THE CHEMISTRY OF ENGINEERING MATERIALS

INTRODUCTION
Materials play an important role for our existence, for our day to day needs, and even for our survival. In
the Stone Age, the naturally accessible materials were stone, wood, bone, fur etc. Gold was the 1st metal used
by mankind followed by copper. In the Bronze Age, copper and its alloy like bronze was used and in the Iron
Age they discovered Iron.

 Engineering Material - part of inanimate matter which is useful to an engineer in the practice of his
profession and used to produce products according to the needs and demand of society.
 Material Science - primarily concerned with the search for basic knowledge about internal structure,
properties and processing of materials and their complex interactions/relationships.
 Material Engineering - mainly concerned with the use of fundamental and applied knowledge of
materials, so that they may be converted into products, as needed or desired by the society.

Note: Material science is the basic knowledge end of materials knowledge spectrum, whereas, material
engineering is applied knowledge end and there is no boundary between the two subjects of interest.

BASIC CONCEPTS OF CRYSTAL STRUCTURE

Solid materials may be classified according to the regularity with which atoms or ions are arranged with
respect to one another. A crystalline material is one in which the atoms are situated in a repeating or periodic
array over large atomic distances.
For those that do not crystallize, this long-range atomic order is absent; these are non-crystalline or
amorphous materials.

Figure 1. Atomic Arrangement of Crystalline and Amorphous Silicon Dioxide

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.
Space Lattice or Lattice is a periodic arrangement of points in space with respect to three dimensional
network of lines. Each atom in lattice, when replaced by a point, is called lattice point, which is an intersection
of this network of lines. Arrangement of such points in 3-D space is called lattice array and 3-D space is called
lattice space.
Tiny blocks formed by arrangements of small groups of atoms are called unit cells. A unit cell is chosen
to represent the symmetry of a crystal structure, and may be defined as:
 Finite representation of infinite lattice
 Small repeat entity
 Basic structural unit
 Building block of crystal structure

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BRAVAIS LATTICES
The French scientist August Bravais, demonstrated in 1850 that only these 14 types of unit cells are
compatible with the orderly arrangements of atoms found in crystals. These three-dimensional configurations of
points are used to describe the orderly arrangement of atoms in a crystal. Each point represents one or more
atoms in the actual crystal, and if the points are connected by lines, a crystal lattice is formed.
The unit vectors a, b and c are called lattice parameters. Based on their length equality or inequality and
their orientation (the angles between them, α, β, and γ) a total of 7 crystal systems can be defined. With the
centering (face, base and body centering) added to these, 14 kinds of 3D lattices, known as Bravais lattices, can
be generated.

Figure 2. Different Bravais Lattices

METALLIC CRYSTAL STRUCTURES

1. Simple Cubic (SC)
- Most elementary crystal structure with three mutually perpendicular axes arbitrarily placed through
one of the corners of a cell.
- Each corner is occupied with one atom
- Example: alpha polonium

Figure 3. Simple Cubic Crystal Structure

2. Face-Centered Cubic (FCC)

- Atoms are arranged at the corners and center of each cube face of the cell.
- Atoms are assumed to touch along face diagonals.
- Has 4 atoms in one unit cell.
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 - Examples: aluminum, copper, gold, lead, silver and nickel
- 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√2

Figure 4. Face-Centered Cubic Crystal Structure

3. Body-Centered Cubic (BCC)

- Atoms are arranged at the corners of the cube with another atom at the cube center.
- Has 2 atoms in one unit cell.
- Examples: alpha iron, chromium, molybdenum & tungsten
- Center and corner atoms touch one another along cube diagonals, and unit cell length a and atomic
4𝑅
radius R are related through: 𝑎 =
√3

Figure 5. Body-Centered Cubic Crystal Structure

4. Hexagonal Closed-Pack (HCP)

- Cell of an HCP lattice is visualized as a top and bottom plane of 7 atoms, forming a regular hexagon
around a central atom. In between, these planes is a half-hexagon of 3 atoms.
- There are two lattice parameters in HCP, a and c, representing the basal and height parameters
respectively.
- Has 6 atoms per unit cell.
- Examples: zinc, lithium, magnesium, beryllium
- Volume is computed as

Figure 6. Hexagonal Closed-Pack Crystal Structure

COORDINATION NUMBER
Coordination number is the number of nearest neighbor atoms or ions surrounding an atom or ion. For
FCC and HCP systems, the coordination number is 12. For BCC, it’s 8. For SC, coordination number is 6.

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ATOMIC PACKING FACTOR (APF)
Atomic packing factor (APF) or packing efficiency indicates how closely atoms are packed in a unit cell
and is given by the ratio of volume of atoms in the unit cell and volume of the unit cell.
Volume of atoms
APF =
Volume of unit cell
 SC = 0.52 or 52%
 FCC = HCP = 0.74 or 74% (26% void space in unit cell)
 BCC = 0.68 or 68%

ALLOTROPY / POLYMORPHISM
Two or more distinct crystal structures for the same material at different temperature and pressure.
Examples: iron (α-iron &γ-iron), carbon (graphite & diamond), tin (α-tin &β-tin)

IMPERFECTIONS OR DEFECTS IN CRYSTALS

In actual crystals, imperfection or defects are always present, which are important to understand, as they
influence the properties of material

Classifications of Defects:
1. Point Defects (Zero Dimensional Defects)
• Imperfect point like regions in crystal (size is one or two atomic diameter)
• Created by thermal fluctuations, quenching (high rate of cooling), severe deformation of crystal
lattice (hammering or rolling) or external bombardment by atoms / high energy particles.
• Types of point defects are vacancy, Schottky imperfections, Interstitialcy, Frenkel defect,
compositional defect, and electronic defect.

2. Line Defects / Dislocations (One Dimensional Defects)

• Linear disturbance of atomic arrangement, which can move very easily on slip plane through
crystal
• Occurs during recrystallization process or during slip
• Created along a line, which is also boundary between slipped and unslipped regions of crystals
• Defect is known as ‘dislocation’ and boundary is known as ‘Dislocation Line’
• Region near dislocation, where distortion is extremely large is called ‘Core of Dislocation’ (very
high local strain)
• Types of line defects are edge dislocation and screw dislocation.

3. Surface / Plane Defects (Two Dimensional Defects)

• Two-dimensional defects in the crystal and arise from change in stacking of atomic planes on or
across the boundary
• Types of surface defects are external defects and internal defects.
• Internal defects include grain boundary, tilt boundary, twin boundary, and stacking fault.

4. Volume Defects (Three Dimensional Defects)

• Bulk defects, which includes pores, cracks, foreign inclusions or other phases

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Engineering materials are subdivided into four areas – metals, polymers, ceramics, and composites.

METALS

Metals are employed for various engineering purposes and to requirements, such as structural members,
pipes, tanks, and building up of engineering machines. Out of all metals, iron is the most popular metal in the
field of engineering. All the metals have a crystalline structure. They have properties that satisfy a wide variety
of design requirements. The manufacturing processes by which they are shaped into products have been
developed and refined over many years.
An alloy is a mixture or compound of two or more elements, at least one of which is metallic. Some
metals are important as pure elements (e.g., gold, silver, copper). Most engineering applications require the
enhanced properties obtained by alloying. Through alloying, it is possible to increase strength, hardness, and
other properties compared to pure metals.

TWO MAIN CATEGORIES OF ALLOY

1. Solid solution - an alloy in which one element is dissolved in another to form a single-phase structure. In
a solid solution, the solvent or base element is metallic, and the dissolved element can be either metallic
or nonmetal.

Two Forms of Solid Solutions

a. Substitutional solid solution - atoms of solvent element are replaced in its unit cell by
dissolved element.
b. Interstitial solid solution - atoms of dissolving element fit into vacant spaces between base
metal atoms in the lattice structure.
In both forms, the alloy structure is generally stronger and harder than either of the component elements.

Figure 7. Substitutional solid solution (left) and Interstitial solid solution (right)

2. Intermediate phases - There are usually limits to the solubility of one element in another. When the
amount of the dissolving element in the alloy exceeds the solid solubility limit of the base metal, a
second phase forms in the alloy. The term intermediate phase is used to describe it because its chemical
composition is intermediate between the two pure elements. Its crystalline structure is also different
from those of the pure metals.

WHY METALS ARE IMPORTANT?

 High stiffness and strength – can be alloyed for high rigidity, strength, and hardness
 Toughness – capacity to absorb energy better than other classes of materials
 Good electrical conductivity – metals are conductors
 Good thermal conductivity – conduct heat better than ceramics or polymers
 Cost – the price of steel is very competitive with other engineering materials

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CLASSIFICATION OF METAL ALLOYS

Metal alloys, by virtue of composition, are often grouped into two classes—ferrous and nonferrous.

FERROUS ALLOYS
Ferrous alloys those of which iron is the prime constituent are produced in larger quantities than any other metal
type. They are especially important as engineering construction materials. Their widespread use is accounted for by three
factors:
(1) iron-containing compounds exist in abundant quantities within the earth’s crust;
(2) metallic iron and steel alloys may be produced using relatively economical extraction, refining, alloying, and
fabrication techniques; and
(3) ferrous alloys are extremely versatile, in that they may be tailored to have a wide range of mechanical and
physical properties. The principal disadvantage of many ferrous alloys is their susceptibility to corrosion.

Figure 8. Classification scheme for the various ferrous alloys.

STEELS
Steels are iron–carbon alloys that may contain appreciable concentrations of other alloying elements; there are
thousands of alloys that have different compositions and/or heat treatments. The mechanical properties are sensitive to the
content of carbon, which is normally less than 1.0 wt%. Some of the more common steels are classified according to
carbon concentration—namely, into low-, medium-, and high carbon types. Subclasses also exist within each group
according to the concentration of other alloying elements.

LOW-CARBON STEELS
Plain carbon steels
• Contain only residual concentrations of impurities other than carbon and a little manganese
• Of all the different steels, those produced in the greatest quantities fall within the low-carbon classification.
• Microstructures consist of ferrite constituents. As a consequence, these alloys are relatively soft and weak
but have outstanding ductility and toughness; are the least expensive to produce.

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 High-strength, low-alloy (HSLA) steels
• Another group of low-carbon alloys are the high-strength, low-alloy (HSLA) steels. They contain other
alloying elements such as copper, vanadium, nickel.
• In normal atmospheres, the HSLA steels are more resistant to corrosion than the plain carbon steels, which
they have replaced in many applications where structural strength is critical (e.g., bridges, towers, support
columns in high-rise buildings, pressure vessels).

MEDIUM-CARBON STEELS
The medium-carbon steels have carbon concentrations between about 0.25 and 0.60 wt%. These alloys may be heat-
treated by austenitizing, quenching, and then tempering to improve their mechanical properties. They are most often
utilized in the tempered condition, having microstructures of tempered marten site. The plain medium-carbon steels have
low harden abilities and can be successfully heat-treated only in very thin sections and with very rapid quenching rates.
Additions of chromium, nickel, and molybdenum improve the capacity of these alloys to be heat-treated giving rise to a
variety of strength–ductility combinations.

HIGH-CARBON STEELS
The high-carbon steels, normally having carbon contents between 0.60 and 1.4 wt%, are the hardest, strongest,
and yet least ductile of the carbon steels. They are usually used in a hardened and tempered condition and, as such, are
especially wear resistant and capable of holding a sharp cutting edge. The tool and die steels are high-carbon alloys,
usually containing chromium, vanadium, tungsten, and molybdenum .These alloying elements combine with carbon to
form very hard and wear resistant carbide compounds. These steels are utilized as cutting tools and dies for forming and
shaping materials, as well as in knives, razors, hacksaw blades, springs, and high-strength wire.

STAINLESS STEEL
The stainless steels are highly resistant to corrosion (rusting) in a variety of environments, especially the ambient
atmosphere. Their predominant alloying element is chromium; a concentration of at least 11 wt% Cr is required.
Corrosion resistance may also be enhanced by nickel and molybdenum additions.
Stainless steels are divided into three classes on the basis of the predominant phase constituent of the microstructure—
martensitic, ferritic, or austenitic.

CAST IRONS
Cast irons are a class of ferrous alloys with carbon contents above 2.14 wt%. They are easily melted and
amenable to casting. Furthermore, some cast irons are very brittle, and casting is the most convenient fabrication
technique. Cementite (Fe3C) is a meta stable compound, and under some circumstances it can be made to dissociate or
decompose to form α-ferrite and graphite. For most cast irons, the carbon exists as graphite, and both microstructure and
mechanical behavior depend on composition and heat treatment. The most common cast iron types are gray, nodular,
white, malleable, and compacted graphite.

Gray iron
• Mechanically, gray iron is comparatively weak and brittle in tension as a consequence of its
microstructure; the tips of the graphite flakes are sharp and pointed and may serve as points of stress
concentration when an external tensile stress is applied. Strength and ductility are much higher under
compressive loads.

Ductile or nodular iron

• Adding a small amount of magnesium and/or cerium to the gray iron before casting produces a distinctly
different microstructure and set of mechanical properties. Graphite still forms, but as nodules or sphere
like particles instead of flakes. The resulting alloy is called ductile or nodular iron,

White cast iron and Malleable iron

• For low-silicon cast irons (containing less than 1.0 wt% Si) and rapid cooling rates, most of the carbon
exists as cementite instead of graphite. A fracture surface of this alloy has a white appearance, and thus it
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 is termed white cast iron. White iron is extremely hard but also very brittle, to the point of being virtually
unmachinable. Its use is limited to applications that necessitate a very hard and wear-resistant surface,
without a high degree of ductility—for example, as rollers in rolling mills. Generally, white iron is used
as an intermediary in the production of yet another cast iron, malleable iron.

Compacted graphite iron (CGI)

• A relatively recent addition to the family of cast irons is compacted graphite iron (abbreviated CGI). As
with gray, ductile, and malleable irons, carbon exists as graphite, whose formation is promoted by the
presence of silicon. Silicon content ranges between 1.7 and 3.0 wt%, whereas carbon concentration is
normally between 3.1 and 4.0 wt%.
• Compared to the other cast iron types, desirable characteristics of CGIs include the following: higher
thermal conductivity, better resistance to thermal shock (i.e., fracture resulting from rapid temperature
changes), and lower oxidation at elevated temperatures.
• Compacted graphite irons are now being used in a number of important applications, including diesel
engine blocks, exhaust manifolds, gearbox housings, brake discs for high-speed trains, and flywheels.

NON-FERROUS ALLOYS
Non-ferrous alloys are materials that does not contain iron in appreciable amounts. Generally more costly than
ferrous metals, non-ferrous metals are used because of desirable properties such as low weight, higher conductivity, non-
magnetic property or resistance to corrosion. Some non-ferrous materials are also used in the iron and steel industries.
Important non-ferrous metals include aluminum, copper, lead, nickel, tin, titanium, and zinc, and alloys such as brass.
Non-ferrous metals are usually refined through electrolysis.

Figure 9. Classification scheme for the various non-ferrous alloys.

SUPERALLOYS
- High-performance alloys designed to meet demanding requirements for strength and resistance to
surface degradation at high service temperatures.
- Many superalloys contain substantial amounts of three or more metals, rather than consisting of one base
metal plus alloying elements.
- Commercially important because they are very expensive.
- Technologically important because of their unique properties.

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Why Superalloys are Important?
 Room temperature strength properties are good but not outstanding
 High temperature performance is excellent – tensile strength, hot hardness, creep resistance, and
corrosion resistance at very elevated temperatures
 Operating temperatures often in the vicinity of 1100°C (2000°F)
 Have many applications and one example is that it is used in systems in which operating efficiency
increases with higher temperatures e.g., gas turbines, jet and rocket engines, steam turbines, and nuclear
power plants

Three Groups of Superalloys

1. Iron-based alloys - in some cases iron is less than 50% of total composition
2. Nickel-based alloys - better high temperature strength than alloy steels
3. Cobalt-based alloys - ~ 40% Co and ~ 20% chromium

METAL FABRICATION TECHNIQUES

Figure 10. Classification scheme of metal fabrication techniques.

FORMING OPERATIONS: FORGING

Mechanically working or deforming a single piece of a
normally hot metal; this may be accomplished by the application of
successive blows or by continuous squeezing, classified as either
closed or open die. For closed die, a force is brought to bear on two
or more die halves having the finished shape. Two dies having simple
geometric shapes (e.g., parallel flat, semicircular) are employed,
normally on large work pieces.

FORMING OPERATIONS: ROLLING

Consists of passing a piece of exerted by the rolls. Cold rolling may be used in the production of sheet,
strip, and foil with a high quality surface finish. Circular shapes as well as I-beams and railroad.
Rails are fabricated using grooved rolls that have rather complicated cross-sectional geometries; seamless
tubing may also be extruded.

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FORMING OPERATIONS: EXTRUSION
A bar of metal is forced through a die orifice by a compressive force
that is applied to a ram; the extruded piece that emerges has the desired
shape and a reduced cross-sectional area. Extrusion products
include rods and tubing that have rather complicated cross-
sectional geometries; seamless tubing may also be extruded.

FORMING OPERATIONS: DRAWING

Drawing is the pulling of a metal piece through a die having a
tapered bore by means of a tensile force that is applied on the exit
side. A reduction in cross section results, with a corresponding
increase in length. The total drawing operation may consist of a
number of dies in a series sequence. Rod, wire, and tubing products
are commonly fabricated in this way.

CASTING
Casting is a fabrication process whereby a molten metal is poured into a mold cavity having the desired
shape; upon solidification, the metal assumes the shape of the mold but experiences some shrinkage. Depending
on the properties and shape of the finished piece, casting may be the most desirable and economical fabrication
process.
The most common casting techniques are sand, die, investment, lost foam, and continuous, the finished
shape is so large or complicated than any other method would be impractical. A particular alloy is so low in
ductility that forming by either hot or cold working would be difficult.

SAND CASTING
A two-piece mold is formed by packing sand around a pattern that has the shape of the intended casting;
gating system is usually incorporated into the mold to expedite the flow of molten metal into the cavity and to
minimize internal casting defects. Sand-cast parts include automotive cylinder, blocks, fire hydrants, and large
pipe fittings.

DIE CASTING
In die casting, the liquid metal is forced into a mold under pressure and at a relatively high velocity and
allowed to solidify with the pressure maintained.

INVESTMENT CASTING
Sometimes called lost-wax casting, the pattern is made from a wax or plastic that has a low melting
temperature. plaster of paris is usually used; mold is then heated, such that the pattern melts and is burned out,
leaving behind a mold cavity having the desired shape. Used in jewelry and dental, crowns and inlays, blades
for gas turbines and jet engine impellers.

LOST FOAM CASTING

A variation of investment casting is lost-foam (or expendable pattern) casting. Here, the expendable
pattern is a foam that can be formed by compressing polystyrene beads into the desired shape and then bonding
them together by heating. With lost-foam casting, complex geometries and tight tolerances are possible.
Furthermore, in comparison to sand casting, lost-foam casting is a simpler, quicker, and less expensive process
and there are fewer environmental wastes. Metal alloys that most commonly use this technique are cast irons
and aluminum alloys; furthermore, applications include automobile engine blocks, cylinder heads, crankshafts,
marine engine blocks, and electric motor frames.

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CONTINUOUS CASTING
These casting and rolling steps may be combined by a continuous casting (sometimes termed strand
casting) process. Using this technique, the refined and molten metal is cast directly into a continuous strand that
may have either a rectangular or circular cross section; solidification occurs in a water-cooled die having the
desired cross-sectional geometry. The chemical composition and mechanical properties are more uniform
throughout the cross sections for continuous castings than for ingot-cast products. Furthermore, continuous
casting is highly automated and more efficient.

POWDER METALLURGY
Another fabrication technique involves the compaction of powdered metal followed by a heat treatment
to produce a denser piece. The process is appropriately called powder metallurgy, frequently designated as P/M.
Powder metallurgy makes it possible to produce a virtually nonporous piece having properties almost equivalent
to those of the fully dense parent material.
Diffusional processes during the heat treatment are central to the development of these properties. This
method is especially suitable for metals having low ductilities, because only small plastic deformation of the
powder particles need occur. Metals with high melting temperatures are difficult to melt and cast, and
fabrication is expedited using P/M. Furthermore, parts that require very close dimensional tolerances (e.g.,
bushings and gears) may be economically produced using this technique.

WELDING
Welding may be considered to be a fabrication technique. In welding, two or more metal parts are joined
to form a single piece when one-part fabrication is expensive or inconvenient. Both similar and dissimilar
metals may be welded. The joining bond is metallurgical (involving some diffusion) rather than just
mechanical, as with riveting and bolting. A variety of welding methods exist, including arc and gas welding, as
well as brazing and soldering.

POLYMERS
Polymers are engineering materials of very high molecular weight. They are created when a large
number of identical repeating monomer units are joined together to make a single large polymer molecule. This
term comes from the Greek words poly, which means “many”, and meros, meaning “parts”. The “mer” is the
smallest repetitive unit in a polymer based on the carbon atom. The atoms in the repeating molecule are strongly
bonded (usually covalent), and the bonds between molecules may be due to weaker secondary bonds or similar
covalent bonds. One of the common examples of polymers is polyethylene.

Polymers are extensively used in food packaging, clothing, home furnishing, transportation, medical
devices, information technology, and other multifarious applications in our modern society. Natural fibers such
as silk, wool, and cotton are polymers and have been used for thousands of years. However, due to some
technological advancement, some of these natural fibers were replaced by synthetic fibers such as rayon, nylon,
and acrylics.

Two chemical classes of polymers are: “thermoplastics” and “thermoset” – terms that describe how
polymers behave when heated. Polymers also fall into two economic groups: “commodity polymers” which are
more economical and “engineering polymers” which are costly.

POLYMERIZATION
Monomer is the individual structural unit of a polymer. Polymerization is a chemical reaction in which
monomer units combine to form larger molecules that contain repeating structural units. Proper polymer names
are derived from the individual structural unit. For example:
Ethylene polymerizes to polyethylene
Propylene polymerizes to polypropylene

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 Styrene polymerizes to polystyrene
Vinyl Chloride polymerizes to polyvinyl chloride

The following are the two main types of polymerization.

1. Chain-reaction Polymerization or Addition Polymerization. In this reaction, monomers simply add to one
another to form the polymer. Examples of this are LDPE, HDPE, PVC, PP, and PS.

Figure 11. Addition polymerization of Polyvinyl Chloride

2. Step-Reaction Polymerization or Condensation Polymerization. Two monomers add in a condensation

reaction under the release of water or another small molecule like hydrogen chloride. Examples of this are
PET, PU and PA.

Figure 12. Condensation Polymerization of Polyamide

POLYMER CHAIN BRANCHING

One of the most common polymers is polyethylene. Polyethylenes with similar molecular weights can
have different properties which depend on the degree and nature of branching. The most immediate difference
is density. High-density polyethylene (HDPE) is resulted when highly linear polyethylene molecules can be
closely packed. Highly branched molecular chains cannot pack cosely together and, hence, produce a low-
density polyethylene (LDPE). The other one is the linear-low density polyethylene (LLDPE) which has short
controlled side branches.

HDPE LDPE LLDPE

(Low degree of short-chain (High degree of short-chain (High degree of short-chain and
branching) branching) long-chain branching)

Figure 13. Polyethylene branching in different densities

COPOLYMER
When a polymer is made by linking only one type of small molecule or monomer, together it is called a
homopolymer. When two different types of monomers are joined in the same polymer chain, the polymer is
called a copolymer while terpolymers contain three monomer types.
The purpose of copolymers is to bring together the favourable properties of two distinctly different
polymers. For example, polyethylene has excellent water vapour barrier properties, but is a very poor oxygen
barrier. On the other hand, polyvinyl alcohol (PVAL, also abbreviated as PVOH) has superior oxygen barrier

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properties, but readily dissolves in water. By making a copolymer of the two, some properties of both can be
incorporated into one polymer.

POLARITY AND MATERIAL PROPERTIES

Polarity is the way in which atoms bond with each other. Atoms share electrons when they come
together in chemical bonding. A polar molecule arises when one of the atoms exerts a stronger attractive force
on the electrons in the bond. The electrons get drawn more towards that atom, thus creating an unequal sharing;
it has a positive and a negative pole similar to a magnet.
A polymer is considered polar if it has a charge either positive or negative. Otherwise, it is nonpolar.
Some examples of polar polymers are polyamide (PA), polycarbonate (PC), and acrylonitrile butadiene styrene
(ABS). The most common nonpolar polymers are polypropylene and polyethylene.

Polarity influences many material properties such as the following.

a. Melting point. Even though two molecules have similar molecular weights, the one with the higher
polarity will have the higher melting point since a greater amount of energy must be put into the
substance to overcome the polar attractions between the molecules.
b. Solubility. Materials are more soluble if they have the same polarity. It follows the simple general
observation that “like dissolves like”. For example, alcohol is soluble to water because they are both
highly polar substances. On the other hand, oil is not soluble to water because they have different
polarities.
c. Barrier is a material property that stops or reduces the permeation of a gas through the material.
Solubility is the prime determinant whether a particular gas will permeate through a particular polymer.
d. Coefficient of friction or stickiness. It occurs where highly polar surfaces attract one another. The
mechanism of adhesive bonding is mostly attributed to maximizing the polar attraction between the
adhesive material and the substrate. Low-polarity materials such as PE and PP are difficult to bond using
adhesives.

FACTORS WHICH AFFECT PROPERTIES OF POLYMERS

Individual polymers have distinct properties. A specific polymer can have completely difference
performance properties. The following shows the factors where polymer’s properties depend on.
1. Elements. Some polymer molecules don’t have the same elements which make it up. For example,
polyethylene and polyvinyl chloride. Polyethylene is made up of hydrogen and carbon atoms alone
while polyvinyl chloride also includes chlorine atoms.
2. Polarity. It is the attraction and repulsion properties of molecules. Molecules exhibit varying degrees
of polarity which depends on the participating atoms. These degrees will affect the melting point,
coefficient of friction, solubility, barrier properties, and adhesiveness of polymers.
3. Size or Molecular Weight. Most polymers are available in a range of molecular weights. Other
properties such as melting point, stiffness, and solubility depend on molecular weight.
4. Molecule’s shape. This will determine how large numbers of the molecules will fit together. It
affects the degree of crystallinity, clarity, barrier, melting point, and other physical properties.
5. Thermal History. In order for a thermoplastic to get into a form that can be shaped, it must be melted
first. So every plastic has a thermal history and changing this will also change the pastic’s
performance characteristics.
6. Mechanical History. Plastic’s final properties are also dependent on its mechanical history. It
describes how plastics flow in the molten state and how it is being stressed when cold.

MOLECULAR STRUCTURE AND PROPERTIES

1. Crystallinity. Highly ordered molecular arrangements are said to be “crystalline”, while completely
random arrangements are “amorphous”. The greater the ordering, the greater the degree of crystallinity.
Generally, a polymer with lower crystallinity will have better clarity than the same polymer with higher

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 levels of crystallinity. Special additives (i.e., nucleating agents) can be used to deliberately induce very
fine crystallinity.
2. Molecular Weight Distribution. In reality, polymers don’t have a specific molecular weight. Molecular
weights reported in specification sheets are average values which mean that some molecules weigh more
than the others. The molecular makeup of two polymers with identical reported molecular weights can
be quite different, depending on the molecular weight spread. The greater the molecular weight
distribution, the easier to melt the plastic.
3. Viscoelasticity. One example of a viscoelastic material is a polymer. Viscoelastic materials are those
which exhibit both viscous and elastic characteristics. Viscoelasticity is also known as anelasticity,
which is present in systems when undergoing deformation. Accordingly, rapid application of a load to
plastic will cause it to bend, and if that load is quickly released, the plastic will return to its original
shape: It behaves like an elastic or a spring.

THERMAL BEHAVIOR
A polymer will go through a series of transition zones as it is heated, identified as rigid, thermoelastic
and thermoplastic rather than going directly from a rigid solid to a melt. A polymer material will exhibit a
unique set of physical properties, characteristic of each zone.
There are three main states in which a polymer can exist and therefore there are two types of typical
transitions the polymer can go through. In the Glassy state, the plastic is brittle; in the Rubbery or Viscoelastic
state, the plastic is soft and/or tough and in the Melt state the plastic is molten. The transition temperature at
which the polymer changes from brittle to soft/tough is called the Glass Transition Temperature (T g). The
transition temperature at which the polymer changes from soft/tough to a melt is called the Melt Temperature
(Tm). Amorphous polymers do not show a clear transition into the melt and therefore do not exhibit a melt
temperature. The change is gradual and the polymer softens with increasing temperature.

Figure 14. Thermal Transition in Polymers

ORIENTATION
Orientation refers to a relative direction of how a particular molecule is arranged. It stretches and aligns
molecules in the direction of the stretching action.
To orient polymer molecules permanently, the material is physically stretched at a temperature below its
glass transition temperature (Tg). The general effect of straightening and aligning polymer chains is to enhance
many desirable properties, such as tensile strength barrier qualities, and T m. The overall advantage is it allows
thinner sections of material to be used. It can be done in one direction (monoaxial) or in two directions (biaxial).

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THERMOPLASTIC AND THERMOSET POLYMERS
In order for a monomer to form a complex polymer structure, it can simply join onto each other to form
long chains as in a thermoplastic, or they can cross-link between the chains in a
three dimensional pattern, resulting in a thermoset plastic.
Thermoplastic polymers form when repeating units called monomers link into chains or branches.
Because they soften when heated, thermoplastic polymers are easy to mold into a variety of shapes and also
lend themselves to recycling. Common uses for thermoplastic polymers include the fabrication of pipes, ropes,
belts, insulators and adhesives.
Thermoset materials are those materials that are made by polymers joined together by chemical bonds,
acquiring a highly crosslinked structure. However, one of the negative aspects of thermosets is its inability to
recycle because once they are crosslinked or cured it is impossible to return to a liquid phase material.
Thermoset materials have the property of not melt or deforming in presence of temperature or heat before pass
to a gaseous state to a liquid state.

CERAMICS
Ceramics are inorganic and nonmetallic materials. Most ceramics are compound between metallic and
non-metallic elements which the interatomic bonds are either totally ionic or predominantly ionic but having
some covalent character. The term ceramic comes from the greek word keramikos, which means “burnt stuff”
indicating that desirable properties of these materials are normally achieve through a high temperature heat
treatment process called firing.

Since ceramics are composed of at least two elements or rather more, their crystal structures are
generally more complex than those for metals. The atomic bonding in these materials ranges from pure ionic to
totally covalent; many ceramics exhibit a combination of these two bonding types, the degree of ionic character
being dependent on the electronegativities of the atoms.

The preceding discussions of the properties of materials have demonstrated that there is a significant
disparity between the physical characteristics of metals and ceramics. Consequently, these materials are used in
totally different kinds of applications and, in this regard, tend to complement each other and also the polymers.
Most ceramic materials fall into an application–classification scheme that includes the following groups:
glasses, structural clay products, white wares, refractories, abrasives, cements, and the newly developed
advanced ceramics. Below is the classification of ceramic materials on the basis of application.

Glass-ceramic materials have been designed to have the following characteristics:

• relatively high mechanical strengths;
• low coefficients of thermal expansion (to avoid thermal shock);
• relatively high temperature capabilities;
• good dielectric properties (for electronic packaging applications);
• good biological compatibility.

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 Some glass-ceramics may be made optically transparent; others are opaque. Possibly the most attractive
attribute of this class of materials is the ease with which they may be fabricated; conventional glass-forming
techniques may be used conveniently in the mass production of nearly pore-free ware.
Glass-ceramics are manufactured commercially under the trade names of Pyroceram, CorningWare,
Cercor, and Vision. The most common uses for these materials are as ovenware, tableware, oven windows, and
range tops—primarily because of their strength and excellent resistance to thermal shock. They also serve as
electrical insulators and as substrates for printed circuit boards and are used for architectural cladding and for
heat exchangers and regenerators.

CLAY PRODUCTS
One of the most widely used ceramic raw materials is clay. This inexpensive ingredient, found naturally
in great abundance, often is used as mined without any upgrading of quality. Another reason for its popularity
lies in the ease with which clay products may be formed; when mixed in the proper proportions, clay and water
form a plastic mass that is very amenable to shaping. The formed piece is dried to remove some of the moisture,
after which it is fired at an elevated temperature to improve its mechanical strength.
Most of the clay-based products fall within two broad classifications: the structural clay products and
the whitewares. Structural clay products include building bricks, tiles, and sewer pipes – applications in which
structural integrity is important. The whiteware ceramics become white after the high-temperature firing.
Included in this group are porcelain, pottery, tableware, china, and plumbing fixtures (sanitary ware). In
addition to clay, many of these products also contain nonplastic ingredients, which influence the changes that
take place during the drying and firing processes, and the characteristics of the finished piece.

REFRACTORIES
Another important class of ceramics that are used in large tonnages is the refractory ceramics. The
salient properties of these materials include the capacity to withstand high temperatures without melting or
decomposing and the capacity to remain unreactive and inert when exposed to severe environments.
Refractory materials are marketed in a variety of forms, but bricks are the most common. Typical
applications include furnace linings for metal refining, glass manufacturing, metallurgical heat treatment, and
power generation. The performance of a refractory ceramic depends to a large degree on its composition. On
this basis, there are several classifications – fireclay refractories, silica refractories, basic refractories, and
special refractories.

ABRASIVE CERAMICS
Abrasive ceramics are used to wear, grind, or cut away other material, which necessarily is softer.
Therefore, the prime requisite for this group of materials is hardness or wear resistance; in addition, a high
degree of toughness is essential to ensure that the abrasive particles do not easily fracture. Furthermore, high
temperatures may be produced from abrasive frictional forces, so some refractoriness is also desirable.

CEMENTS
Several familiar ceramic materials are classified as inorganic cements: cement, plaster of paris, and lime,
which, as a group, are produced in extremely large quantities. The characteristic feature of these materials is
that when mixed with water, they form a paste that subsequently sets and hardens. This trait is especially useful
in that solid and rigid structures having just about any shape may be expeditiously formed.
Also, some of these materials act as a bonding phase that chemically binds particulate aggregates into a
single cohesive structure. Under these circumstances, the role of the cement is similar to that of the glassy
bonding phase that forms when clay products and some refractory bricks are fired. One important difference,
however, is that the cementitious bond develops at room temperature.

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COMPOSITES
A composite is considered to be any multiphase material that exhibits a significant proportion of the
properties of both constituent phases such that a better combination of properties is realized. It is a multiphase
material that is artificially made, as opposed to one that occurs or forms naturally. In designing composite
materials, scientists and engineers have ingeniously combined various metals, ceramics, and polymers to
produce a new generation of extraordinary materials. Most composites have been created to improve
combinations of mechanical characteristics such as stiffness, toughness, and ambient and high-temperature
strength.

Two Phases of Composite Materials

• Matrix phase - which is continuous and surrounds the other phase,
• Dispersed phase. - the one that is being surrounded by the matrix.

The properties of composites are a function of the properties of the constituent phases, their relative amounts,
and the geometry of the dispersed phase. Dispersed phase geometry in this context means the shape of the
particles and the particle size, distribution, and orientation. The dispersed phase for particle-reinforced
composites is equiaxed (i.e., particle dimensions are approximately the same in all directions); for fiber
reinforced composites, the dispersed phase has the geometry of a fiber (i.e., a large length-to-diameter ratio).
Structural composites are multilayered and designed to have low densities and high degrees of structural
integrity. For nanocomposites dimensions of the dispersed phase particles are on the order of nanometers.

PARTICLE-REINFORCED COMPOSITES
Large-particle and dispersion-strengthened composites are the two subclassifications of particle-
reinforced composites. The distinction between these is based on the reinforcement or strengthening
mechanism. The term large is used to indicate that particle–matrix interactions cannot be treated on the atomic
or molecular level; rather, continuum mechanics is used. For most of these composites, the particulate phase is
harder and stiffer than the matrix. These reinforcing particles tend to restrain movement of the matrix phase in
the vicinity of each particle. In essence, the matrix transfers some of the applied stress to the particles, which
bear a fraction of the load. The degree of reinforcement or improvement of mechanical behavior depends on
strong bonding at the matrix–particle interface.

FIBER-REINFORCED COMPOSITES
Technologically, the most important composites are those in which the dispersed phase is in the form of
a fiber. Design goals of fiber-reinforced composites often include high strength and/or stiffness on a weight
basis. These characteristics are expressed in terms of specific strength and specific modulus parameters, which
correspond, respectively, to the ratios of tensile strength to specific gravity and modulus of elasticity to specific
gravity. Fiber-reinforced composites with exceptionally high specific strengths and moduli have been produced
that use low-density fiber and matrix materials.
The mechanical characteristics of a fiber-reinforced composite depend not only on the properties of the
fiber, but also on the degree to which an applied load is transmitted to the fibers by the matrix phase. Important
to the extent of this load transmittance is the magnitude of the interfacial bond between the fiber and matrix
phases. Under an applied stress, this fiber–matrix bond ceases at the fiber ends, yielding a matrix deformation
pattern, in other words, there is no load transmittance from the matrix at each fiber extremity.

STRUCTURAL COMPOSITES
A structural composite is a multi-layered and normally low-density composite used in applications
requiring structural integrity, ordinarily high tensile, compressive, and torsional strengths and stiffness’s. The
properties of these composites depend not only on the properties of the constituent materials, but also on the
geometrical design of the structural elements. Laminar composites and sandwich panels are two of the most
common structural composites.

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NANOCOMPOSITES
The material’s world is experiencing a revolution with the development of a new class composite
materials—the nanocomposites. Nanocomposites are composed of nanosized particles (or nanoparticles) that
are embedded in a matrix material. They can be designed to have mechanical, electrical, magnetic, optical,
thermal, biological, and transport properties that are superior to conventional filler materials; furthermore, these
properties can be tailored for use in specific applications. For these reasons, nanocomposites are becoming
infused in a number of modern technologies.
Two factors account for these size-induced properties of nanoparticles: (1) the increase in ratio of
particle surface area to volume; and (2) particle size.
Surface atoms behave differently than atoms located in the interior of a material. Consequently, as the size of a
particle decreases, the relative ratio of surface atoms to bulk atoms increases; this means that surface
phenomena begin to dominate. Furthermore, for extremely small particles, quantum effects begin to appear.

ENGINEERING NANOMATERIALS

DEFINING NANOMATERIALS
Every year, engineers find a way to invent and develop technologies that could alter the future.
Holographic computers, artificial intelligence, sense and avoid drones, zero-emissions vehicles, and brain
organoids – these are just some of the newly developed technologies, which some people thought impossible.
From macrotechnologies, now, technologies are being designed and produced at a very small scale called
nanotechnologies.
Nanotechnology is science, engineering, and technology conducted at the nanoscale, which is about 1 to
100 nanometers. One of the main products of nanotechnologies is nanomaterials. These are nano-scale particles,
tubes, rods, or fibres. They are also used in healthcare, electronics, cosmetics, textiles, information technology
and environmental protection.

PROPERTIES OF NANOMATERIALS
There are parameters that should be assessed both for the nanomaterials as they are made and for
nanomaterials as they are used. The main parameters which are relevant to the safety of nanoparticles include:
1. Physical properties
 Their size, shape, specific surface area, and ratio of width and height
 Whether they stick together
 Size distribution
 How smooth or bumpy their surface is
 Structure, including crystal structure and any crystal defects
 How well they dissolve

2. Chemical properties
 Molecular structure
 Composition, including purity, and known impurities or additives
 Whether it is held in a solid, liquid or gas
 Surface chemistry
 Attraction to water molecules or oils and fats

HOW TO MANUFACTURE NANOMATERIALS

In the International System of Units (SI), the prefix "nano" means one-billionth, or 10-9. It’s difficult to
imagine just how small that is, so here are some examples:
 A sheet of paper is about 100,000 nanometers thick
 A strand of human DNA is 2.5 nanometers in diameter

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  On a comparative scale, if the diameter of a marble was one nanometer, then diameter of the Earth
would be about one meter.

Nanomanufacturing is manufacturing at the nanoscale. It involves scaled-up, reliable, and cost-effective

manufacturing of nanoscale materials, structures, devices, and systems. It also includes research, development,
and integration of top-down processes and increasingly complex bottom-up or self-assembly processes.

There are two basic approaches to nanomanufacturing:

 Top-down - reduces large pieces of materials all the way down to the nanoscale, like someone carving a
model airplane out of a block of wood. This approach requires larger amounts of materials and can lead
to waste if excess material is discarded.
 Bottom-up - creates products by building them up from atomic- and molecular-scale components, which
can be time-consuming.

Within the top-down and bottom-up categories of nanomanufacturing, there are a growing number of new
processes that enable nanomanufacturing. Among these are:
 Chemical vapor deposition - a process in which chemicals react to produce very pure, high-
performance films
 Molecular beam epitaxy - one method for depositing highly controlled thin films
 Atomic layer epitaxy - a process for depositing one-atom-thick layers on a surface
 Dip pen lithography - a process in which the tip of an atomic force microscope is "dipped" into a
chemical fluid and then used to "write" on a surface, like an old fashioned ink pen onto paper
 Nanoimprint lithography - a process for creating nanoscale features by "stamping" or "printing"
them onto a surface
 Roll-to-roll processing - a high-volume process to produce nanoscale devices on a roll of ultrathin
plastic or metal
 Self-assembly - describes the process in which a group of components come together to form an
ordered structure without outside direction

POTENTIAL EFFECTS OF NANOMATERIALS

A. In health. There is experimental evidence of a range of possible interactions with biological systems and
health effects of manufactured nanoparticles. In experimental systems in the laboratory, they can affect
the formation of the fibrous protein tangles, which are similar to those seen in some diseases, including
brain diseases. Airborne particles might cause effects in the lungs but also on the heart and blood
circulation similar to those already known for particulate air pollution. There is some evidence that
nanoparticles might lead to genetic damage, either directly or by causing inflammation.
B. In environment. Wider use of nanomaterials will lead to increases in environmental exposure. Since they
are minute, little is known about how they may then behave in air, water or soil. As a result of their
diversity, nanomaterials may have a wide range of effects. Some kill bacteria or viruses. Experiments so
far have also shown possible harmful effects on invertebrates and fish, including effects on behavior,
reproduction and development. There is less research to date on soil systems and terrestrial species, and
it is not clear whether laboratory results relate to what may happen out in the real world.

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