Plastics: Microstructure and Engineering Applications

Plastics

Microstructure and Engineering Applications

Fourth Edition

Nigel Mills

University of Birmingham, UK

Mike Jenkins

University of Birmingham, UK

Stephen Kukureka

University of Birmingham, UK

Table of Contents

Cover image

Title page

Copyright

Preface

Chapter 1. Introduction

1.1. Plastics and polymers

1.2. The development of the macromolecular concept

1.3. Classes of polymer

1.4. The plastics age

1.5. Properties of common thermoplastics

1.6. Polymer processing and product features

1.7. Conclusions

Chapter 2. Molecular structures and polymer manufacture

2.1. Introduction

2.2. Polymerization

2.3. Molecular weight distribution

2.4. Chain regularity

2.5. Branched and cross-linked polymers (thermosets and rubbers)

2.6. Bonding and intermolecular forces in polymers

2.7. Industrial polymer production and economics of manufacture

2.8. Grades and applications of commodity plastics

Chapter 3. Amorphous polymers and the glass transition

3.1. Introduction

3.2. Modelling the shape of a polymer molecule

3.3. The glass transition temperature

Chapter 4. Semi-crystalline polymers

4.1. Introduction

4.2. Structure and shape

4.3. Percentage (or degree of) crystallinity

4.4. Crystalline phase orientation

4.5. Crystallization kinetics

4.6. Modulus of spherulitic polyethylene

Chapter 5. Processing

5.1. Introduction

5.2. Heat transfer mechanisms

5.3. Melt flow of thermoplastics

5.4. Extrusion

5.5. Processes involving melt inflation

5.6. Injection moulding

5.7. Thermoset processing – reaction injection moulding

5.8. Additive manufacturing

Chapter 6. Effects of melt processing

6.1. Introduction

6.2. Microstructural changes

6.3. Macroscopic effects

6.4. Fusion of particle and bead polymers

Chapter 7. Viscoelastic behaviour

7.1. Introduction

7.2. Linear viscoelastic models

7.3. Creep design

7.4. Cyclic deformation and dynamic mechanical analysis

Chapter 8. Yielding

8.1. Molecular mechanisms of yielding

8.2. Yield under different stress states

8.3. Yield on different time scales

8.4. Orientation hardening

8.5. Micro-yielding

Chapter 9. Fracture

9.1. Introduction

9.2. Fracture surfaces and their interpretation

9.3. Crack initiation

9.4. Crack growth

9.5. Impact tests

Chapter 10. The ageing of polymers

10.1. Introduction: ageing, degradation and environmental effects

10.2. Degradation during processing

10.3. Degradation at elevated temperatures

10.4. Fire

10.5. Weathering

10.6. Environmental stress cracking

10.7. Physical ageing (enthalpy or volume relaxation)

10.8. Secondary crystallization

Chapter 11. Transport properties

11.1. Gases

11.2. Liquids

11.3. Solids

11.4. Light

11.5. Thermal barriers

Chapter 12. Electrical properties

12.1. Conducting polymers

12.2. Volume and surface resistivity

12.3. Insulation and applications of semiconducting polymers

12.4. Dielectric behaviour

12.5. Flexible switches and electrets

Chapter 13. Multi-component polymers – improving the properties of polymers

13.1. Introduction

13.2. Rubber toughening

13.3. Polymer blends

13.4. Phase-separated structures

13.5. Foams

13.6. Short fibre reinforcement

Chapter 14. Design: Materials, shape selection and design for the environment

14.1. Introduction

14.2. Polymer selection

14.3. Shape selection to optimize stiffness

14.4. Product shapes for injection moulding

14.5. Instrument panel case study

14.6. Materials selection, design for the environment and sustainability

Chapter 15. Engineering case studies

15.1. Introduction

15.2. Pipes for natural gas distribution

15.3. Bicycle helmets

15.4. Dynamic climbing ropes

15.5. Blood bag case study

15.6. Ultrahigh molecular weight polyethylene for hip joint implants

Appendix A. Diffusion of heat or impurities

Appendix B. Polymer melt flow analysis

Appendix C. Mechanics concepts

Further reading

Index

Copyright

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Preface

This is the fourth edition of an established textbook intended for undergraduates or master's degree students on Materials Science and Engineering or related degree courses, such as polymer technology or mechanical or chemical engineering. It will also be suitable for scientists and engineers who require an introduction to the properties and applications of plastics. Aspects of mechanical design specific to plastics products are emphasized, as are explanations of physical properties in terms of microstructure. In these respects, it differs from texts emphasizing primarily chemical aspects of polymers or mechanical design in terms of stress analysis.

When plastics are used, or are substituted for other materials, products should be designed to suit the appropriate polymer processing technology. Therefore the merits and limitations of these processes must be understood. Processing has permanent consequences for the microstructure of the product, and these must be anticipated and used to advantage if possible. This interlocking nature of different aspects of plastics technology provides a challenge to engineers. By exploring the relationships between the properties of plastics and their microstructure, we begin to see the possibilities and the limitation of this class of materials. This book emphasizes concepts and links between polymer engineering and other areas of science and technology.

Major changes were made in preparing this fourth edition. The first four chapters have been substantially rewritten and restructured; after an introductory chapter, they cover molecular structures in Chapter 2, amorphous polymers in Chapter 3 and partially crystalline polymers in Chapter 4. These are followed by revised and updated chapters on processing and its effects, viscoelasticity, fracture and yielding in Chapters 5–9. A new Chapter 10 covers ageing of polymers followed by Chapter 11 on transport properties and a revised Chapter 12 on electrical properties of polymers. Chapter 13 covers methods of improving the properties of polymers, and Chapter 14 discusses aspects of design with polymers – in particular materials, shape selection and design for the environment. Finally, there are some engineering case studies in Chapter 15. Overall, the material has been developed and thoroughly updated, and the principles of polymer structure–property relationships set out more clearly. The derivation of many key equations is included, since their assumptions and principles should be recognized. However, there are three appendices covering mathematical details which are not always treated in materials science and engineering courses: Appendices A and B cover diffusion (of heat or impurities) and polymer melt flow analysis, while Appendix C provides some mechanics concepts. There is also a completely updated Further Reading section.

The first three editions of this book were entirely the work of our late, esteemed colleague Nigel Mills (1943–2014). As an inspiring and dedicated researcher and teacher, he developed the courses and the material that formed the basis of the first three editions over many years, both in industry and then at the University of Birmingham. We are forever in his debt and feel honoured to be able to revise and prepare this new edition for a new generation of students.

We also have acknowledgements to some of those students, postgraduate and undergraduate, who helped with this edition. Rob Arnold, Amrita Bhogal and Will Hamby contributed, and we also had help from Ben Colgan, Lucy Feather, Will Savage and Jordan Thompson. We are grateful for their help but of course, any errors remaining are our own.

Mike Jenkins

Stephen Kukureka

Birmingham, July 2019

Chapter 1

Introduction

Abstract

The words plastics and polymers are often used interchangeably and there are no strict definitions that are widely accepted. The word ‘Plastics’ comes from Latin or Greek words suggesting ‘able to be moulded’. The word ‘polymer’ comes from the Greek words ‘poly’ meaning many and ‘mer’ meaning unit. Polymers are based on large molecules or macromolecules composed of chemical building blocks known as the ‘repeat unit’. In practice, the word ‘plastics’ tends to be used only in the plural by people in the industry, to avoid confusion with the adjective ‘plastic’ used to describe permanent changes of shape or ‘plastic deformation’ which can occur in any material. Also ‘plastics’ commonly refer to commercial materials containing not only polymer macromolecules but also additives such as colourants, stabilizers, flow modifiers and other chemicals needed to produce stable commercial materials. This chapter begins with an overview of the development of the macromolecular concept and then briefly explores the various classes of polymer, their properties and their processing.

Keywords

Injection mouldings; Plastic deformation; Plastics; Polymers; Semi-crystalline polymers; Thermoplastics

1.1 Plastics and polymers

1.2 The development of the macromolecular concept

1.3 Classes of polymer

1.4 The plastics age

1.5 Properties of common thermoplastics

1.5.1 Product appearance

1.5.2 Density

1.5.3 Thermal properties

1.5.4 Mechanical properties

1.6 Polymer processing and product features

1.6.1 Blow mouldings

1.6.2 Extruded products

1.6.3 Injection mouldings

1.6.4 Thermoformed products

1.6.5 Blown film

1.6.6 Injection blow moulded bottles

1.7 Conclusions

1.1. Plastics and polymers

The words plastics and polymers are often used interchangeably and there are no strict definitions that are widely accepted. The word ‘Plastics’ comes from Latin or Greek words suggesting ‘able to be moulded’. The word ‘polymer’ comes from the Greek words ‘poly’ meaning many and ‘mer’ meaning unit. Polymers are large molecules or macromolecules composed of chemical building blocks known as the ‘repeat unit’. In practice, the word ‘plastics’ tends to be used only in the plural by people in the industry, to avoid confusion with the adjective ‘plastic’ used to describe permanent changes of shape or ‘plastic deformation’ which can occur in any material. Also ‘plastics’ commonly refer to commercial materials containing not only polymer macromolecules but also additives such as colourants, stabilizers, flow modifiers and other chemicals needed to produce stable commercial materials.

1.2. The development of the macromolecular concept

Plastics were in use for quite some time before their chemical basis was understood. In 1844, a process known as vulcanization was patented. The process was based on the inclusion of sulphur into natural rubber for the purpose of improving the elasticity and reducing the ‘tackiness’. The inventor was Charles Goodyear. Later, Nelson Goodyear (Charles' brother) patented the idea of incorporating additional sulphur into the mix to yield much harder materials that became known as ebonite and vulcanite. These materials were used in telephone housings, dental plates and the nib feeds in fountain pens. In the 1860s, Alexander Parkes worked on and eventually patented a new ‘plastic’ that was based on an earlier, unstable and explosive substance called cellulose nitrate. Parkes developed a process that yielded a stable and mouldable ‘plastic’ material. Unfortunately, the new material called ‘Parkesine’ was expensive and the product was quite variable in terms of quality. In the early 1900s, what is now termed the first synthetic polymer was developed. ‘Bakelite’ was introduced by Leo Baekeland. The material was polymeric phenol formaldehyde and a very wide variety of products were made from Bakelite from clothing buttons to electrically-insulated heat-resistant housings.

Up to 1920, the long-chain nature of these materials was not recognized, but that year, a controversial paper was published which introduced the idea that ‘polymers’ were actually long-chain (macro) molecules composed of repeating units. The idea was not well-received. Over the next 10 years, the author Hermann Staudinger worked hard to convince the scientific community that his idea was correct and in conjunction with findings from other scientists (Wallace Carothers, for example); by the 1930s, there was widespread acceptance of the concept of a macromolecule and the subject of polymer science blossomed. Staudinger's wife later wrote that her husband encountered opposition in all his lectures. Only in 1929 was there no opposition from the audience: ‘this both astonished and pleased us’. Once Staudinger's macromolecular concept was accepted, it was the dawn of the ‘age of plastics’. From 1930 to 1960, a wide range of (now very familiar) polymers were commercialized including polyamide (PA), polystyrene (PS), poly(methyl methacrylate) and poly(ethylene terephthalate) (PET). In 1953, Staudinger was awarded the Nobel Prize for his work. The repeat units for a range of polymers are shown in Tables 2.1 and 2.2 (Chapter 2).

1.3. Classes of polymer

There are several classifications and terms associated with polymers. Two key terms are thermoplastics and thermosets. Thermoplastic polymers can be subdivided into two subclasses (or morphologies): amorphous (Greek meaning without shape or form) and semi-crystalline (note that the term partially crystalline is also used in this context). Products made from thermoplastic polymers can be reformed or reshaped on heating. Thermosets, in contrast, undergo a permanent chemical change when the initial components react and their shape cannot be changed by heating.

Amorphous polymers (which may be thermoplastic or thermoset) consist of a system of chains that are coiled and entangled with no long-range order; a single molecular coil is illustrated in Fig. 1.1. The chains do not pack well and there is unoccupied space or free volume in the material. The free volume in an amorphous polymer is in the region of 10%. Amorphous polymers do not melt, but they do soften as they transition from glass to liquid. In an industrial context, the softening point of a thermoplastic is readily determined using a Vicat test. In this test, a flat-ended needle contacts the surface of a polymer sample. Heat is applied to the sample either by immersion in a heated bath or via some form of direct contact heating system. The Vicat softening temperature is defined as the temperature at which the needle penetrates the sample to a depth of 1   mm. A more precise determination of softening point is by the glass to liquid transition temperature (Tg) and methods of measuring it will be described later.

Semi-crystalline polymers are composed of superstructures called spherulites (Fig. 1.2), which comprise thin crystalline layers (lamellae) radiating from a central nucleus. The interlamellar regions are amorphous. Semi-crystalline polymers exhibit a melting point. On close inspection, they also exhibit a Tg (although it is less marked than in an amorphous polymer).

Thermosetting polymers cannot be reformed on heating; their shape is fixed after processing. This is due to the formation of cross-links between chains via covalent bonding. Another class of polymers is known as elastomers. Polymers in this class exhibit very high degrees of reversible elongation under relatively low loads. Materials conventionally called rubbers (natural or synthetic) fall into this category. Both thermosets and elastomers are amorphous networks of cross-linked molecules. However, in thermosets, the Tg is typically above their operating temperature and in elastomers the Tg is typically below room temperature.

In thermosets and rubbers, the cross-linking reaction that occurs in the production of thermosets also enables good adhesion to other materials. Therefore, epoxy and polyester resin matrices are used for fibre-reinforced composites, amino resins are used for bonding fibreboard and phenolics are used for bonding fibres in brake pads. In comparison with thermoplastics, the industrial consumption of thermosets is almost static, reflecting a loss of some markets to thermoplastics with a high temperature resistance.

Figure 1.1 A simulation of a polymer molecular coil.

Figure 1.2 Spherulite formation in a thin polymer film (optical microscopy). In this instance, the crystallizing polymer is constrained within two glass coverslips, which cause the growth to be disc-like instead of spherical. Growth occurs until the growth fronts impinge as shown on the right side of the image.

Rubber consumption is dominated by tyre production. In this application and others such as conveyor belts and pressure hoses, thin layers of either steel wire or polymeric fibre reinforcement take the main mechanical loads. These layers, with rubber interlayers, allow flexibility in bending, whereas the reinforcement limits the in-plane stretching of the product. The applications are dominated by natural rubber and styrene butadiene copolymer rubber. Other rubbers have specialized properties: butyl rubbers have low air permeability, and nitrile rubbers have good oil resistance, while silicone rubbers have high and low temperature resistance. Rubbers play a relatively small role in this book, but the rubbery behaviour of the amorphous phase in semi-crystalline thermoplastics is important.

1.4. The plastics age

Global polymer production in 1950 was in the region of 1.5 million tonnes. In the 65 years that followed, there was a continuous increase leading to a production of over 320 million tonnes in 2015. Thermoplastics represent the overwhelming majority of polymer production: in 2015, in the region of 270 million tonnes of thermoplastics were produced. Indicative figures for global consumption by thermoplastic type are shown in Table 1.1 The first four in the table are regarded as commodity thermoplastics. Many manufacturers compete to supply these. Prices change quite rapidly, in response to the price of crude oil. The low density of thermoplastics, ranging from 900   kg   m −³ for polypropylene (PP) to 1400   kg   m −³ for polyvinyl chloride (PVC), means that the material costs are low in volume terms. The remaining thermoplastics in Table 1.1 are called engineering thermoplastics because of their superior mechanical properties, but the distinction is a fine one. They are produced on a smaller scale and have prices about twice that of commodity thermoplastics. Finally, there are speciality plastics which only sell a few thousand tonnes per annum. An example is polytetrafluoroethylene, which has unique low friction properties. Recycling marks on products allow the common plastics to be readily identified. Sometimes, numbers are used in place of the abbreviation for the polymer name.

Table 1.1

The spectacular growth in the production of polymers can be understood when the versatility of polymeric materials is considered.

Polymers have advantages over metals of being:

• self-coloured, by adding about 0.1% of dispersed pigment. There are no painting costs, and the product maintains its colour if scratched

• electrical insulators. There is no need for insulating layers between live parts and the body of product, and assembly is simplified

• thermal insulators

• of low density, so lightweight products can be made

• impact resistant, with a high yield strain, so thin panels do not dent if locally loaded

Polymers have advantages over ceramics or glasses of being:

• tough, so impacts are unlikely to cause brittle fracture

• of low melting point, so the energy costs for processing are low

• capable of being moulded into complex shapes with the required final dimensions (they are ‘net-shaped’, with no final machining stage)

In addition:

• Polymers can be sustainable. Monomers can be produced from natural and sustainable sources

• Some polymers are biodegradable

• Polymers are viscoelastic and can be used to absorb energy

1.5. Properties of common thermoplastics

1.5.1. Product appearance

Assuming the material is unpigmented, translucent products are semi-crystalline, e.g. PE. Some thin (<1   mm) or highly oriented products appear transparent, in spite of being semi-crystalline (e.g. PET bottles), because the crystals are too small to scatter light. Some thicker PP products appear translucent, but thin mouldings, especially if the PP is nucleated (Section 4.5), will appear nearly transparent. Transparent mouldings thicker than 1   mm will be one of the glassy polymers (PVC, PS, PC, etc.). If a thin film of molten, unpigmented plastic is opaque to light, it is likely to contain some form of filler.

1.5.2. Density

An electronic densitometer can measure the density of small (<10   g) pieces, using Archimedes principle. The pieces are weighed in air and then again suspended in water. Table 1.2 gives the densities (together with glass transition temperatures and melting points) of the main polymers. They are arranged in classes, in order of increasing density. The density of semi-crystalline plastics increases with crystallinity, so a range is given. If a significant amount of a reinforcing or toughening material is added, the density changes, making it more difficult to identify the polymer.

1.5.3. Thermal properties

Table 1.2 shows the temperature Tm at which the crystalline phase melts, or, for non-crystalline polymers, the glass transition temperature Tg at which the glass changes into a melt. Crude estimates of the Tg and Tm can be found by using a hot plate; at sufficiently high temperatures, polymer samples can be observed to soften and flow to a limited degree. Accurate determination of Tg and Tm requires the use of more specialist analytical equipment such as differential scanning calorimetry (described in Chapter 4).

Table 1.2

T m , crystal melting temperature; T g , glass transition temperature.

Figure 1.3 (A) Crazes in and (B) broken pieces of a polystyrene pen body after a bending experiment.

1.5.4. Mechanical properties

The stiffness of a polymer sample can be estimated through the use of a flexural test. In its most simple form, a polymer sample (say 100   mm long, 20   mm wide, 2   mm thick) is supported close to either end of the beam on metallic bars of circular cross section. A load is applied in the centre of the beam and the deflection is recorded. The Young's modulus can be calculated from the following equation (for an associated test standard, see ASTM D790)

(1.1)

where E B is the modulus of elasticity in bending, L is the support span, b is the width of the beam, d is the thickness of the beam and m is the slope of the tangent to the linear section of the load–deflection curve. Modulus values for polymers vary: Low-density polyethylene (LDPE) is of much lower modulus (circa 100   MPa) than most other plastics (1–3   GPa); it is also relatively soft in that the surface can be marked with a finger nail.

Brittle fracture in a polymer can be readily demonstrated using a clear-body (PS) disposable ballpoint pen. If the body of the pen is subjected to a deflection of about 10   mm (using the 3-point bend apparatus described above) and the deflection maintained at this value for a period of about 30s and the load released, the pen returns to its original shape. Close inspection of the body of the pen (by holding it up to a light source) reveals multiple parallel reflective planes (Fig. 1.39(A)); these are called crazes and indicate the presence of multiple fine cracks in the material. If the loading is repeated until the body of the pen fails, brittle failure occurs (Fig. 1.3(B)). Crazing and brittle failure occurs in glassy amorphous polymers.

In contrast to the brittle failure of PS, LDPE can exhibit ductile yielding. Again, this can be easily demonstrated by using LDPE strapping used in a ‘four-pack’ of drink cans (0.42   mm thick polymer). If a section is cut out and pulled slowly (by hand), parts of the strapping undergo tensile necking followed by cold drawing of the thin region (Fig. 1.4). Note how the shoulder of the neck moves into the un-necked region.

Figure 1.4 Necking and cold drawing of low-density polyethylene strapping from a four-pack drink can.

1.6. Polymer processing and product features

Polymers are plastics materials; they are mouldable and can be formed into a wide variety of complex shapes using some form of mould. Thermoplastics are moulded through the application of heat such that they become formable. A range of descriptors are used to describe this, including ‘soft’ and ‘pliable’, but the key molecular aspect is that the polymer chains must be mobilized such that they can flow and the material can take the form of the mould. This is accomplished either by heating above Tg or Tm according to the morphology of the chosen polymer, for example, to be moulded; PS needs to be heated above Tg, whereas PE needs to be heated above Tm.

Once the mould is filled, the polymer is cooled to allow the shape to stabilize. The shape stabilization mechanism depends on whether or not the polymer can crystallize. If the polymer is non-crystallizable, the shape stabilization mechanism is simply glass formation and the polymer must be cooled to a temperature below Tg. If the polymer is crystallizable, the shape stabilization mechanism is crystallization and the process must be given sufficient time to occur.

Polymers can be moulded using a wide range of processing methods and the aim of this section is to briefly introduce some common polymer processing techniques and illustrate the typical forms that each technique can produce.

1.6.1. Blow mouldings

These are hollow containers, usually with an opening of smaller diameter than the body. Both ends of the moulding may be cut off to produce a tubular product or one end cut off for a bucket-shaped container. The wall thickness varies with position, and there is a weld line across the closed end of the container (Fig. 1.5). Sometimes, near-parallel lines are visible on the inner surface; these indicate the extrusion direction when the parison (tubular preform) emerged from a die. The weld location on the base of a high-density polyethylene (HDPE) milk bottle aligns with the external surface line from the mould split. Stiff HDPE tool boxes can be created by allowing the two sides of the blow moulding to come into contact at some locations and form welds (Fig. 1.6). The 0.4   mm thick hinge region is created by pressing the HDPE with metal bars, and the ‘click shut’ catches are also part of the blow moulding.

1.6.2. Extruded products

These have a constant cross section. Examples are domestic gutters or downpipes, or (replacement) window frames, made from PVC. For pipes, the outer surface is in contact with a sizing die, whereas the inner surface cools in air and can change shape slightly. The pipe wall provides the bending stiffness and resistance against weathering. Pipes for various communication cables in the United Kingdom are green with a corrugated exterior, but a smooth inner wall. Fig. 1.7 shows a pipe for electrical cable, with an outer red corrugated layer bonded to a smooth inner black layer (details of the process are given in Chapter 14). Such pipes offer maximum resistance to crushing by soil loads for a given weight of polymer.

1.6.3. Injection mouldings

Injection mouldings can contain a variety of surface feature such as T junctions (where ribs meet a surface) and holes. Fig. 1.8 shows the underside of the heater unit in a typical electric kettle showing the ribbed PA injection moulding. The point where the sprue, which feeds the melt into the mould cavity, has been removed should be visible as a slightly rough, often circular region. On the concave side of the product, circular surface marks indicate the location of ejector pins, which push the cold moulding from the mould. Fig. 1.9, of a moulded box, shows the ejector pin marks on the inside of the box and a moulded-in hinge between the two halves.

Figure 1.5 Sectioned blow moulded bottle, showing the weld line in the base.

Figure 1.6 Section through a blow moulded high-density polyethylene tool box (45   mm thick). Both lid and base of the box are hollow, with reinforcing welds at intervals interior.

Figure 1.7 Section through an extruded high-density polyethylene pipe, with corrugations at 18   mm intervals, for buried electric cables.

Figure 1.8 Underside of the heater unit in a typical electric kettle showing the ribbed polyamide (PA) injection moulding.

If the surface of the mould is textured, the moulded product will also be textured. This is shown in the surface of a polypropylene seat section of a stackable chair (Fig. 1.10). The seat surface has a moulded-in texture, which increases the coefficient of friction with clothing and also disguises scratches. In this example, the seat sides are ‘bent over’, providing a place to grip the seat and also increasing the bending stiffness of the seat.

Figure 1.9 Section through an injection moulded polypropylene box for a micrometer. The moulded-in hinge has whitened in use.

Figure 1.10 Texture on the upper side of a polypropylene chair.

1.6.4. Thermoformed products

These tend to be curved panels or shallow containers. They have a variable thickness because only the convex side contacts a metal die. They can be as thin as 0.1   mm, as a sheet of melt is stretched before contact with the cold mould, or as thick as 10   mm. There will be no signs of any injection point or ejector pins. Typical examples are disposable coffee cups (Fig. 1.11(A)), margarine containers, baths, shower trays and chocolate box inserts.

The thermoforming process can be reversed on heating. Exposing a thermoformed PS cup to a temperature of 120   °C causes a gradual shape reversion to a nearly flat sheet (Fig. 1.11(B)). The thermoforming process involved the elastic stretching and molecular orientation in a sheet of polymer melt, and this orientation was locked-in to the cup when it cooled. On reheating, the polymer attempts to return to its original shape.

1.6.5. Blown film

The blown film process creates a continuous tube of film, usually less than 0.25   mm thick, which is flattened and rolled up. It can be cut into lengths and welded to produce products such as supermarket carrier bags.

1.6.6. Injection blow moulded bottles

Carbonated drinks are often contained in bottles made from PET; the moulded neck threads shown in Fig. 1.12 have T sections. The internal pressure of 4   bar in the carbonated drink bottle can only be resisted by a lightweight bottle if the polymer is oriented to increase its strength. The location of the injection sprue is in the centre of the base of the PET bottle. The relaxation of chain extension is apparent when an empty PET bottle is placed in an oven at 120   °C for 1   hour. There is shrinkage in both length and diameter, indicating that the PET has been biaxially oriented. The base and the neck become milky in appearance, due to the crystallization of these initially amorphous regions. The shrinkage in these regions is relatively low.

Figure 1.11 (A) Section through a thermoformed polystyrene disposable coffee cup, with shallow corrugations in the 0.2   mm thick sidewall. (B) The corrugations were outlined in felt-tip pen and then the cup heat reverted to 0.8   mm thick sheet.

Figure 1.12 Details of the neck region of an injection blow moulded polyethylene terephthalate bottle. The bottle on the left has been heat treated at 120   °C, while the neck of a preform is shown on the right.

Figure 1.13 Range of size scales in polymer science.

1.7. Conclusions

This chapter has shown that polymers can be considered over a range of size or length scales from that of the repeat unit to that of the final product and this is illustrated in Fig. 1.13. This chapter has also shown that polymers can be processed using a variety of techniques to produce a wide range of product forms with properties that are a function of chemical structure, microstructure and macrostructure. These themes and the relationship between them are explored in the chapters that follow.

Chapter 2 considers the production of polymers and their molecular architectures. Chapter 3 considers the properties of coiled and entangled amorphous polymers. Chapter 4 considers the microstructures associated with semi-crystalline polymers and the crystallization process. The processing of polymers is considered in Chapter 5 and then a wide range of polymer properties and applications are explored in Chapters 6–12. Chapter 13 considers ways of improving the properties of polymers through the development of multicomponent materials. Chapter 14 explores the effect of material and shape selection on the performance of a polymer product. Chapter 15 contains a series of case studies to illustrate various concepts presented in this book.

Chapter 2

Molecular structures and polymer manufacture

Abstract

Polymers can be considered on a range of length scales from that of molecules to that of the final products. This chapter focuses on the molecular level and begins with an overview of two industrially significant polymerization routes, addition and step-growth polymerization, in which monomer is converted to polymer. These polymerization routes can be used to produce a wide range of commercially important polymeric materials including polyethylenes and polyamides (PAs). The concept that polymer systems are composed of a distribution of chain lengths is considered, and two key measures of molecular weight, the number-average and weight-average molecular weight, are introduced. Chain regularity and architecture are then discussed in relation to the morphology of the polymer. The industrial polymerization of a range of commercially important polymers is also explored.

Keywords

Initiation; Molecular weight; Polymerization; Polymers; Propagation; Termination

2.1 Introduction

2.2 Polymerization

2.2.1 Addition polymerization

2.2.2 Step-growth polymerization

2.3 Molecular weight distribution

2.3.1 Number-average and weight-average molecular weight

2.3.2 Size-exclusion chromatography

2.3.3 Viscometry and the viscosity-average molecular weight

2.3.4 The importance of Mn and Mw

2.4 Chain regularity

2.4.1 Stereoregular addition polymers

2.4.2 Copolymerization

2.4.3 Block copolymers

2.5 Branched and cross-linked polymers (thermosets and rubbers)

2.5.1 Chain branching

2.5.2 Thermosets

2.5.3 Rubbers

2.6 Bonding and intermolecular forces in polymers

2.7 Industrial polymer production and economics of manufacture

2.7.1 Monomer manufacture

2.7.2 Polymerization processes

2.7.3 The economics of scale

2.7.4 Additives

2.8 Grades and applications of commodity plastics

2.8.1 Polyethylenes (polyethenes)

2.8.1.1 Density and melt flow index

2.8.2 Polypropylene

2.8.3 Polyvinyl chloride

2.8.4 Polystyrene and toughened derivatives

2.1. Introduction

Polymers can be considered on a range of length scales from that of molecules to that of the final products. This chapter focuses on the molecular level and begins with an overview of two industrially significant polymerization routes, addition and step-growth polymerization, in which monomer is converted to polymer. These polymerization routes can be used to produce a wide range of commercially important polymeric materials including polyethylenes and polyamides (PAs).

The concept that polymer systems are composed of a distribution of chain lengths is considered, and two key measures of molecular weight, the number-average and weight-average molecular weight, are introduced. Chain regularity and architecture are then discussed in relation to the morphology of the polymer. The industrial polymerization of a range of commercially important polymers is also explored.

2.2. Polymerization

The conversion of monomer into polymer can be accomplished via several synthetic routes, but most commercial polymers are produced via addition or step-growth C double bond) by a free-radical species. The monomer is converted into the polymer by the opening of the double bond. Step-growth polymerization is often characterized by the loss (or elimination) of a small molecule such as H2O or HCl and a wide range of ‘high-performance’ polymers can be produced using this type of polymerization. Examples include polycarbonate (PC), polyethersulphone, polyetheretherketone, poly(phenylene sulphide), polyamide (PA) and poly(para-phenylene terephthalamide) which is known commercially as ‘Kevlar’ or ‘Twaron’.

2.2.1. Addition polymerization

Addition polymerization (also known as free-radical polymerization) has three stages: initiation, propagation and termination. The reaction can be initiated by the thermal decomposition of an unstable initiator molecule, such as a peroxide, to produce free radicals, e.g., benzoyl peroxide decomposes via a two-stage process that yields phenyl radicals and CO2. Note that the decomposition temperature of this type of initiator must be selected in accordance with the polymerization temperature, i.e., if the initiator decomposes above the selected polymerization temperature, there will be no initiation.

Some initiators decompose on exposure to light (photolysis), e.g., α,α′-azobisisobutyronitrile (AIBN) decomposes when irradiated with light of wavelength 360   nm.

Ionizing radiation may also initiate polymerization; exposure to α and β particles or γ and X-rays can result in the formation of free radical species.

–CN radicals may recombine to form (CH3)2–C(CN)–C(CN)–(CH3)2, which no longer functions as an initiator. The efficiency of the initiator can be described by an efficiency factor (f). If all the radicals initiate chain growth, f   =   1, i.e., the initiator is 100% efficient. However, most initiators lie in the range f , then attacks the covalent π bond in the monomer, leaving a free radical on the monomer

Initiator decomposition is slow compared with the succeeding propagation steps, in which a monomer adds to the growing chain, with the free radical transferring to the chain end

Chain growth ceases when there is termination. A free radical is either destroyed, as in the combination reaction when two chains link,

  →   ∼∼CH2–CH2–CH2–CH2∼∼

or chain transfer may occur to continue polymerization of another chain

The length of the polymer chain is controlled by the termination step. This may occur naturally as a result of a reaction with impurities in the monomer or with a specific chain transfer agent, such as a thiol compound, containing the weak S–H bond. Chain transfer agents are added to limit the chain length and molecular weight of the polymer and this offers a way of controlling the melt flow characteristics of the polymer (Section 3.2.4).

Table 2.1

Addition polymers are named according to the following convention: they consist of the prefix, poly-plus the monomer name. Table 2.1 gives some examples and the corresponding names.

2.2.2. Step-growth polymerization

More complex polymer structures can be made by step-growth polymerization (the alternative name is polycondensation polymerization because a by-product of water or other small molecule is often produced). In step-growth polymerization, usually two monomer structures alternate in the chain. Each monomer molecule has reactive groups at both ends: they are difunctional. For example, a diol can react with a dibasic acid,

where R and R′ represent unspecified chemical (or spacer) groups, while the two-way arrows indicate that the polymerization process is reversible. To move the reaction equilibrium to the right, water must be removed from the reactor. The product still has reactive groups at both ends and therefore polymerization occurs leading to the formation of a polyester.

In cases where there is no elimination of a small molecule, the polymerization is termed a polyaddition. The polyurethane reaction between a diisocyanate and a diol produces no by-products, which is clearly an advantage if the polymer is formed in a mould (there are no by-products to become trapped in the polymer and result in porosity in the polymer