ASSIGMENT 1

ENGINEERING MATERIALS
BFM 1113

Name : Sharifah Syahira Bte Syed Mohamad

Matrix Card : FB10060
CONTENTS

Bil . Title Page

1 Intoduction Of Polymer 1–2

2 Polymer Materials

• Multicomponent Polymer Materials

3 Polymer Structure

• Mers

• Polymer Chains (Thermoplastics and Thermosets)

• Types of Polymers

4 Polymer Materials

• Monomers and repeat units

Microstructure

Polymer architecture

Chain length

Monomer arrangement in copolymers

INTRODUCTION OF POLYMER

The word polymer literally means "many parts." A polymeric solid material may be
considered to be one that contains many chemically bonded parts or units which
themselves are bonded together to form a solid. Two industrially important polymeric
materials are plastics and elastomers. Plastics are a large and varied group of synthetic
materials which are processed by forming or molding into shape. Just as we have many
types of metals such as aluminum and copper, we have many types of plastics such as
polyethylene and nylon. Plastics can be divided into two classes, thermoplastics and
thermosetting plastics, depending on how they are structurally and chemically bonded.
Elastomers or rubbers can be elastically deformed a large amount when a force is applied
to them and can return to their original shape (or almost) when the force is released.

A polymer is a large molecule (macromolecule) composed of repeating structural units

typically connected by covalent chemical bonds. While polymer in popular usage
suggests plastic, the term actually refers to a large class of natural and synthetic materials
with a wide variety of properties.

Because of the extraordinary range of properties accessible in polymeric materials, they

play an essential and ubiquitous role in everyday life, ranging from familiar synthetic
plastics and elastomers to natural biopolymers such as DNA and proteins that are
essential for life. A simple example is polyethylene, whose repeating unit is based on
ethylene (IUPAC name ethene) monomer. Most commonly, as in this example, the
continuously linked backbone of a polymer used for the preparation of plastics consists
mainly of carbon atoms. However, other structures do exist; for example, elements such
as silicon form familiar materials such as silicones, examples being silly putty and
waterproof plumbing sealant. The backbone of DNA is in fact based on a phosphodiester
bond, and repeating units of polysaccharides (e.g. cellulose) are joined together by
glycosidic bonds via oxygen atoms.

Natural polymeric materials such as shellac, amber, and natural rubber have been in use
for centuries. Biopolymers such as proteins and nucleic acids play crucial roles in
biological processes. A variety of other natural polymers exist, such as cellulose, which is
the main constituent of wood and paper. The list of synthetic polymers includes synthetic
rubber, Bakelite, neoprene, nylon, PVC, polystyrene, polyethylene, polypropylene,
polyacrylonitrile, PVB, silicone, and many more. Polymers are studied in the fields of
polymer chemistry, polymer physics, and polymer science.

Appearance of real linear polymer chains as recorded using an atomic force microscope on surface under liquid
medium. Chain contour length for this polymer is ~204 nm; thickness is ~0.4 nm.
POLYMER MATERIALS

A Polymer is a huge molecule also known as macromolecule composed of replicating

structural units linked by chemical bonds of covalent. Polymer materials can be organic
or inorganic and natural or synthetic in origin. Polymers are important materials for
roughly every industry in the form of paper, fibers, cloths, building materials, adhesives,
ceramics, plastics, liquid crystals, coatings, concretes and photo resists. They are
significant in engineering, medicine, biology, nutrition, space exploration, environment
and health.

Natural inorganic polymers comprise of diamonds, sand, agates, feldspars, graphite,

agates, quartz, mica, and talc. Natural organic polymers comprise of poly carbohydrates
such as cellulose and starch, proteins and nucleic acids. Synthetic inorganic polymers
comprise of boron nitride, high temperature superconductors, glasses and concrete.
Synthetic polymers utilized for structural constituents weigh up significantly less than
metals, assisting to decrease the utilization of fuel in aircraft and vehicles. They also
outperform nearly all metals when considered on the basis of strength per weight.
Polymers can also be used for purposes of engineering such as bearings and gears.

Fibers are one of the polymer materials which are sturdy in one direction and they are too
longer. Cotton, silk, and wool are fibers natural in nature which are utilized by humans
since many years. Nylon, rayon, acrylic and polyester are the man-made fibers. The
amalgamations of weight, durability and strength have prepared these materials as
essential in modern industry.

Nylon is also polymers that have some unique properties which makes it different from
other materials. Elasticity is the main property of nylon. Nylons are extremely elastic but
when the limits of elastics are over stretched the material do not return in its original
shape. Similar to synthetic fibers, nylon has a huge electrical resistance. Elastomers are
also considered as polymeric materials which can be distorted by way of applying force,
and after removal of force, the materials gets back to its original shape. Materials of
plastic have properties linking elastomers and fibers which are flexible and hard.
Adhesives and coatings are usually originated from polymers and are the members of
different groupings. Industrially essential coatings and adhesives comprise of sealants
and caulks, laminates, liquid crystals, cement and ceramic.

Processed materials of polymer are usually a mixture of the materials and the polymer for
modifying its properties, helpful in processing and initiating new properties. Additives
can be liquids, gases or solids. Classic additives are antioxidants, fillers, plasticizers,
reinforcements and colorants. Numerous polymers are thermoplastics and they can be
reformed and used by way of pressure and heat in the manufacture of further
thermoplastic materials. It is really difficult to recycle thermo-sets polymers as they do
not melt but prior to softening they get degraded.

Composite material is a material system composed of combination or mixture of more

than two constituents that vary in material composition or form and are significantly
mysterious in each other. In law, composites can be created by mixture of more than two
materials- organic, inorganic or metallic but the elements are more controlled. Main
structural elements are particles, fibers, layers, fillers, matrices and flakes. Advanced
composites include structural materials developed for applications of high-technology
such as structures of air frame, in favor of which further materials are not adequately
stiff. In these materials, very strong and stiff continuous or discontinuous whiskers, fibers
or miniature particles are isolated in the matrix. Nowadays, the utilization of fiber
resistant materials has grown rapidly in applications of engineering. Choice of
composites as compared to monolithic materials is stated by the selection of properties.

Thus, nowadays wide range of polymer materials are available with their distinct
properties and are useful in several ways in different fields.

Multicomponent Polymer Materials

Multicomponent polymer materials are widely used in many industries because by

appropriate mixing of different polymers and fillers one can design materials with
desirable properties. The structure-property relationship in such materials is difficult to
understand without microscopic analysis. AFM is very helpful in this analysis at scales
from hundreds of microns to nanometers. The specific shape of individual components as
well as variations in their mechanical and electric properties allow them to be
distinguished from one another in AFMM images. The images of two nanocomposites,
polyparaxylylene with Si particles and polypropylene with clay, are shown in Figures
10a–b. Si particles, which are seen as small spheres with radii varying in the 5–10nm
range, are dispersed in the polymer matrix. Small sheets of layered clay mineral, some of
them in aggregates, are seen as edge-on structures in several locations in Figure 10b. The
presence of aggregates indicates that the exfoliation process, which could separate the
filler into multiple sheets with thickness down to molecular size, was not optimized.
 Phase images of polyparaxylylene filled with Ag particles (a) and polypropylene filled with clay particles (b)

(a) –(b) Force Volume maps of 500nm and 100nm areas of polystyrene-b-polybutadiene-b-polystyrene film showing
surface locations with different mechanical properties. Brighter areas as one marked with a green cross are
characterized by AvZ curve shown below (a) and common for polystyrene; darker areas as one marked with a blue
cross – by AvZ curve shown below (b) and common for polybutadiene.

Height (left) and phase (right) images of roofing material at different temperatures: (a) 25°C, (b) (-10°C) and (c) (-
35°C).
POLYMER STRUCTURE

Engineering polymers include natural materials such as rubber and synthetic materials
such as plastics and elastomers. Polymers are very useful materials because their
structures can be altered and tailored to produce materials

1) With a range of mechanical properties

2) In a wide spectrum of colors and

3) With different transparent properties.

Mers
A polymer is composed of many simple molecules that are repeating structural units
called monomers. A single polymer molecule may consist of hundreds to a million
monomers and may have a linear, branched, or network structure. Covalent bonds hold
the atoms in the polymer molecules together and secondary bonds then hold groups of
polymer chains together to form the polymeric material. Copolymers are polymers
composed of two or more different types of monomers
 Mer –
The repeating unit in a polymer chain
Monomer –
A single mer unit (n=1)
Polymer –
Many mer-units along a chain (n=103 or more)
Degree of Polymerization –
The average number of mer-units in a chain.

A polymer is an organic material and the backbone of every organic material is a chain of
carbon atoms. The carbon atom has four electrons in the outer shell. Each of these
valence electrons can form a covalent bond to another carbon atom or to a foreign atom.
The key to the polymer structure is that two carbon atoms can have up to three common
bonds and still bond with other atoms. The elements found most frequently in polymers
and their valence numbers are: H, F, Cl, Bf, and I with 1 valence electron; O and S with 2
valence electrons; n with 3 valence electrons and C and Si with 4 valence electrons.

he ability for molecules to form long chains is a vital to producing polymers. Consider
the material polyethylene, which is made from ethane gas, C 2H6. Ethane gas has a two
carbon atoms in the chain and each of the two carbon atoms share two valence electrons
with the other. If two molecules of ethane are brought together, one of the carbon bonds
in each molecule can be broken and the two molecules can be joined with a carbon to
carbon bond. After the two mers are joined, there are still two free valence electrons at
each end of the chain for joining other mers or polymer chains. The process can continue
liking more mers and polymers together until it is stopped by the addition of anther
chemical (a terminator), that fills the available bond at each end of the molecule. This is
called a linear polymer and is building block for thermoplastic polymers.
The polymer chain is often shown in two dimensions, but it should be noted that they
have a three dimensional structure. Each bond is at 109° to the next and, therefore, the
carbon backbone extends through space like a twisted chain of TinkerToys. When stress
is applied, these chains stretch and the elongation of polymers can be thousands of times
greater than it is in crystalline structures.

The length of the polymer chain is very important. As the number of carbon atoms in the
chain is increased to beyond several hundred, the material will pass through the liquid
state and become a waxy solid. When the number of carbon atoms in the chain is over
1,000, the solid material polyethylene, with its characteristics of strength, flexibility and
toughness, is obtained. The change in state occurs because as the length of the molecules
increases, the total binding forces between molecules also increases.

It should also be noted that the molecules are not generally straight but are a tangled
mass. Thermoplastic materials, such as polyethylene, can be pictured as a mass of
intertwined worms randomly thrown into a pail. The binding forces are the result of van
der Waals forces between molecules and mechanical entanglement between the chains.
When thermoplastics are heated, there is more molecular movement and the bonds
between molecules can be easily broken. This is why thermoplastic materials can be
remelted.
There is another group of polymers in which a single large network, instead of many
molecules is formed during polymerization. Since polymerization is initially
accomplished by heating the raw materials and brining them together, this group is called
thermosetting polymers or plastics. For this type of network structure to form, the mers
must have more than two places for boning to occur; otherwise, only a linear structure is
possible. These chains form jointed structures and rings, and may fold back and forth to
take on a partially crystalline structure.

Since these materials are essentially comprised of one giant molecule, there is no
movement between molecules once the mass has set. Thermosetting polymers are more
rigid and generally have higher strength than thermoplastic polymers. Also, since there is
no opportunity for motion between molecules in a thermosetting polymer, they will not
become plastic when heated.
Types of polymers

• Commodity plastics
o PE = Polyethylene
o PS = Polystyrene
o PP = Polypropylene
o PVC = Poly(vinyl chloride)
o PET = Poly(ethylene terephthalate)
• Specialty or Engineering Plastics
o Teflon (PTFE) = Poly(tetrafluoroethylene)
o PC = Polycarbonate (Lexan)
o Polyesters and Polyamides (Nylon)
PROPERTIES OF POLYMER MATERIALS

Polymer properties are broadly divided into several classes based on the scale at which
the property is defined as well as upon its physical basis. The most basic property of a
polymer is the identity of its constituent monomers. A second set of properties, known as
microstructure, essentially describe the arrangement of these monomers within the
polymer at the scale of a single chain. These basic structural properties play a major role
in determining bulk physical properties of the polymer, which describe how the polymer
behaves as a continuous macroscopic material. Chemical properties, at the nano-scale,
describe how the chains interact through various physical forces. At the macro-scale, they
describe how the bulk polymer interacts with other chemicals and solvents

Monomers and Repeat Units

The identity of the monomer residues (repeat units) comprising a polymer is its first and
most important attribute. Polymer nomenclature is generally based upon the type of
monomer residues comprising the polymer. Polymers that contain only a single type of
repeat unit are known as homopolymers, while polymers containing a mixture of repeat
units are known as copolymers. Poly(styrene), for example, is composed only of styrene
monomer residues, and is therefore classified as a homopolymer. Ethylene-vinyl acetate,
on the other hand, contains more than one variety of repeat unit and is thus a copolymer.
Some biological polymers are composed of a variety of different but structurally related
monomer residues; for example, polynucleotides such as DNA are composed of a variety
of nucleotide subunits.

A polymer molecule containing ionizable subunits is known as a polyelectrolyte or

ionomer.

Microstructure

The microstructure of a polymer (sometimes called configuration) relates to the physical

arrangement of monomer residues along the backbone of the chain[8]. These are the
elements of polymer structure that require the breaking of a covalent bond in order to
change. Structure has a strong influence on the other properties of a polymer. For
example, two samples of natural rubber may exhibit different durability, even though
their molecules comprise the same monomers.

Polymer Architecture

Branch point in a polymer

An important microstructural feature determining polymer properties is the polymer

architecture. The simplest polymer architecture is a linear chain: a single backbone with
no branches. A related unbranching architecture is a ring polymer. A branched polymer
molecule is composed of a main chain with one or more substituent side chains or
branches. Special types of branched polymers include star polymers, comb polymers,
brush polymers, dendronized polymers, ladders, and dendrimers.

Branching of polymer chains affects the ability of chains to slide past one another by
altering intermolecular forces, in turn affecting bulk physical polymer properties. Long
chain branches may increase polymer strength, toughness, and the glass transition
temperature (Tg) due to an increase in the number of entanglements per chain. The effect
of such long-chain branches on the size of the polymer in solution is characterized by the
branching index. Random length and atactic short chains, on the other hand, may reduce
polymer strength due to disruption of organization and may likewise reduce the
crystallinity of the polymer.
A good example of this effect is related to the range of physical attributes of
polyethylene. High-density polyethylene (HDPE) has a very low degree of branching, is
quite stiff, and is used in applications such as milk jugs. Low-density polyethylene
(LDPE), on the other hand, has significant numbers of both long and short branches, is
quite flexible, and is used in applications such as plastic films. Dendrimers are a special
case of polymer where every monomer unit is branched. This tends to reduce
intermolecular chain entanglement and crystallization. Alternatively, dendritic polymers
are not perfectly branched but share similar properties to dendrimers due to their high
degree of branching.

The architecture of the polymer is often physically determined by the functionality of the
monomers from which it is formed. This property of a monomer is defined as the number
of reaction sites at which may form chemical covalent bonds. The basic functionality
required for forming even a linear chain is two bonding sites. Higher functionality yields
branched or even crosslinked or networked polymer chains. An effect related to
branching is chemical crosslinking - the formation of covalent bonds between chains.
Crosslinking tends to increase Tg and increase strength and toughness. Among other
applications, this process is used to strengthen rubbers in a process known as
vulcanization, which is based on crosslinking by sulfur. Car tires, for example, are highly
crosslinked in order to reduce the leaking of air out of the tire and to toughen their
durability. Eraser rubber, on the other hand, is not crosslinked to allow flaking of the
rubber and prevent damage to the paper.

A cross-link suggests a branch point from which four or more distinct chains emanate. A
polymer molecule with a high degree of crosslinking is referred to as a polymer network.
[11]
Sufficiently high crosslink concentrations may lead to the formation of an infinite
network, also known as a gel, in which networks of chains are of unlimited extent—
essentially all chains have linked into one molecule
Chain Length

The physical properties of a polymer are strongly dependent on the size or length of the
polymer chain.. For example, as chain length is increased, melting and boiling
temperatures increase quickly. Impact resistance also tends to increase with chain length,
as does the viscosity, or resistance to flow, of the polymer in its melt state. Chain length
is related to melt viscosity roughly as 1:103.2, so that a tenfold increase in polymer chain
length results in a viscosity increase of over 1000 times. Increasing chain length
furthermore tends to decrease chain mobility, increase strength and toughness, and
increase the glass transition temperature (Tg). This is a result of the increase in chain
interactions such as Van der Waals attractions and entanglements that come with
increased chain length.These interactions tend to fix the individual chains more strongly
in position and resist deformations and matrix breakup, both at higher stresses and higher
temperatures.

A common means of expressing the length of a chain is the degree of polymerization,

which quantifies the number of monomers incorporated into the chain. As with other
molecules, a polymer's size may also be expressed in terms of molecular weight. Since
synthetic polymerization techniques typically yield a polymer product including a range
of molecular weights, the weight is often expressed statistically to describe the
distribution of chain lengths present in the same. Common examples are the number
average molecular weight and weight average molecular weight. The ratio of these two
values is the polydispersity index, commonly used to express the "width" of the
molecular weight distribution. A final measurement is contour length, which can be
understood as the length of the chain backbone in its fully extended state.
The flexibility of an unbranched chain polymer is characterized by its persistence length.

Mechanical Properties

The bulk properties of a polymer are those most often of end-use interest. These are the
properties that indictate how the polymer actually behaves on a macroscopic scale.

Tensile Strength

The tensile strength of a material quantifies how much stress the material will endure
before suffering permanent deformation.[28][29] This is very important in applications that
rely upon a polymer's physical strength or durability. For example, a rubber band with a
higher tensile strength will hold a greater weight before snapping. In general, tensile
strength increases with polymer chain length and crosslinking of polymer chains.

Young's Modulus of Elasticity

Young's Modulus quantifies the elasticity of the polymer. It is defined, for small strains,
as the ratio of rate of change of stress to strain. Like tensile strength, this is highly
relevant in polymer applications involving the physical properties of polymers, such as
rubber bands. The modulus is strongly dependent on temperature.

Transport Properties

Transport properties such as diffusivity relate to how rapidly molecules move through the
polymer matrix. These are very important in many applications of polymers for films and
membranes.

Chemical properties
The attractive forces between polymer chains play a large part in determining a polymer's
properties. Because polymer chains are so long, these interchain forces are amplified far
beyond the attractions between conventional molecules. Different side groups on the
polymer can lend the polymer to ionic bonding or hydrogen bonding between its own
chains. These stronger forces typically result in higher tensile strength and higher
crystalline melting points.

The intermolecular forces in polymers can be affected by dipoles in the monomer units.
Polymers containing amide or carbonyl groups can form hydrogen bonds between
adjacent chains; the partially positively charged hydrogen atoms in N-H groups of one
chain are strongly attracted to the partially negatively charged oxygen atoms in C=O
groups on another. These strong hydrogen bonds, for example, result in the high tensile
strength and melting point of polymers containing urethane or urea linkages. Polyesters
have dipole-dipole bonding between the oxygen atoms in C=O groups and the hydrogen
atoms in H-C groups. Dipole bonding is not as strong as hydrogen bonding, so a
polyester's melting point and strength are lower than Kevlar's (Twaron), but polyesters
have greater flexibility.

Ethene, however, has no permanent dipole. The attractive forces between polyethylene
chains arise from weak van der Waals forces. Molecules can be thought of as being
surrounded by a cloud of negative electrons. As two polymer chains approach, their
electron clouds repel one another. This has the effect of lowering the electron density on
one side of a polymer chain, creating a slight positive dipole on this side. This charge is
enough to attract the second polymer chain. Van der Waals forces are quite weak,
however, so polyethylene can have a lower melting temperature compared to other
polymers.