Fundamentals of Materials: Behavior and Manufacturing Properties

Manufacturing Engineering and Technology
Fundamentals of Materials: Behavior and

Manufacturing Properties
1. The Structure of Metals
2. Mechanical Behavior, Testing and
Manufacturing Properties of Materials
3. Physical Properties of Materials
4. Metal Alloys: Structure and Strengthening by
Heat Treatment
5. Ferrous Metals and Alloys: Production,
General Properties and Applications
2005 Pearson Education South Asia Pte Ltd
Manufacturing Engineering and Technology
Fundamentals of Materials: Behavior and

Manufacturing Properties
6. Nonferrous Metals and Alloys: Production,
7. Polymers: Structure, General Properties and
Applications
8. Ceramics, Graphite and Diamond: Structure,
9. Composite Materials: Structure, General
Properties, and Applications
7. Polymers: Structure, General Properties and Applications
Chapter Objectives
• Structure of polymers, polymerization processes, crystallinity, and glass-
transition temperature.
• How temperature and deformation rate affect the properties of
thermoplastics.
• Differences between thermoplastics and thermosets.
• Properties and applications of polymers, their advantages and limitations.

Chapter Outline
1. Introduction
2. The Structure of Polymers
3. Thermoplastics
4. Thermosetting Plastics
5. Additives in Plastics
6. General Properties and Applications of Thermoplastics
7. General Properties and Applications of Thermosetting Plastics
8. Biodegradable Plastics
9. Elastomers (Rubbers)

7.1 Introduction
• Plastics are one of numerous polymeric materials and have extremely large molecules (macromolecules or giant molecules).
• The advantages of polymers in terms of the following characteristics:
• Corrosion resistance and resistance to chemicals
• Low electrical and thermal conductivity
• Low density
• High strength-to-weight ratio (particularly when reinforced)
• Noise reduction

7.1 Introduction
• Noise reduction
• Ease of manufacturing and complexity of design possibilities
• Relatively low cost
• Other characteristics that may or may not be desirable (depending on the application), such as low strength
and stiffness (Table 7.1), high coefficient of thermal expansion, low useful-temperature range—up to about
350°C, and lower dimensional stability in service over a period of time.

7.1 Introduction

7.1 Introduction
• Plastics can be formed, machined, cast, and joined into various shapes with relative ease.
• Plastics are available commercially as film, sheet, plate, rods, and tubing of various cross-sections.
• An outline of the basic process of making various synthetic polymers is given in Fig. 7.1.

7.1 Introduction

7.2 The Structure of Polymers
• The properties of polymers depend largely on the structures of individual polymer molecules, molecule shape and size, and
how molecules are arranged to form a polymer structure.
• Polymers are long-chain molecules that are formed by polymerization (that is, by the linking and cross-linking of different
monomers).
• A monomer is the basic building block of a polymer.
• The word mer (from the Greek meros, meaning part) indicates the smallest repetitive unit; its use is similar to that of the term
unit cell in crystal structures of metals.

• The term polymer means many mers (or units), generally repeated
hundreds or thousands of times in a chainlike structure.
• Fig 7.2 shows the molecular structure of various polymers. These
are examples of the basic building blocks for plastics.


• In condensation polymerization polymers are produced by the formation of bonds
between two types of reacting mers.
• Fig 7.3 shows the examples of polymerization. (a) Condensation polymerization of
nylon 6,6 and (b) addition polymerization of polyethylene molecules from ethylene
mers.


• This process is also known as step-growth or step-reaction polymerization,
because the polymer molecule grows step-by-step until all of one reactant is
consumed.
• In addition polymerization (also called chain-growth or chain-reaction
polymerization), bonding takes place without reaction by-products,

Molecular Weight
• The sum of the molecular weights of the mers in a representative chain is known as the molecular weight of
the polymer.
• The spread of the molecular weights in a chain is referred to as the molecular weight distribution (MWD).
• A polymer’s molecular weight and its MWD have a strong influence on its properties.

Molecular Weight
• Fig 7.4 shows the effect of molecular weight and degree of
polymerization on the strength and viscosity of polymers.

Degree of Polymerization
• It is convenient to express the size of a polymer chain in terms of the degree of polymerization (DP), which
is defined as the ratio of the molecular weight of the polymer to the molecular weight of the repeating unit.
• The higher the DP, the higher is the polymer’s viscosity or its resistance to flow.
• High viscosity adversely affects the ease of shaping and, thus, raises the overall cost of processing.

Bonding
• During polymerization, the monomers are linked together by covalent bonds, forming a polymer chain.
• Because of their strength, covalent bonds also are called primary bonds.
• The polymer chains are, in turn, held together by secondary bonds, such as van der Waals bonds, hydrogen
bonds, and ionic bonds.
• Secondary bonds are weaker than primary bonds by one to two orders of magnitude.

Linear Polymers
• The chain-like polymers shown in Fig. 7.2 are called linear polymers because of their sequential structure.
• Fig 7.5 shows the schematic illustration of polymer chains. (a) Linear structure— thermoplastics such as acrylics, nylons,
polyethylene, and polyvinyl chloride have linear structures. (b) Branched structure, such as in polyethylene. (c) Cross-
linked structure—many rubbers or elastomers have this structure, and the vulcanization of rubber produces this structure.
(d) Network structure, which is basically highly cross-linked—examples are thermosetting plastics, such as epoxies and
phenolics.


Branched Polymers
• The properties of a polymer depend not only on the type of monomers but also on their
arrangement in the molecular structure.
• In branched polymers (Fig. 7.5b), side-branch chains are attached to the main chain
during the synthesis of the polymer.

Cross-linked Polymers
• Generally three-dimensional in structure, cross-linked polymers have adjacent chains linked by covalent bonds
(Fig. 7.5c).
• Polymers with a cross-linked chain structure are called thermosets, or thermosetting plastics.
• Fig 7.6 shows the behavior of polymers as a function of temperature and (a) degree of crystallinity and (b) cross-
linking. The combined elastic and viscous behavior of polymers is known as viscoelasticity.


Network polymers
• These polymers consist of spatial (three-dimensional) networks of three
or more active covalent bonds (Fig. 7.5d).
• A highly cross-linked polymer also is considered a network polymer.

Copolymers and terpolymers
• If the repeating units in a polymer chain are all of the same type, the molecule is called a homopolymer.
• Copolymers contain two types of polymers (for example, styrene-butadiene, which is used widely for
automobile tires).
• Terpolymers contain three types (for example, ABS (acrylonitrilebutadiene-styrene), which is used for
helmets, telephones, and refrigerator liners).

Example 7.1 Dental and medical bone cement
Polymethylmethacrylate (PMMA) is an acrylic polymer commonly
used in dental and medical applications as an adhesive and
commonly is referred to as bone cement. There are a number of
forms of PMMA, but this example describes one common form
involving an addition-polymerization reaction. PMMA is delivered
in two parts: a powder and a liquid, which are mixed by hand. The
liquid wets and partially dissolves the powder, resulting in a liquid
with viscosity on the order of 0.1 Ns/m 2 similar to that of vegetable
oil. The viscosity increases markedly until a “dough” state is
reached in about five minutes and fully hardens from the dough
state in an additional five minutes.

The powder consists of high molecular weight
poly[(methylmethacrylate)- costyrene] particles of about 50 micro-
meter in diameter, containing a small volume fraction of benzoyl
peroxide. The liquid consists of a methyl methacrylate (MMA)
monomer, with a small amount of dissolved n,n dimethyl-p-
toluidine (DMPT). When the liquid and powder are mixed, the
MMA wets the particles (dissolving a surface layer of the PMMA
particles) and the DMPT cleaves the benzoyl peroxide molecule
into
two parts to form a catalyst with a free electron (sometimes
referred to as a free radical). The resulting catalyst causes rapid
growth of PMMA from the MMA mers, so that the final material is
a composite of high molecular weight PMMA particles
interconnected by PMMA chains. A schematic diagram of fully set
bone cement is shown in Fig. 7.7.

7.2.2 Crystallinity
• Polymers such as polymethylmethacrylate, polycarbonate, and polystyrene are generally amorphous; that is,
the polymer chains exist without long-range order.
• The crystalline regions in polymers are called crystallites.
• Fig 7.8 shows the amorphous and crystalline regions in a polymer.
• The crystalline region (crystallite) has an orderly arrangement of molecules. The higher the crystallinity, the
harder, stiffer, and less ductile the polymer.

7.2.2 Crystallinity

7.2.2 Crystallinity
• These crystals are formed when the long molecules arrange themselves in an orderly manner, similar to
the folding of a fire hose in a cabinet or of facial tissues in a box.
• A partially crystalline (semi-crystalline) polymer can be regarded as a two-phase material, one phase
being crystalline and the other amorphous.
• By controlling the rate of solidification during cooling and the chain structure, it is possible to impart
different degrees of crystallinity to polymers, although never 100%.

7.2.2 Crystallinity
Effects of crystallinity
• The mechanical and physical properties of polymers are greatly influenced by the degree of crystallinity:
as crystallinity increases, polymers become stiffer, harder, less ductile, more dense, less rubbery, and
more resistant to solvents and heat (Fig. 7.6).
• The increase in density with increasing crystallinity is called crystallization shrinkage and is caused by a
more efficient packing of the molecules in the crystal lattice.

7.2.3 Glass-transition temperature
• The temperature at which a transition occurs is called the glass-transition temperature, T g, also called the glass point or
glass temperature.
• To determine Tg, the specific volume of the polymer is determined and plotted against temperature, and marked by a sharp
change in the slope of the curve.
• Fig 7.9 shows the Specific volume of polymers as a function of temperature. Amorphous polymers, such as acrylic and
polycarbonate, have a glass-transition temperature, but do not have a specific melting point, Partly crystalline polymers, such
as polyethylene and nylons, contract sharply while passing through their melting temperatures during cooling.


• The glass-transition temperature varies with different
polymers (Table 7.2).

7.2.4 Polymer Blends
• The brittle behavior of amorphous polymers below their glass-transition temperature can be reduced by blending them—
usually with small quantities of an elastomer.
• These polymer blends are known as rubber modified polymers.
• Advances in blending involve several components, creating polyblends that utilize the favorable properties of different
polymers.
• Miscible blends (mixing without separation of two phases) are created by a process similar to the alloying of metals that
enables polymer blends to become more ductile.

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Manufacturing Engineering and Technology

Fundamentals of Materials: Behavior and

Fundamentals of Materials: Behavior and

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

2005 Pearson Education South Asia Pte Ltd

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