of the following classes of materials, give two specific examples that are a regular part
of your life. Specify the object that each material is found in and explain why the material is used
in each specific application. Hint: One example answer for part (a) would be that aluminum is a
metal used in the base of some pots and pans for even heat distribution. It is also a lightweight
metal that makes it useful in kitchen cookware. Note that in this partial answer to part (a), a
specific metal is described for a specific application.
Atomic Structure
Materials scientists and engineers have developed a set of instruments in order to characterize the
structure of materials at various length scales. We can examine and describe the structure of
materials at five different levels:
1. Atomic Structure;
2. Short- And Long-Range Atomic Arrangements;
3. Nanostructure;
4. Microstructure;
5. Macrostructure

Atomic Structure:
Materials are composed of atoms, which are the basic building blocks. Atoms consist of a
nucleus (containing protons and neutrons) surrounded by electrons. The arrangement and
bonding of atoms determine the properties of materials.
Crystal Structure:
Many engineering materials have a crystalline structure, where atoms are arranged in a regular,
repeating pattern. Crystals can be categorized into different crystal systems, such as cubic,
tetragonal, orthorhombic, etc. Crystal defects, such as vacancies, dislocations, and grain
boundaries, can influence material properties.
Microstructure:
Microstructure refers to the arrangement of crystals, grains, or phases in a material. It is the
structure of materials at a length of 0.1 to 100 micrometers (often written as µm and pronounced
as “microns”) It includes factors like grain size, grain boundaries, phase composition, and
distribution.
Macrostructure
This is the structure of a material at a macroscopic level where the length scale is > 100 µm.
Features that constitute macrostructure include porosity, surface coatings, and internal and
external microcrack

The Atom
An atom is composed of a nucleus surrounded by electrons. The nucleus contains neutrons and
positively charged protons and carries a net positive charge. The negatively charged electrons
are held to the nucleus by an electrostatic attraction. The electrical charge q carried by each
electron and proton is 1.60 × 10-19 coulomb (C).
The atomic number of an element is equal to the number of protons in each atom. Thus, an iron
atom, which contains 26 protons, has an atomic number of 26. The atom as a whole is
electrically neutral because the number of protons and electrons are equal.
Most of the mass of the atom is contained within the nucleus. The mass of each proton and
neutron is 1.67× 10-24 g, but the mass of each electron is only 9.11×10 -28g. The atomic mass M,
which is equal to the total mass of the average number of protons and neutrons in the atom in
atomic mass units, is also the mass in grams of the Avogadro constant NA of atoms. The
quantity NA = 6.022 ×1023 atoms mol is the number of atoms or molecules in a mole. Therefore,
the atomic mass has units of g/mol. An alternative unit for atomic mass is the atomic mass unit,
or amu, which is 1/12 the mass of carbon 12 (i.e., the carbon atom with twelve nucleons—six
protons and six neutrons). As an example, one mole of iron contains 6.022 × 1023 atoms and has
a mass of 55.847 g, or 55.847 amu. Calculations including a material’s atomic mass and the
Avogadro constant are helpful to understanding more about the structure of a material.
Example
Calculate the number of atoms in 100 g of silver (Ag)
The number of atoms can be calculated from the atomic mass and the Avogadro constant
the atomic mass, or weight, of silver is 107.868 g/mol.
The number of atoms is
100 g ×6.02 ×1023 mol
The number of Ag atom=
107.868 g /mol

= 5.58 ×1023.

Quantum Numbers and Electronic Configuration

Bohr atomic model highlights that electrons are assumed to revolve around the atomic nucleus in
discrete orbitals, and the position of any particular electron is more or less well defined in terms
of its orbital. The energies of electrons are quantized; that is, electrons are permitted to have only
specific values of energy. An electron may change energy, but in doing so it must make a
quantum jump either to an allowed higher energy (with absorption of energy) or to a lower
energy (with emission of energy).
The energy level to which each electron belongs is determined by four quantum numbers. The
size, shape, and spatial orientation of an electron’s probability density are specified by three of
these quantum numbers. Bohr energy levels separate into electron subshells, and quantum
numbers dictate the number of states within each subshell. Shells are specified by a principal
quantum number n, which may take on integral values beginning with unity; sometimes these
shells are designated by the letters K, L, M, N, O, and so on, which correspond, respectively, to n
= 1, 2, 3, 4, 5, . . . , as indicated in the table below

Table 1.0 The Number of Available Electron States in Some of the Electron Shells and Subshells

Note also that this quantum number, and it only, is also associated with the Bohr model. This
quantum number is related to the distance of an electron from the nucleus, or its position. The
four quantum numbers are the principal quantum number n, the azimuthal or secondary quantum
number L, the magnetic quantum number ml, and the spin quantum number ms. The principal
quantum number reflects the grouping of electrons into sets of energy levels known as shells.
Azimuthal quantum numbers describe the energy levels within each shell and reflect a further
grouping of similar energy levels, usually called orbitals. The magnetic quantum number
specifies the orbitals associated with a particular azimuthal quantum number within each shell.
Finally, the spin quantum number (ms) is assigned values of + 1/2 and -1/2, which reflect the two
possible values of “spin” of an electron
The Pauli Exclusion Principle stipulates that each electron state can hold no more than two
electrons, which must have opposite spins. Thus, s, p, d, and f subshells may each accommodate,
respectively, a total of 2, 6, 10, and 14 electrons. The table above summarizes the maximum
number of electrons that may occupy each of the first four shells.
Of course, not all possible states in an atom are filled with electrons. For most atoms, the
electrons fill up the lowest possible energy states in the electron shells and subshells, two
electrons (having opposite spins) per state. When all the electrons occupy the lowest possible
energies in accord with the foregoing restrictions, an atom is said to be in its ground state.
For emphasis sake, the energy structure for a sodium atom is represented schematically below

The electron configuration or structure of an atom represents the manner in which these states
are occupied. In the conventional notation the number of electrons in each subshell is indicated
by a superscript after the shell–subshell designation. For example, the electron configurations for
hydrogen, helium, and sodium are, respectively, 1s1, 1s2, and 1s2 2s2 2p6 3s1.
Valence electrons are those that occupy the outermost shell. These electrons are extremely
important; as will be seen, they participate in the bonding between atoms to form atomic and
molecular aggregates. Furthermore, many of the physical and chemical properties of solids are
based on these valence electrons. Some atoms have what are termed stable electron
configurations; that is, the states within the outermost or valence electron shell are completely
filled. Normally this corresponds to the occupation of just the s and p states for the outermost
shell by a total of eight electrons, as in neon, argon, and krypton; one exception is helium, which
contains only two 1s electrons. These elements (Ne, Ar, Kr, and He) are the inert, or noble,
gases, which are virtually unreactive chemically. Some atoms of the elements that have unfilled
valence shells assume stable electron configurations by gaining or losing electrons to form
charged ions, or by sharing electrons with other atoms. This is the basis for some chemical
reactions, and also for atomic bonding in solids.
Atomic Stability and Electronegativity

If an atom has a valence of zero, the element is inert (non-reactive). An example is argon, which has the
electronic structure:

Other atoms prefer to behave as if their outer s and p levels are either completely full, with eight
electrons, or completely empty. Aluminum has three electrons in its outer s and p levels. An
aluminum atom readily gives up its outer three electrons to empty the 3s and 3p levels. The
atomic bonding and the chemical behavior of aluminum are determined by how these three
electrons interact with surrounding atoms. On the other hand, chlorine contains seven electrons
in the outer 3s and 3p levels. The reactivity of chlorine is caused by its desire to fill its outer
energy level by accepting an electron. Electronegativity describes the tendency of an atom to
gain an electron. Atoms with almost completely filled outer energy levels—such as chlorine—
are strongly electronegative and readily accept electrons. Atoms with nearly empty outer levels
—such as sodium—readily give up electrons and have low electronegativity. High atomic
number elements also have low electronegativity because the outer electrons are at a greater
distance from the positive nucleus, so that they are not as strongly attracted to the atom.

Atomic Bond
There are four important mechanisms by which atoms are bonded in engineered materials. These
are
1. Metallic bonds;
2. Covalent bonds;
3. Ionic bonds;
4. Van der Waals bonds

The first three types of bonds are relatively strong and are known as primary bonds (relatively
strong bonds between adjacent atoms resulting from the transfer or sharing of outer orbital
electrons). The van der Waals bonds are secondary bonds and originate from a different
mechanism and are relatively weaker.
METALLIC BOND
The metallic elements have electropositive atoms that donate their valence electrons to form a
“sea” of electrons surrounding the atoms. The metallic bond, as the name says, is the dominant
(though not the only) bond in metals and their alloys.
Aluminum, for example, gives up its three valence electrons, leaving behind a core consisting of
the nucleus and inner electrons. Since three negatively charged electrons are missing from this
core, it has a positive charge of three. The valence electrons move freely within the electron sea
and become associated with several atom cores. The positively charged ion cores are held
together by mutual attraction to the electrons, thus producing a strong metallic bond. Because
their valence electrons are not fixed in any one position, most pure metals are good electrical
conductors of electricity at relatively low temperatures (T < 300 K). Under the influence of an
applied voltage, the valence electrons move, causing a current to flow if the circuit is complete.
In general, the melting points of metals are relatively high. From an optical properties viewpoint,
metals make good reflectors of visible radiation. Owing to their electropositive character, many
metals such as iron tend to undergo corrosion or oxidation. Many pure metals are good
conductors of heat and are effectively used in many heat transfer applications. We emphasize
that metallic bonding is one of the factors in our efforts to rationalize the trends observed with
respect to the properties of metallic materials. The easy movement of the electrons gives the high
electrical conductivity of metals. The metallic bond has no directionality, so that metal ions tend
to pack to give simple, high-density structures, like ball bearings shaken down in a box.

Figure 2.0 The metallic bond forms when atoms give up their valence electrons, which then form an
electron sea. The positively charged atom cores are bonded by mutual attraction to the negatively
charged electrons.
Covalent Bond
Materials with covalent bonding are characterized by bonds that are formed by sharing of
valence electrons among two or more atoms. For example, a silicon atom, which has a valence of
four, obtains eight electrons in its outer energy shell by sharing its valence electrons with four
surrounding silicon atoms. . Each instance of sharing represents one covalent bond; thus, each
silicon atom is bonded to four neighboring atoms by four covalent bonds. In order for the
covalent bonds to be formed, the silicon atoms must be arranged so the bonds have a fixed
directional relationship with one another. A directional relationship is formed when the bonds
between atoms in a covalently bonded material form specific angles, depending on the material.
In the case of silicon, this arrangement produces a tetrahedron, with angles of 109.5° between the
covalent bonds. The above explanation is illustrated in the figure below:

Figure 2.1 (a) Covalent bonding requires that electrons be shared between atoms in such a way that
each atom has its outer sp orbitals filled. (b) In silicon, with a valence of four, four covalent bonds must
be formed. (c) Covalent bonds are directional. In silicon, a tetrahedral structure is formed with angles of
109.5° required between each covalent bond.

Covalent bonds are very strong. As a result, covalently bonded materials are very strong and
hard. For example, diamond (C), silicon carbide (SiC), silicon nitride (Si3N4), and boron nitride
(BN) all have covalent bonds. These materials also exhibit very high melting points, which
means they could be useful for high-temperature applications. On the other hand, the high
temperature needed for processing presents a challenge. The materials bonded in this manner
typically have limited ductility because the bonds tend to be directional. The electrical
conductivity of many covalently bonded materials (i.e., silicon, diamond, and many ceramics) is
not high since the valence electrons are locked in bonds between atoms and are not readily
available for conduction.
The Ionic Bond
When more than one type of atom is present in a material, one atom may donate its valence
electrons to a different atom, filling the outer energy shell of the second atom. Both atoms now
have filled (or emptied) outer energy levels, but both have acquired an electrical charge and
behave as ions.
The atom that contributes the electrons is left with a net positive charge and is called a cation,
while the atom that accepts the electrons acquires a net negative charge and is called an anion.
The oppositely charged ions are then attracted to one another and produce the ionic bond. For
example, the attraction between sodium and chloride ions produces sodium chloride (NaCl), or
table salt.
Ionic bonding is perhaps the easiest to describe and visualize. It is always found in compounds
that are composed of both metallic and nonmetallic elements, elements that are situated at the
horizontal extremities of the periodic table. Atoms of a metallic element easily give up their
valence electrons to the nonmetallic atoms. In the process all the atoms acquire stable or inert gas
configurations and, in addition, an electrical charge; that is, they become ions. Sodium chloride
(NaCl) is the classic ionic material. A sodium atom can assume the electron structure of neon
(and a net single positive charge) by a transfer of its one valence 3s electron to a chlorine atom.
After such a transfer, the chlorine ion has a net negative charge and an electron configuration
identical to that of argon. In sodium chloride, all the sodium and chlorine exist as ions.
Figure 2.3: An ionic bond is created between two unlike atoms with different electronegativities. When
sodium donates its valence electron to chlorine, each becomes an ion, attraction occurs, and the ionic
bond is formed.

Van der Waals Bonding

Van der Waals bonding describes a dipolar attraction between uncharged atoms. Without them,
water would boil at -800C, and life as we know it on earth would not exist. Secondary bonding
exists between virtually all atoms or molecules, but its presence may be obscured if any of the
three primary bonding types is present. Secondary bonding is evidenced for the inert gases,
which have stable electron structures, and, in addition, between molecules in molecular
structures that are covalently bonded.
Secondary bonding forces arise from atomic or molecular dipoles. In essence, an electric dipole
exists whenever there is some separation of positive and negative portions of an atom or
molecule. The bonding results from the coulombic attraction between the positive end of one
dipole and the negative region of an adjacent one, as indicated in the figure below. Dipole
interactions occur between induced dipoles, between induced dipoles and polar molecules (which
have permanent dipoles), and between polar molecules. Hydrogen bonding, a special type of
secondary bonding, is found to exist between some molecules that have hydrogen as one of the
constituents.

Figure 2.12 Schematic illustration of van der Waals bonding between two dipoles

If two electrical charges +q and -q are separated by a distance d, the dipole moment is defined as
q d. Atoms are electrically neutral. Also, the centers of the positive charge (nucleus) and negative
charge (electron cloud) coincide. Therefore, a neutral atom has no dipole moment. When a
neutral atom is exposed to an internal or external electric field, the atom may become polarized
(i.e., the centers of positive and negative charges separate). This creates or induces a dipole
moment (Figure 2-15). In some molecules, the dipole moment does not have to be induced—it
exists by virtue of the direction of bonds and the nature of atoms. These molecules are known as
polarized molecules. An example of such a molecule that has a permanently built-in dipole
moment is water (Figure 2-16).
Molecules or atoms in which there is either an induced or permanent dipole moment attract each
other. The resulting force is known as the van der Waals force. Van der Waals forces between
atoms and molecules have their origin in interactions between dipoles that are induced or in
some cases interactions between permanent dipoles that are present in certain polar molecules.
What is unique about these forces is they are present in every material.
There are three types of van der Waals interactions, namely London forces, Keesom forces,
and Debye forces. If the interactions are between two dipoles that are induced in atoms or
molecules, we refer to them as London forces (e.g., carbon tetrachloride) (Figure 2-15). When an
induced dipole (that is, a dipole that is induced in what is otherwise a non-polar atom or
molecule) interacts with a molecule that has a permanent dipole moment, we refer to this
interaction as a Debye interaction. An example of Debye interaction would be forces between
water molecules and those of carbon tetrachloride. If the interactions are between molecules that
are permanently polarized (e.g., water molecules attracting other water molecules or other polar
molecules), we refer to these as Keesom interactions. The attraction between the positively
charged regions of one water molecule and the negatively charged regions of a second water
molecule provides an attractive bond between the two water molecules (Figure 2-16). The
bonding between molecules that have a permanent dipole moment, known as the Keesom force,
is often referred to as a hydrogen bond, where hydrogen atoms represent one of the polarized
regions. Thus, hydrogen bonding is essentially a Keesom force and is a type of van der Waals
force

Figure 2-15 Illustration of London forces, a type of a van der Waals force, between atoms.

Figure 2-16 The Keesom interactions are formed as a result of polarization of molecules or groups of
atoms. In water, electrons in the oxygen tend to concentrate away from the hydrogen. The resulting
charge difference permits the molecule to be weakly bonded to other water molecules.
Assignment
Write briefly on mixed bonding