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Report 192 ISSN: 0889-3144 Polyvinyl Alcohol: Materials, Processing and Applications E. Ogur Volume 16, Number

Report 192

ISSN: 0889-3144

Polyvinyl Alcohol:

Materials, Processing and Applications

E. Ogur

Volume 16, Number 12, 2005

Expert overviews covering the science and technology of rubber and plastics

E. Ogur Volume 16, Number 12, 2005 Expert overviews covering the science and technology of rubber

RAPRA REVIEW REPORTS VOLUME 16

Series Editor Mrs. F. Gardiner, Smithers Rapra Technology

Rapra Review Reports comprise a unique source of polymer-related information with useful overviews accompanied by abstracts from hundreds of relevant documents. A Rapra Review Report is an excellent starting point to improve subject knowledge in key areas. Subscribers to this series build up a bank of information over each year, forming a small library at a very reasonable price. This series would be an asset to corporate libraries, academic institutions and research associations with an interest in polymer science.

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RAPRA REVIEW REPORTS

A Rapra Review Report comprises three sections, as follows:

1. A commissioned expert review, discussing a key topic of current interest, and referring to the References and Abstracts section. Reference numbers in brackets refer to item numbers from the References and Abstracts section. Where it has been necessary for completeness to cite sources outside the scope of the Rapra Abstracts database, these are listed at the end of the review, and cited in the text as a.1, a.2, etc.

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Source of original article Title
Source of
original article
Title

Location

aid retrieval. Source of original article Title Location Item 1 Macromolecules 33, No.6, 21st March 2000,

Item 1

Macromolecules

33, No.6, 21st March 2000, p.2171-83 EFFECT OF THERMAL HISTORY ON THE RHEOLOGICAL BEHAVIOR OF THERMOPLASTIC POLYURETHANES Pil Joong Yoon; Chang Dae Han Akron,University

The effect of thermal history on the rheological behaviour of ester- and ether- based commercial thermoplastic PUs (Estane 5701, 5707 and 5714 from B.F.Goodrich) was investigated. It was found that the injection moulding temp. used for specimen preparation had a marked effect on the variations of dynamic storage and loss moduli of specimens with time observed during isothermal annealing. Analysis of FTIR spectra indicated that variations in hydrogen bonding with time during isothermal annealing very much resembled variations of dynamic storage modulus with time during isothermal annealing. Isochronal dynamic temp. sweep experiments indicated that the thermoplastic PUs exhibited a hysteresis effect in the heating and cooling processes. It was concluded that the microphase separation transition or order-disorder transition in thermoplastic PUs could not be determined from the isochronal dynamic temp. sweep experiment. The plots of log dynamic storage modulus versus log loss modulus varied with temp. over the entire range of temps. (110-190C) investigated. 57 refs.

the entire range of temps. (110-190C) investigated. 57 refs. GOODRICH B.F. USA Accession no.771897 Authors and
the entire range of temps. (110-190C) investigated. 57 refs. GOODRICH B.F. USA Accession no.771897 Authors and

GOODRICH B.F.

USA

temps. (110-190C) investigated. 57 refs. GOODRICH B.F. USA Accession no.771897 Authors and affiliation Abstract

Accession no.771897

Authors and

affiliation

Abstract

Companies or

organisations

mentioned

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Previous Titles Still Available

Volume 1

Report 1

Conductive Polymers, W.J. Feast

Report 2

Medical, Surgical and Pharmaceutical Applications of Polymers, D.F. Williams

Report 3

Advanced Composites, D.K. Thomas, RAE,

Farnborough.

Report 4

Liquid Crystal Polymers, M.K. Cox, ICI, Wilton.

Report 5

CAD/CAM in the Polymer Industry, N.W. Sandland and M.J. Sebborn, Cambridge Applied Technology.

Report 8

Engineering Thermoplastics, I.T. Barrie, Consultant.

Report 10

Reinforced Reaction Injection Moulding, P.D. Armitage, P.D. Coates and A.F. Johnson

Report 11

Communications Applications of Polymers,

R.

Spratling, British Telecom.

Report 12

Process Control in the Plastics Industry, R.F. Evans, Engelmann & Buckham Ancillaries.

Volume 2

Report 13

Injection Moulding of Engineering Thermoplastics, A.F. Whelan, London School of Polymer Technology.

Report 14

Polymers and Their Uses in the Sports and Leisure

Industries, A.L. Cox and R.P. Brown, Rapra Technology

Ltd.

Report 15

Polyurethane, Materials, Processing and Applications,

G.

Woods, Consultant.

Report 16

Polyetheretherketone, D.J. Kemmish, ICI, Wilton.

Report 17

Extrusion, G.M. Gale, Rapra Technology Ltd.

Report 18

Agricultural and Horticultural Applications of Polymers, J.C. Garnaud, International Committee for Plastics in Agriculture.

Report 19

Recycling and Disposal of Plastics Packaging, R.C. Fox, Plas/Tech Ltd.

Report 20

Pultrusion, L. Hollaway, University of Surrey.

Report 21

Materials Handling in the Polymer Industry,

H.

Hardy, Chronos Richardson Ltd.

Report 22

Electronics Applications of Polymers, M.T.Goosey, Plessey Research (Caswell) Ltd.

Report 23

Offshore Applications of Polymers, J.W.Brockbank, Avon Industrial Polymers Ltd.

Report 24

Recent Developments in Materials for Food Packaging, R.A. Roberts, Pira Packaging Division.

Volume 3

Report 25

Foams and Blowing Agents, J.M. Methven, Cellcom Technology Associates.

Report 26

Polymers and Structural Composites in Civil Engineering, L. Hollaway, University of Surrey.

Report 27

Injection Moulding of Rubber, M.A. Wheelans,

Consultant.

Report 28

Adhesives for Structural and Engineering Applications, C. O’Reilly, Loctite (Ireland) Ltd.

Report 29

Polymers in Marine Applications, C.F.Britton, Corrosion Monitoring Consultancy.

Report 30

Non-destructive Testing of Polymers, W.N. Reynolds, National NDT Centre, Harwell.

Report 31

Silicone Rubbers, B.R. Trego and H.W.Winnan, Dow Corning Ltd.

Report 32

Fluoroelastomers - Properties and Applications,

D.

Cook and M. Lynn, 3M United Kingdom Plc and

3M Belgium SA.

Report 33

Polyamides, R.S. Williams and T. Daniels, T & N Technology Ltd. and BIP Chemicals Ltd.

Report 34

Extrusion of Rubber, J.G.A. Lovegrove, Nova Petrochemicals Inc.

Report 35

Polymers in Household Electrical Goods, D.Alvey, Hotpoint Ltd.

Report 36

Developments in Additives to Meet Health and Environmental Concerns, M.J. Forrest, Rapra Technology Ltd.

Volume 4

Report 37

Polymers in Aerospace Applications, W.W. Wright, University of Surrey.

Report 38

Epoxy Resins, K.A. Hodd

Report 39

Polymers in Chemically Resistant Applications,

D.

Cattell, Cattell Consultancy Services.

Report 40

Internal Mixing of Rubber, J.C. Lupton

Report 41

Failure of Plastics, S. Turner, Queen Mary College.

Report 42

Polycarbonates, R. Pakull, U. Grigo, D. Freitag, Bayer AG.

Report 43

Polymeric Materials from Renewable Resources, J.M. Methven, UMIST.

Report 44

Flammability and Flame Retardants in Plastics,

J.

Green, FMC Corp.

Report 45

Composites - Tooling and Component Processing, N.G. Brain, Tooltex.

Report 46

Quality Today in Polymer Processing, S.H. Coulson, J.A. Cousans, Exxon Chemical International Marketing.

Report 47

Chemical Analysis of Polymers, G. Lawson, Leicester

Polytechnic.

Report 48

Plastics in Building, C.M.A. Johansson

Volume 5

Report 49

Blends and Alloys of Engineering Thermoplastics, H.T. van de Grampel, General Electric Plastics BV.

Report 50

Automotive Applications of Polymers II, A.N.A. Elliott, Consultant.

Report 51

Biomedical Applications of Polymers, C.G. Gebelein, Youngstown State University / Florida Atlantic

University.

Report 52

Polymer Supported Chemical Reactions, P. Hodge, University of Manchester.

Report 53

Weathering of Polymers, S.M. Halliwell, Building Research Establishment.

Report 54

Health and Safety in the Rubber Industry, A.R. Nutt, Arnold Nutt & Co. and J. Wade.

Report 55

Computer Modelling of Polymer Processing,

E.

Andreassen, Å. Larsen and E.L. Hinrichsen, Senter for

Industriforskning, Norway.

Report 56

Plastics in High Temperature Applications,

J.

Maxwell, Consultant.

Report 57

Joining of Plastics, K.W. Allen, City University.

Report 58

Physical Testing of Rubber, R.P. Brown, Rapra Technology Ltd.

Report 59

Polyimides - Materials, Processing and Applications, A.J. Kirby, Du Pont (U.K.) Ltd.

Report 60

Physical Testing of Thermoplastics, S.W. Hawley, Rapra Technology Ltd.

Volume 6

Report 61

Food Contact Polymeric Materials, J.A. Sidwell, Rapra Technology Ltd.

Report 62

Coextrusion, D. Djordjevic, Klöckner ER-WE-PA GmbH.

Report 63

Conductive Polymers II, R.H. Friend, University of Cambridge, Cavendish Laboratory.

Report 64

Designing with Plastics, P.R. Lewis, The Open University.

Report 65

Decorating and Coating of Plastics, P.J. Robinson, International Automotive Design.

Report 66

Reinforced Thermoplastics - Composition, Processing and Applications, P.G. Kelleher, New Jersey Polymer Extension Center at Stevens Institute of Technology.

Report 67

Plastics in Thermal and Acoustic Building Insulation, V.L. Kefford, MRM Engineering Consultancy.

Report 68

Cure Assessment by Physical and Chemical Techniques, B.G. Willoughby, Rapra Technology Ltd.

Report 69

Toxicity of Plastics and Rubber in Fire, P.J. Fardell, Building Research Establishment, Fire Research Station.

Report 70

Acrylonitrile-Butadiene-Styrene Polymers, M.E. Adams, D.J. Buckley, R.E. Colborn, W.P. England and D.N. Schissel, General Electric Corporate Research and Development Center.

Report 71

Rotational Moulding, R.J. Crawford, The Queen’s University of Belfast.

Report 72

Advances in Injection Moulding, C.A. Maier, Econology Ltd.

Volume 7

Report 73

Reactive Processing of Polymers, M.W.R. Brown, P.D. Coates and A.F. Johnson, IRC in Polymer Science and Technology, University of Bradford.

Report 74

Speciality Rubbers, J.A. Brydson.

Report 75

Plastics and the Environment, I. Boustead, Boustead Consulting Ltd.

Report 76

Polymeric Precursors for Ceramic Materials, R.C.P. Cubbon.

Report 77

Advances in Tyre Mechanics, R.A. Ridha, M. Theves, Goodyear Technical Center.

Report 78

PVC - Compounds, Processing and Applications, J.Leadbitter, J.A. Day, J.L. Ryan, Hydro Polymers Ltd.

Report 79

Rubber Compounding Ingredients - Need, Theory and Innovation, Part I: Vulcanising Systems, Antidegradants and Particulate Fillers for General Purpose Rubbers, C. Hepburn, University of Ulster.

Report 80

Anti-Corrosion Polymers: PEEK, PEKK and Other Polyaryls, G. Pritchard, Kingston University.

Report 81

Thermoplastic Elastomers - Properties and Applications, J.A. Brydson.

Report 82

Advances in Blow Moulding Process Optimization, Andres Garcia-Rejon,Industrial Materials Institute, National Research Council Canada.

Report 83

Molecular Weight Characterisation of Synthetic Polymers, S.R. Holding and E. Meehan, Rapra Technology Ltd. and Polymer Laboratories Ltd.

Report 84

Rheology and its Role in Plastics Processing, P. Prentice, The Nottingham Trent University.

Volume 8

Report 85

Ring Opening Polymerisation, N. Spassky, Université Pierre et Marie Curie.

Report 86

High Performance Engineering Plastics, D.J. Kemmish, Victrex Ltd.

Report 87

Rubber to Metal Bonding, B.G. Crowther, Rapra Technology Ltd.

Report 88

Plasticisers - Selection, Applications and Implications, A.S. Wilson.

Report 89

Polymer Membranes - Materials, Structures and Separation Performance, T. deV. Naylor, The Smart Chemical Company.

Report 90

Rubber Mixing, P.R. Wood.

Report 91

Recent Developments in Epoxy Resins, I. Hamerton, University of Surrey.

Report 92

Continuous Vulcanisation of Elastomer Profiles,

A.

Hill, Meteor Gummiwerke.

Report 93

Advances in Thermoforming, J.L. Throne, Sherwood Technologies Inc.

Report 94

Compressive Behaviour of Composites, C. Soutis, Imperial College of Science, Technology and Medicine.

Report 95

Thermal Analysis of Polymers, M. P. Sepe, Dickten & Masch Manufacturing Co.

Report 96

Polymeric Seals and Sealing Technology, J.A. Hickman, St Clair (Polymers) Ltd.

Volume 9

Report 97

Rubber Compounding Ingredients - Need, Theory and Innovation, Part II: Processing, Bonding, Fire Retardants, C. Hepburn, University of Ulster.

Report 98

Advances in Biodegradable Polymers, G.F. Moore & S.M. Saunders, Rapra Technology Ltd.

Report 99

Recycling of Rubber, H.J. Manuel and W. Dierkes, Vredestein Rubber Recycling B.V.

Report 100

Photoinitiated Polymerisation - Theory and Applications, J.P. Fouassier, Ecole Nationale Supérieure de Chimie, Mulhouse.

Report 101

Solvent-Free Adhesives, T.E. Rolando, H.B. Fuller

Company.

Report 102

Plastics in Pressure Pipes, T. Stafford, Rapra Technology Ltd.

Report 103

Gas Assisted Moulding, T.C. Pearson, Gas Injection Ltd.

Report 104

Plastics Profile Extrusion, R.J. Kent, Tangram Technology Ltd.

Report 105

Rubber Extrusion Theory and Development, B.G. Crowther.

Report 106

Properties and Applications of Elastomeric Polysulfides, T.C.P. Lee, Oxford Brookes University.

Report 107

High Performance Polymer Fibres, P.R. Lewis, The Open University.

Report 108

Chemical Characterisation of Polyurethanes, M.J. Forrest, Rapra Technology Ltd.

Volume 10

Report 109

Rubber Injection Moulding - A Practical Guide, J.A. Lindsay.

Report 110

Long-Term and Accelerated Ageing Tests on Rubbers, R.P. Brown, M.J. Forrest and G. Soulagnet, Rapra Technology Ltd.

Report 111

Polymer Product Failure, P.R. Lewis, The Open University.

Report 112

Polystyrene - Synthesis, Production and Applications, J.R. Wünsch, BASF AG.

Report 113

Rubber-Modified Thermoplastics, H. Keskkula, University of Texas at Austin.

Report 114

Developments in Polyacetylene - Nanopolyacetylene, V.M. Kobryanskii, Russian Academy of Sciences.

Report 115

Metallocene-Catalysed Polymerisation, W. Kaminsky, University of Hamburg.

Report 116

Compounding in Co-rotating Twin-Screw Extruders,

Y.

Wang, Tunghai University.

Report 117

Rapid Prototyping, Tooling and Manufacturing, R.J.M. Hague and P.E. Reeves, Edward Mackenzie Consulting.

Report 118

Liquid Crystal Polymers - Synthesis, Properties and Applications, D. Coates, CRL Ltd.

Report 119

Rubbers in Contact with Food, M.J. Forrest and J.A. Sidwell, Rapra Technology Ltd.

Report 120

Electronics Applications of Polymers II, M.T. Goosey, Shipley Ronal.

Volume 11

Report 121

Polyamides as Engineering Thermoplastic Materials, I.B. Page, BIP Ltd.

Report 122

Flexible Packaging - Adhesives, Coatings and Processes, T.E. Rolando, H.B. Fuller Company.

Report 123

Polymer Blends, L.A. Utracki, National Research Council Canada.

Report 124

Sorting of Waste Plastics for Recycling, R.D. Pascoe, University of Exeter.

Report 125

Structural Studies of Polymers by Solution NMR, H.N. Cheng, Hercules Incorporated.

Report 126

Composites for Automotive Applications, C.D. Rudd, University of Nottingham.

Report 127

Polymers in Medical Applications, B.J. Lambert and F.-W. Tang, Guidant Corp., and W.J. Rogers, Consultant.

Report 128

Solid State NMR of Polymers, P.A. Mirau, Lucent Technologies.

Report 129

Failure of Polymer Products Due to Photo-oxidation, D.C. Wright.

Report 130

Failure of Polymer Products Due to Chemical Attack, D.C. Wright.

Report 131

Failure of Polymer Products Due to Thermo-oxidation, D.C. Wright.

Report 132

Stabilisers for Polyolefins, C. Kröhnke and F. Werner, Clariant Huningue SA.

Volume 12

Report 133

Advances in Automation for Plastics Injection Moulding, J. Mallon, Yushin Inc.

Report 134

Infrared and Raman Spectroscopy of Polymers, J.L. Koenig, Case Western Reserve University.

Report 135

Polymers in Sport and Leisure, R.P. Brown.

Report 136

Radiation Curing, R.S. Davidson, DavRad Services.

Report 137

Silicone Elastomers, P. Jerschow, Wacker-Chemie GmbH.

Report 138

Health and Safety in the Rubber Industry, N. Chaiear, Khon Kaen University.

Report 139

Rubber Analysis - Polymers, Compounds and Products, M.J. Forrest, Rapra Technology Ltd.

Report 140

Tyre Compounding for Improved Performance, M.S. Evans, Kumho European Technical Centre.

Report 141

Particulate Fillers for Polymers, Professor R.N. Rothon, Rothon Consultants and Manchester Metropolitan University.

Report 142

Blowing Agents for Polyurethane Foams, S.N. Singh, Huntsman Polyurethanes.

Report 143

Adhesion and Bonding to Polyolefins, D.M. Brewis and I. Mathieson, Institute of Surface Science & Technology, Loughborough University.

Report 144

Rubber Curing Systems, R.N. Datta, Flexsys BV.

Volume 13

Report 145

Multi-Material Injection Moulding, V. Goodship and J.C. Love, The University of Warwick.

Report 146

In-Mould Decoration of Plastics, J.C. Love and

V.

Goodship, The University of Warwick.

Report 147

Rubber Product Failure, Roger P. Brown.

Report 148

Plastics Waste – Feedstock Recycling, Chemical Recycling and Incineration, A. Tukker, TNO.

Report 149

Analysis of Plastics, Martin J. Forrest, Rapra Technology

Ltd.

Report 150

Mould Sticking, Fouling and Cleaning, D.E. Packham, Materials Research Centre, University of Bath.

Report 151

Rigid Plastics Packaging - Materials, Processes and Applications, F. Hannay, Nampak Group Research &

Development.

Report 152

Natural and Wood Fibre Reinforcement in Polymers,

A.K. Bledzki, V.E. Sperber and O. Faruk, University of

 

Kassel.

Report 153

Polymers in Telecommunication Devices, G.H. Cross, University of Durham.

Report 154

Polymers in Building and Construction, S.M. Halliwell,

BRE.

Report 155

Styrenic Copolymers, Andreas Chrisochoou and Daniel Dufour, Bayer AG.

Report 156

Life Cycle Assessment and Environmental Impact of Polymeric Products, T.J. O’Neill, Polymeron Consultancy Network.

Volume 14

Report 157

Developments in Colorants for Plastics, Ian N. Christensen.

Report 158

Geosynthetics, David I. Cook.

Report 159

Biopolymers, R.M. Johnson, L.Y. Mwaikambo and

N.

Tucker, Warwick Manufacturing Group.

Report 160

Emulsion Polymerisation and Applications of Latex, Christopher D. Anderson and Eric S. Daniels, Emulsion Polymers Institute.

Report 161

Emissions from Plastics, C. Henneuse-Boxus and

T.

Pacary, Certech.

Report 162

Analysis of Thermoset Materials, Precursors and Products, Martin J. Forrest, Rapra Technology Ltd.

Report 163

Polymer/Layered Silicate Nanocomposites, Masami Okamoto, Toyota Technological Institute.

Report 164

Cure Monitoring for Composites and Adhesives, David

R.

Mulligan, NPL.

Report 165

Polymer Enhancement of Technical Textiles, Roy W. Buckley.

Report 166

Developments in Thermoplastic Elastomers, K.E. Kear

Report 167

Polyolefin Foams, N.J. Mills, Metallurgy and Materials, University of Birmingham.

Report 168

Plastic Flame Retardants: Technology and Current Developments, J. Innes and A. Innes, Flame Retardants Associates Inc.

Volume 15

Report 169

Engineering and Structural Adhesives, David J. Dunn, FLD Enterprises Inc.

Report 170

Polymers in Agriculture and Horticulture, Roger P. Brown.

Report 171

PVC Compounds and Processing, Stuart Patrick.

Report 172

Troubleshooting Injection Moulding, Vanessa Goodship, Warwick Manufacturing Group.

Report 173

Regulation of Food Packaging in Europe and the USA, Derek J. Knight and Lesley A. Creighton, Safepharm Laboratories Ltd.

Report 174

Pharmaceutical Applications of Polymers for Drug Delivery, David Jones, Queen's University, Belfast.

Report 175

Tyre Recycling, Valerie L. Shulman, European Tyre Recycling Association (ETRA).

Report 176

Polymer Processing with Supercritical Fluids, V. Goodship and E.O. Ogur.

Report 177

Bonding Elastomers: A Review of Adhesives & Processes, G. Polaski, J. Means, B. Stull, P. Warren, K. Allen, D. Mowrey and B. Carney.

Report 178

Mixing of Vulcanisable Rubbers and Thermoplastic Elastomers, P.R. Wood.

Report 179

Polymers in Asphalt, H.L. Robinson, Tarmac Ltd, UK.

Report 180

Biocides in Plastics, D. Nichols, Thor Overseas Limited.

Volume 16

Report 181

New EU Regulation of Chemicals: REACH, D.J. Knight, SafePharm Laboratories Ltd.

Report 182

Food Contact Rubbers 2 - Products, Migration and Regulation, M.J. Forrest.

Report 183

Adhesion to Fluoropolymers, D.M. Brewis and R.H. Dahm, IPTME, Loughborough University.

Report 184

Fluoroplastics, J.G. Drobny.

Report 185

Epoxy Composites: Impact Resistance and Flame Retardancy, Debdatta Ratna.

Report 186

Coatings and Inks for Food Contact Materials, Martin Forrest, Smithers Rapra.

Report 187

Nucleating Agents, Stuart Fairgrieve, SPF Polymer Consultants.

Report 188

Silicone Products for Food Contact Applications, Martin Forrest, Smithers Rapra.

Report 189

Degradation and Stabilisation of Polymers, Stuart Fairgrieve, SPF Polymer Consultants

Report 190

Electrospinning Jon Stanger, New Zealand Institute for Plant and Food Research

Nick Tucker, New Zealand Institute for Plant and Food Research

Mark Staiger, University of Canterbury, New Zealand

Polyvinyl Alcohol: Materials, Processing and Applications

Vannessa Goodship and Daniel Jacobs

ISBN: 978-1-84735-095-4

Polyvinyl Alcohol: Materials, Processing and Applications

Contents

1. Introduction

 

3

2. Application Scope

4

3. Manufacture

6

4. Polymer Chemistry

7

4.1

Viscosity in Solution

7

5. Water Solubility

 

8

6. PVAL Film Properties

9

6.1 Barrier Proporties

9

6.2 Other Film Properties

10

 

6.2.1 Mechanical Properties

10

6.2.2 Plasticiser Effects

10

6.2.3 Oil and Solvent Resistance

10

6.2.4 Water Sensitivity and Hygroscopy

10

6.2.5 Characteristics

Adhesion

10

6.2.6 Antistatic

10

7. Solution Processing

 

10

8. Melt Processing

11

8.1 Extrusion

12

8.2 Injection Moulding

12

8.3 Film Moulding

 

12

8.4 Blow Moulding

13

9. Packaging

13

9.1

Active Packaging

13

10. PVAL in Medicine: Hydrogels

13

11. Biopolymers

 

14

12. Blends

15

13. Blends of PVAL

15

13.1 PVAL-Starch Blends

15

13.2 Other Blends

 

16

 

13.2.1

PVAL/Gelatin Blends

16

Polyvinyl Alcohol: Materials, Processing and Applications

14.

Degradability

17

14.1 Biodegradable Plastics

18

14.2 Oil-Based Naturally Degradable Polymers

18

14.3 Photo-degradable Plastics

18

15.

Plastics and Biodegradable Plastics Disposal

19

15.1 Composting

20

15.2 Incineration

21

15.3 Landfilling

21

16.

Conclusion

21

References

22

Abbreviations and Acronyms

22

 

Subject Index

00

Company Index

00

Author contact details:

Vannessa Goodship WMG, Univeristy of Warwick, Coventry, CV4 7AL

Daniel Jacobs WMG, Univeristy of Warwick, Coventry, CV4 7AL

The views and opinions expressed by authors in Rapra Review Reports do not necessarily reflect those of Smithers Rapra Technology or the editor. The series is published on the basis that no responsibility or liability of any nature shall attach to Smithers Rapra Technology arising out of or in connection with any utilisation in any form of any material contained therein.

Polyvinyl Alcohol: Materials, Processing and Applications

Poly(vinyl alcohol):

Properties, Applications and Disposal

This review report is produced to provide a concise introduction to poly(vinyl alcohol); the material itself, processing, applications and disposal. It will also consider comparable properties of similar materials with which this material is likely to compete. The definitions and requirements of materials that wish to operate in the ‘green’ arena will also be introduced.

Poly(vinyl alcohol) is the most commercially important water soluble plastic in use. It is tasteless, odourless, it will biodegrade and is biocompatible. As well as being soluble in water, it is slightly soluble in ethanol, but insoluble in other organic solvents. As environmental concerns over the disposal of plastic wastes have grown and focus has switched towards product life cycle and disposal, poly(vinyl alcohol) has a readymade and viable disposal route. In light of increasing environmental legislation, this will allow it to be utilised in non-traditional areas of use. With increasing interest in the use of biodegradable and sustainable alternatives for mass applications, poly(vinyl alcohol) provides an interesting point of comparative study on

a oil-based synthetic material with the properties of a ‘green polymer’.

It is also be readily blended with a number of natural

materials and can exhibit properties that are compatible with a range of applications. The inclusion of natural fibres and fillers can give further improvements in mechanical properties without compromising overall degradability. Therefore, the potential benefits of this material given its water soluble characteristics are huge, but this must be offset against practical considerations of its long term life cycle in changeable environmental conditions.

In the future biodegradable materials could be used

within a variety of product applications, but there are,

at present, significant penalties in terms of performance,

cost and availability. The predominant benefit which can be attributed to biopolymer usage is that the materials themselves can be biodegradable. This of course makes them an increasingly attractive proposition for manufacturers who are faced with increasingly stringent EU legislative requirements when it comes

to the environmental performance of their products, or those who wish to tap the market of the environmentally conscious consumer. This review will try to capture current and future trends in this area.

1. Introduction

Like all common polymers poly(vinyl alcohol) can be abbreviated. However, unlike polymers such as polypropylene (PP), in which the abbreviations are universally used, poly(vinyl alcohol) does not have a singularly recognised abbreviation. Therefore according to various literature sources it is referred to as PVAL, PVOH or PVA and therefore all these terms, although confusing, are correct in the context of the standards to which they were used.

The terminology that shall be used here is PVAL in accordance to British Standard BS EN ISO 15023-1:2006 (a.1).

Poly(vinyl alcohol) and its properties have been known to scientists for a long time. It was first prepared by Hermann and Haehnel, Germany, in 1924. It is made by hydrolysing polyvinyl acetate (PVA or PVAc – dependent on where you look).

Worldwide consumption of PVAL had reached several hundred thousand tonnes annually in 2006; this is widely predicted to increase by about 2.5% annually between 2006 and 2011. There are a number of worldwide producers of this material with the majority of production based in Asian countries. China has the largest share of the market as of commercial trading figures for 2006 with 45% of the entire market with this figure likely to expand. Japan and the United States are also both large producers and consumers of PVAL materials. Kuraray (Japan) is the largest single manufacturer of PVAL accounting for 16% of all world capacity and offering over 50 different grades of this material.

Trade names for PVAL (PVOH or PVA) include Elvanol (DuPont), Mowiol (Kuraray) and Poval (Kuraray).

The material exists in the marketplace as fully hydrolysed, medium hydrolysed or partially hydrolysed copolymers or custom blends. Most of the market is dominated by sales of the fully hydrolysed grade of material. This difference in hydrolysis will be explained in Section 4. In line with international standards, grades of this material are presented in terms of the degree of hydrolysis and the viscosity in water at specified conditions. An indication of the range of hydrolysis levels available in the marketplace is shown in Table 1.

Polyvinyl Alcohol: Materials, Processing and Applications

 

Table 1 Selection of grades of PVAL offered by Kuraray

 
 

Grade

Viscosity DIN 53015 (a.2) (mPa-s)*

Degree of hydrolysis (saponification) (mol. - %)

Partially hydrolysed

Mowiol 3-85

3.4-4.0

84.2-86.2

Partially hydrolysed

PVA 220

27.0-33.0

87.0-89.0

Partially hydrolysed

PVA 225

45.0-52.0

86.5-89.0

Medium Hydrolysed

PVA CST

24.0-30.0

95.5-96.5

Medium Hydrolysed

PVA 613

14.5-18.5

92.5-94.5

Fully hydrolysed

PVA 117

25.0-30.0

98.0-99.0

Fully hydrolysed

Mowiol 4-98

4.0-5.0

98.0-98.8

Fully hydrolysed

Mowiol 56-98

52.0-60.0

98.0-98.8

*of a 4% aqueous solution at 20 °C

 

Using 2008 commercial prices as a general guide, PVAL materials are priced according to viscosity.

Low viscosity materials (classed as having a viscosity less than 0.01 Pa-s), were trading for half the price per tonne (150 Euros), than high viscosity materials (>0.03 Pa-s) which were trading at 300 Euros per tonne. Medium viscosity materials (0.01-0.03 Pa-s) were trading at 200 Euros. However, like all oil-based plastics prices are highly variable.

2. Application Scope

The major uses of PVAL depend on region. In the United States and Western Europe the majority of PVAL is consumed in the production of poly(vinyl butyral) (PVB). This is used in the inner layer of laminated safety glass for automobile window screens. It is made by reacting PVAL with butyraldehyde [CH 3 (CH 2 ) 2 CHO] and this market is one which is expected to grow in the future.

PVAL finds other uses in a broad range of products produced for example as a protective colloid in the manufacture of polymer emulsions. Other applications include: the binding of pigments and fibres, dip coated articles, protective strippable coatings, the manufacture of detergents and cleansing agents, adhesives, emulsion paints, and solution cast film. These applications all involve the use of the PVAL in solution as its thermal degradation at about 150 °C (crystalline melting point of PVAL ranges from 180 °C to 240 °C), limits its ability to be used in conventional thermoplastic processing equipment without modification. When PVAL is plasticised, it

is possible to avoid thermal dehydration however, some properties are sacrificed.

In China the largest market is as a polymerisation aid in emulsified polyvinyl acetate and polyvinyl chloride (PVC). Therefore, much of the PVAL produced today is used as a protective colloid in the manufacture of polymer emulsions.

The use of emulsifying agents improves the quality of synthesis of PVC and helps properties such as the ability to absorb plasticisers and the production of uniform grain sizes. Other materials commonly used as emulsifying agents are methyl cellulose derivatives or combinations. Two PVAL materials of differing molecular weight may be used together synergistically improving the process.

In the formation of emulsified polyvinyl acetate, PVAL acts as a protective colloid. PVAL has excellent properties in emulsion such as ‘wet tackiness’, high strength and it is highly resistant to creep. As with the formation of PVC, the structure of the PVAL affects the emulsion performance of the polyvinyl acetate. For this process, PVAL with an active surface is also required, therefore partially hydrolysed grades are utilised which have residual acetate groups which are hydrophobic in nature.

In Japan Vinylon spun fibre is the biggest use of PVAL. It is used in a variety of applications from the manufacture of traditional Japanese dress, canvas, cement reinforcement, agriculture, fishing nets, ropes and paper making (which is the largest market). It can be produced by either dry or wet spinning. This is a different process to spinning from a melt, which is called melt spinning and used for production of fibres

Polyvinyl Alcohol: Materials, Processing and Applications

such as polyethylene (PE), PP, polyamide (PA) and polyester. In the case of vinylon a spinning solution is used with most production then carried out by wet spinning. The product is staple fibre. The solution is spun into fibres which pass through a water bath before being drawn and cut into fibres. Dry spinning uses hot air instead of water, drawing and then collection of the filament yarn onto spindles. Vinylon is characterised by a lighter weight (specific gravity of 1.3) than natural fibres such as wool or cotton. It is abrasion resistant, durable and resistance to weathering, chemicals and rotting and has properties similar to cotton in fibre form.

Demand is also increasing for PVAL fibres as a safer replacement for asbestos fibres and in the use of polarising optical films for liquid crystal displays (LCD) (a.3). The PVAL material is used for optical applications which effectively prevent reflection of light at the surface of image display devices such as plasma display panels (PDP), cathode ray tubes (CRT) and LCD, and exhibits excellent scratch resistance. The film, used for preventing reflection of light has excellent scratch resistance and can be produced at a low cost. In a typical application, the film is formed by successively laminating a hard coat layer, a first high refractivity layer, a second high refractivity layer, and a low refractivity layer.

The water solubility and biodegradability of this material are the key properties for its usage. This has also attracted the recent attention of a packaging industry keen to address environmentally friendly solutions to the issue of plastic waste. This will be discussed in Section 5.

Other important areas where PVAL water solubility is used include textile sizing agents – the PVAL is applied to protect the textile fibres during production (such as knitting or weaving and so on), then once made the garment can be washed to remove the PVAL.

PVAL adhesives are used widely with cellulose materials as they give excellent adhesion to them. They are, therefore, used in a range of applications from postage stamps, labels, paper bags to book binding and make an ideal glue for papercraft activities.

Commercially, PVAL is the most important plastic for production of water soluble film. It is characterised by excellent film-forming, emulsifying, and adhesive properties. It has a high tensile strength, good flexibility, good oxygen barrier properties and good solvent resistance properties.

All the applications so far involve the use of the PVAL in solution as its thermal degradation is about 150 °C (crystalline melting point of PVAL ranges from 180 °C to 240 °C). Therefore until recently this limited its ability to be used in conventional thermoplastic processing equipment. However, when PVAL is plasticised, it is possible to avoid thermal dehydration. Melt processing applications are discussed in Section 8.

Therefore, PVAL finds use in variety of market sectors such as (a.3):

PVAL was investigated in the 1970s for use in controlled release of agrochemicals using combinations with pesticides. It is also used in current production of seed tapes. For these kind of applications the polymer must degrade without impact (be it chemical or biological) to the surrounding environment. Therefore, degradation and disposal issues will also be discussed later in the review.

PVAL is used in the manufacture of laundry bags and hamper liners for use in health care facilities. The filled bag is sealed shut with an attached adhesive strip. When placed in the washer, the adhesive and bag break down completely during the hot washing and disinfection. The bags are impervious to bacteria and viruses during normal use, as well as resistant to gases, solvents, and cool liquids, reducing the risk of contamination and thereby protecting hospital staff.

In food industries, PVAL is used as a binding and coating agent. The film coating is used in applications where moisture barrier protection properties are required. PVAL protects active components and other ingredients from oxygen, e.g., tablet coating formulations intended for products such as food supplement tablets.

Other more unusual products include the biodegradable PVAL pet waste bag for picking up pet waste and eco- disposal. It can be placed in the bin or flushed down the toilet. For lazy (or inept) golfers, there are water soluble golf balls made from PVAL. For golfers not willing to look for their balls, these can be abandoned on courses

Polyvinyl Alcohol: Materials, Processing and Applications

to biodegrade naturally. For those who wish to practise their swings while at sea, they can be hit straight into the sea to dissolve.

This variety of sectors and applications areas are possible because poly(vinyl alcohol) has a number of useful and tailorable properties. It is odourless and non-toxic, it has excellent film forming, emulsifying, and adhesive properties. It also has good resistance to grease, oils and a large number of solvent materials. It has good mechanical performance with high tensile strength and flexibility, it also has high oxygen and aroma barrier properties. However, these properties are all dependent on the level of humidity. Water, which acts as a plasticiser, causes a reduction in tensile strength, but also increases the elongation and tear strength of the material.

The sheer range of applications for this material make it an interesting material of study. However, first a more fundamental introduction to PVAL manufacture and material properties will be given.

3. Manufacture

The first commercial production of PVAL was by the company Wacker (Germany) with the trademark Synthofil, which was used as medical sutures. In 1930, Japanese researchers Sakurada, Yazawa and Tomanari successfully wet spun PVAL. In 1950 this was realised commercially as Vinylon fibre (see Section 2). This fibre has high heat resistance amongst other interesting properties.

Unlike other members of the vinyl group, PVAL is not polymerised from a monomer in direct polymerisation,

but prepared by hydrolysis of poly(vinyl acetate) (PVAc) in alcohol solution. This is a rubbery, synthetic polymer and partial or complete hydrolysis of the PVAc

is used to prepare PVAL. The reaction proceeds via

free radical mechanism or suspension polymerisation. Partial or complete hydrolysis removes acetate groups from the PVAc. The resultant material PVAL has the same degree of polymerisation as the original PVAc material. Therefore by varying the degree of polymerisation of the original PVAc a number of

different grades of material with different properties can be produced. The reaction can be controlled to produce any degree of replacement of acetate groups. Other materials can be used to produce co-polymer materials which also replace the acetate group. Monomers such as ethylene and acrylate esters are commercially used

in this way.

Once converted from PVAc the hydrolysed alcohol

product is typically in the 87% to 99% range. If

it is above 98% it can be considered to be fully

hydrolysed with an expected crystallinity value of 40-50% Highly but not fully hydrolysed PVAL has

a degree of crystallinity of 30-40% and a melting

point of 225 °C. The reduced crystallinty in partially hydrolysed grades is due to the residual acetate groups. Other factors affecting crystallinity are the amount of plasticiser and water present in the compound. The production process used (acid or base catalysed) also has an effect. A lower crystallinity means lower

strength but increased water solubility compared to fully hydrolysed (higher crystallinity) grades which can be considered as homopolymers as opposed to mixed vinyl acetate and vinyl alcohol co- polymer. Chemical representations commonly used to represent PVAL are shown in Figure 1.

commonly used to represent PVAL are shown in Figure 1. Figure 1 Molecule of PVAL (left)

Figure 1 Molecule of PVAL (left) and chemical representations (right and centre)

Polyvinyl Alcohol: Materials, Processing and Applications

4. Polymer Chemistry

The physical characteristics and specific functional uses depend on the both the degree of polymerisation and hydrolysis produced. PVAL is classified into classes namely: partially hydrolysed and fully hydrolysed.

PVAL is crystalline in nature, this is unusual since it is an atactic linear polymer, meaning the positioning of the side chains of secondary alcohol groups is random. This is generally accompanied by an inability to crystallise. In fact PVAc is not crystalline, but PVAL which contains smaller hydroxyl groups, is typically crystalline regardless of stereoregularity. This is because hydroxyl groups do not disrupt the crystalline lattice structure as their small size allows them to ‘slot’ in. However, in contrast, the presence of residual acetate groups greatly diminishes the crystal formation and the degree of hydrogen bonding because of their more bulky nature.

Therefore, polymers that are highly hydrolysed have a high tendency to crystallise and to undergo hydrogen bonding. As the degree of hydrolysis increases, the molecules will very readily crystallise, and hydrogen bonds will keep them associated if they are not fully dispersed prior to dissolution. At degrees of hydrolysis above 98%, manufacturers of PVAL advocate a minimum temperature of 96 °C to ensure that the highest molecular weight components have enough thermal energy to go into solution.

Increasing levels of hydrolysis leads to increasing crystallinity

This also allows a level of control to be exerted over the crystallinity produced and the physical characteristics and specific functional uses of PVAL vary with this property. The crystallinity affects the water solubility, strength, gas permeability and thermal characteristics. Since the crystallinity is dependent on both the degree of hydrolysis and the average molecular weight of the polymer it also depends on the degree of polymerisation that occurs.

The level of hydrolysis will therefore have a direct effect on the properties and it is necessary to distinguish these materials into levels (partially, medium, fully hydrolysed). The actual degree of hydrolysis depends on how many percentage mol of residual acetate groups remain, as PVAL is characterised by the presence of the polar OH groups in the structure. For ISO 15023 (a.1), the level must be equal to or above 70%.

Because PVAL refers to the material that can be both fully and partly hydrolysed, it can actually be considered in partially hydrolysed cases to be a co-polymer of vinyl acetate and vinyl alcohol monomer (which does not actually exist). The monomer components may be distinguished if necessary using the convention V-AL and V-OAc.

Therefore PVAL is characterised by the presence of polar alcohol (OH-groups), and these groups give rise to reduced water solubility and also allow other reactions to take place.

Increasing hydrolysis leads to:

In many cases, however, a partially or fully hydrolysed material may be used for the same application. For example in adhesives, where water resistance is required, a fully hydrolysed material may be used and where water resistance is not an issue, a partially or fully hydrolysed material may be used.

It is a water-soluble synthetic polymer that is it is made from petrochemicals. So although it is biodegradable, it is not a biopolymer. A biopolymer is a material made from a biomaterial such as plant starch. This distinction will be discussed in Section 10.

4.1 Viscosity in Solution

In water solution partially hydrolysed PVAL (88% and below) has a stable viscosity which does not change over time. However, the viscosity of a solution of highly hydrolysed material will show a gradual increase in viscosity over time, and if left long enough may even gel. This tendency to increase in viscosity over time, increases fairly linearly with concentration.

The films produced from partially hydrolysed solutions are characterised with poor water and heat resistance. Those from fully hydrolysed grades have the opposite properties being water and creep resistant properties. Through the use of additives it is possible to stabilise or destabilise those changes in viscosity which occur.

Polyvinyl Alcohol: Materials, Processing and Applications

5. Water Solubility

The main use of PVAL is when it is dissolved in water. Poly(vinyl alcohol) is among a group of water-soluble plastics that have a long history of use in niche applications. Many of these polymers are biologically stable when they are in the solid state but will biodegrade readily once they are dissolved. As PVAL is formed by hydrolysis of PVAc, by controlling the degree of hydrolysis, its solubility can be modified, which results in grades that will dissolve only in hot or cold water. Some grades can be mass produced by extrusion, injection moulding or film blowing (to produce potentially readily disposable components), but others must be cast from solution.

Single dose laundry blocks or liquids have become commonplace in many households. These are water soluble films used for the packaging (as you will find

if you accidentally get them wet, they become very

sticky.) Surprisingly the first use of water soluble packaging was in the 1960s, this was for carrying harmful chemicals in agriculture. It is relatively more recently that they have become such a commonplace item for household detergents and cleaning items.

As already mentioned, the solubility depends on a number of factors such as the degree of polymerisation and degree of hydrolysis. The degree of hydrolysis is particularly important because of the inherent chemical structure. The many hydroxyl groups mean it has a high affinity for water and the hydrogen bonding between the hydroxyl groups impedes the overall solubility.

In contrast, partly hydrolysed PVAL contains acetate groups. This acts in the opposite way to weaken the

hydrogen bonding and increase solubility and there is

a relationship between temperature of solubility and

presence of acetate groups. Therefore, the behaviour

of PVAL in solution is quite complex.

However, generally a partially hydrolysed version of the same material will be more soluble at a lower temperature with solubility increasing as hydrolysis levels increase.

Commercial water-soluble films can be tailored to dissolve in water at very specific temperatures.

PVAL is not the only water soluble polymer on the market. Other water soluble polymers are shown in Table 2.

Table 2 Water-soluble polymers

Type

Production

Source

PVAL

Synthetic*

Non-renewable*

Ethylene vinyl

Synthetic*

Non-renewable*

alcohol (EVOH)

Cellulose

Natural

Renewable

acetate

(cellulose)

Chitosan

Natural

Renewable

(invertebrates)

* made from fossil fuels

 

The term non-renewable source refers to the use of fossil fuels, which are finite in nature. PVAL and EVOH are highly unusual, synthetic crude oil-based polymers in that they dissolve in water. EVOH is most commonly used as an oxygen barrier layer in multi-layer film packaging (see Section 7.1) although it is expensive to use and the high price limits its applications elsewhere. PVAL is also the only polymer consisting of a carbon-carbon backbone that biodegrades. Polymers made from renewable resources include plant-based materials such as plant starch (which can be renewed by re-planting crops) and animals sources such as chitosan (found in insect exo-skeletons). Chitosan also has good gas barrier properties and is used as a coating for other biodegradable polymers and edible coatings. Both cellulose acetate and chitosan are water-soluble.

The water solubility of polymer materials means that they can end up as pollutants in water ecosystems (river, ocean) and affect aquatic life if they are not monitored and removed. Removal is done by microorgasms for PVAL and other similar potentially water soluable pollutants include polyacylics, polycarboxylates, polyethers and polyglutamic. For PVAL, research as far back as 1936 (a.6) found that PVAL in waste water was biodegraded by a phytopathogenic organism of fungal origin, Fusarium lini. The by-products being water and carbon dioxide. Since then many studies have been carried out on PVAL degradation in both aerobic conditions and soil samples with satisfactory results. The actual biodegradation mechanisms are beyond the scope of this review however the reader is referred to a survey carried out by Chiellini and co-workers (a.7) in 2003 for an overview of this subject.

The solubility of PVAL makes a big difference to the final application. For example consider three alternative PVAL materials that can be considered as very soluble, moderately soluble and slightly

Polyvinyl Alcohol: Materials, Processing and Applications

soluble. A guide to potential applications based on this property is shown in Table 3.

Table 3 Solubility as application guide

Very soluble

Moderately

Slightly soluble

soluble

Pharmaceutical

Loose fill

Food packaging

capsules which

packaging

dissolve to

release drugs

Medical sutures

Agricultural

Diaper films

films

Detergent single

Single use food service items

Medical

dose blocks

containers

Life span short

Life span:

Life span: high – must survive until disposal

medium

As we have seen, the solubility of PVAL depends on both the molecular weight and the level of hydrolysis. To add to this, PVAL that is partly hydrolysed is less dependent on temperature to be soluble. For highly hydrolysed grades however, it may be necessary for solutions to reach temperatures just under 100 °C before dissolution occurs. For disposal of items such as food packaging, diaper films and medical containers, left to degrade in the environment, it is unlikely that they would ever reach high enough temperatures to dissolve in rain water for example. It is therefore, necessary to consider whether degradation by environmental conditions or degradation by dissolving into water is the required outcome. Methods of degradation will be covered later in Section 14.

Partially hydrolysed PVAL is easier to dissolve than fully hydrolysed PVAL

6. PVAL Film Properties

PVAL is the most commercially important water soluble film, therefore, it is worth taking a look at the major properties of these materials.

Given their water soluble nature it is probably not surprising that the first consideration is that the resultant mechanical properties depend on humidity. High humidity produces a film which is soft and tough. Low humidity gives a hard and brittle material. These depend initially on the degree of polymerisation since tensile strength and elongation increase with degree of polymerisation

and partly hydrolysed materials are weaker than fully hydrolysed materials.

A higher degree of polymerisation gives increasing strength, but humidity has the effect of a plasticiser, swelling the structure to make it softer and tough.

6.1 Barrier Proporties

PVAL materials have excellent oxygen barrier properties (and also act as a barrier to carbon dioxide and nitrogen). These values are comparable to the performance of EVOH and much better than the common commodity packaging materials listed in Table 4.

Table 4 Oxygen permeability of common materials and PVAL (30 μm film, 50% humidity)

Material

Oxygen Permeability (ml/m 2 /day)

Hot water soluble PVOH

0.24

Warm water soluble PVOH

0.36

Cold water soluble PVOH

1.85

EVOH

0.29-2.4

Nylon 6

26-38

PET

40-80

PVC

50-390

High-density polyethylene (HDPE)

1700-2400

PP

2,000-10,000

Low-density polyethylene (LDPE)

12,000

An increase in dissolution temperature (and crystallinity) improves the performance of the oxygen barrier. However, the downside is the affinity to water. Water vapour will permeate through the films and therefore PVAL is a poor barrier to water vapour. Interestingly this is the opposite of polyethylene which allows oxygen to pass through its structure but not water vapour. Wet PVAL film has little strength but a dry film has good tensile properties.

PVAL has found application as a barrier layer in flexible packaging but not in rigid packaging (such as bottles) where EVOH and PA are utilised. Whilst aluminium of micrometer thickness is traditionally used in flexible packaging, creating a virtually perfect barrier, using plastics by lamination or co-extrusion gives high (but not perfect) barrier performance but at a better cost

Polyvinyl Alcohol: Materials, Processing and Applications

performance. Other flexible packaging barrier materials used in this way include poly(vinylidene chloride) (PVDC), EVOH or PA.

However, it needs to be considered that PVAL, EVOH and PA are only effective barriers in a dry state. Therefore, sandwich constructions in which they are protected by materials with water barrier properties are necessary to maintain the oxygen barrier properties of these materials.

6.2 Other Film Properties

6.2.1 Mechanical Properties

Degree of polymerisation affects both the tensile strength and elongation film properties, so that as the degree of polymerisation increases so does the strength. The tensile strength also increases with a rise in the degree of hydrolysis.

However, as well as these factors, the humidity also has

a marked effect on physical properties.

At low humidities, PVAL film is hard and brittle,

whilst at high humidity it is soft and flexible due to the plasticising effect of the water vapour. This dependence

is greater for partially hydrolysed grades than for those

that are fully hydrolysed.

Humidity leads to increased flexibility and softness.

6.2.2 Plasticiser Effects

Water acts as a plasticiser for PVAL whether by the action of humidity or as a solution. At low humidities the same effect can be achieved by glycols which serve to prevent the PVAL film from becoming hard and brittle. For thermal processing techniques such as injection moulding it is necessary to add plasticiser to prevent premature degradation. These will be discussed further in the thermal processing section.

6.2.3 Oil and Solvent Resistance

PVAL is highly resistant to oils (animal, vegetable or mineral origin) and organic solvents (aromatic and aliphatic hydrocarbons, esters, ethers and ketones). This resistance like many of the other properties of PVAL is

affected by the degree of polymerisation and the degree of hydrolysis.

6.2.4 Water Sensitivity and Hygroscopy

PVAL films will swell and take up water if immersed. Partially hydrolysed grades have higher levels of hygroscopy and solubility to water vapour than fully hydrolysed grades.

These factors and the rate of swelling can all be decreased by heat treatment which increases the crystallinity of the film.

6.2.5 Adhesion Characteristics

As the degree of hydrolysis increases there is a change in the relative number of acetate and hydroxyl groups present. This in turn creates changes in the adhesion character of the film.

When used as an adhesive agent, low degrees of hydrolysis give adhesion to hydrophobic surfaces, higher degrees of hydrolysis lead to adhesion to hydrophilic (strong affinity for water) surfaces.

6.2.6 Antistatic

PVAL is resistant to static build up and this property can be useful in packaging applications where atmospheric dust is present.

7. Solution Processing

The spinning of Vinylon fibres from solution, primarily of interest only to the Japanese market has already been discussed. Another process using PVAL in solution to spin fibres is electrospinning. In this case very thin, nano-sized fibres can be produced, allowing the resultant fibres to be used in a range of medical and filtration applications. The major drawback with electrospinning is the volumes that can be produced. If large volume equipment comes onto the market, this type of manufacture could be applicable to more than just niche markets.

Since many applications described here are carried out in solution, it is worth considering how these

Polyvinyl Alcohol: Materials, Processing and Applications

solutions are made. These methods can also be used to differentiate between a fully hydrolysed and partially hydrolysed grade.

It has been shown that the solubility is dependent on

two factors, degree of polymerisation and hydrolysis. Fully hydrolysed grades are not really soluble at room temperature so a stirred water/PVAL mixture will need to be heated to nearly boiling to ensure full dissolution.

For partially hydrolysed grades, the plasticiser effect of the water and solubility means the solute (PVAL in this case) tends to form lumps if prepared in the same way as fully hydrolysed grades, therefore in this case, the PVAL should be added slowly to the solution whilst stirring. The temperature can be raised if necessary to speed this process up.

Whilst solution concentrations obviously vary from application to application, a 10% solution is a very common dilution rate for PVAL and can therefore be considered as an indicator of the levels of PVAL used in solution for the purposes here.

8. Melt Processing

PVAL has a decomposition temperature of 180 °C. However it does not melt below 180 °C, and has

a melting point range of between 180 and 240 °C.

Some properties are shown in Table 5. Therefore thermal processing of PVAL presented a considerable challenge worldwide.

Table 5 Properties of PVAL

Property

Typical value

Density

1.19-1.31 g/cm³

Melting point

180-240 °C (dependent on degree of hydrolysis)

Boiling point

228

°C

Degradation temperature (unplasticised)

180

°C

Unplasticised PVAL degrades at temperatures above 180 °C due to water elimination from the chemical structure. Further degradation can cause discoloration and crosslinking to occur as the hydroxyl and acetate side groups are eliminated. Whilst the melting point of PVAL can vary between 180-240 °C depending on the level of hydrolysis, the effect of the relatively

low degradation reaction temperature means that melt processing applications a limited to only materials with low hydrolysis levels or materials that a heavily plasticised (which generally meant sacrificing the useful properties inherent in the PVAL materials in the first place).

Therefore, until the last decade, the unwelcome onset of thermal and shear degradation during melt processing of PVAL limited the use of conventional thermoplastic melt technology. Application of PVAL was limited to aqueous solutions and cast films. However, advances in PVAL polymer formulation mean that the properties of PVAL can now be retained during thermoplastics processing and it is possible to produce water-soluble, non-toxic, biodegradable plastics by conventional thermoplastics forming techniques. A brief description of some of these techniques follows.

Extrusion

Process for producing either pellets for other heat forming processes such as injection moulding, sheets (which can also be used for thermoforming) or profiles such as tubes, pipes and rods.

Film blowing

Process for producing thin films products such as shrink wraps and carrier bag film.

Injection Moulding

High shear and pressure process for production of complex and mass produced components such as mobile phone covers, lids, automotive door handles, motorcycle helmets.

Thermoforming

Low pressure process which deforms sheet material into relatively simple shapes such as trays, cups and shallow tubs.

Blow Moulding

Inflation production process which produces hollow articles such as bottles, containers and tanks.

Melt spinning

Production of thin fibre strand produced from molten plastic passed through a multi-holed profile. (This is not to be confused with spinning from a solution, as in the production of Vinylon fibre or electrospinning which produces PVAL nano-fibres and is also a solution process.)

Polyvinyl Alcohol: Materials, Processing and Applications

PVAL melt processing temperatures tend to range between 180 and 240 °C. This depends on the level of hydrolysis and specific formulation and additives used. Generally fully hydrolysed grades, which have higher melting points, require higher temperatures to be used. They also tend to be harder to process. To improve the processibility of PVAL it is necessary to use a plasticiser and lubricants which lower melt temperature and viscosity and therefore allow lower processing temperatures to be utilised. The degree of degradation is strongly influenced by acetate groups which liberate acetic acid during processing which catalyses further degradation to occur. Higher levels of hydrolysis 98 mol% are more resistant to degradation that 88 mol%. Temperature rather than shear appears to be a dominant factor in this.

In such applications, the basic PVAL must be plasticised so as to reduce its melting point, and obtain a thermal processing window for processing. In general plasticisers, such as glycerol, polyethylene glycol, sorbitol and other compounds have been used.

Mowiflex TC is an example of a thermoplastic melt processable material currently sold by Kuraray. This can be used to produce blown and sheet film as well as injection moulded components. As expected of PVAL, it is moisture sensitive and sold in moisture resistant bags, however, it can be dried if needed at 60-80 °C for 6-8 hours using conventional air drying equipment. Therefore, it can be treated like other moisture sensitive materials such as Nylon routinely used in processing.

8.1 Extrusion

Tubing and hoses produced by extrusion retain many of the properties recognisable from solution processing. They are highly flexible and retain excellent solvent resistance to oils, greases and other chemicals.

Processing is carried out on standard extruders with low residence times. Keeping residence times as low as possible is one key factor in successful processing of PVAL materials. Thermal damage produces discoloration of PVAL products, as it does with many other thermoplastic components.

8.2 Injection Moulding

For injection moulding of PVAL, recommended mould tool temperatures are in the 70-80 °C range with melt temperatures ranging from 190-220 °C. This is similar

to parameters used to process polyethylenes. This can be performed on conventional equipment using hot or cold runners to produce a variety of moulded components. With the fast cycling time possible with injection moulding it is possible to mass produce a variety of components and products very rapidly and economically.

An example component is exhibited in the Science Museum, London, UK. This is a biodegradable mobile phone casing developed by researchers at the University of Warwick's, Warwick Manufacturing Group, in conjunction with PVAXX Research & Development Ltd. A water soluble mobile phone case was the component. However, this idea had a twist. By imagining the components end-of-life and burying the case after use with a sunflower seed beneath it, the phone biodegraded and the sunflower seed began to grow and eventually flowered. This was timed with the growing awareness of the problem of plastic waste and sustainability, as well as the newly introduced European Union WEEE Directive (waste electrical and electronic equipment) (a.8) which covered the ever growing problem of electrical waste. Therefore, discarded mobile phones were a hot topic and this application captured public attention. However, problems of water proofing the product for use (in rain or wet environments for instance), mean as yet this application is not in commercial production.

8.3 Film Moulding

An extrudable PVAL material for blown film application was marketed by A. Schulman, Akron, USA under the name Aquasol. It is reported to have the same physical properties as the cast film and could be used in conventional polyolefin melt equipment. The target market to be biodegradable replacement for LDPE (a.9). Most of the market in these film applications is for disposable packaging.

Table 6 shows a typical range of properties shown by various grades of PVAL in comparison to other film materials. Most marked here is the tear strength and tensile strength which is actually comparable to that produced by a polypropylene material. PVAL materials also show good puncture resistance and impact strength. However performance is markedly affected by the degree of hydrolysis and therefore the crystallinity of the base material as well as the molecular weight, distribution and branch structure.

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Table 6 Properties of PVAL and common films at 25 μm

 

Property

PVAL

Cellophane

PVC

LLDPE

OPP

Light transmission (%)

60-66

58-66

48-58

54-58

70-86

Light reflected (%)

81

60

80

22

80

Tear strength (Elmendorf) (g/mil)

260-3000

20-40

390-780

290-980

4-6

Tensile Strength (MPa)

40-90

55-131

20-76

17-19

25-30

Elongation at break (%)

110-400

-

5-250

50-600

70 -100

LLDPE – linear low-density polyethylene OPP – orientated polypropylene

 

Blow up ratios may vary according to supplier of PVAL material. According to Kuraray, the grade Mowiflex TC can achieve a blow up ratio (inflation ratio) of 1:8.

8.4 Blow Moulding

While PVAL can be used as a barrier layer in multi-layer bottles, generally EVOH is used for rigid packaging applications as produced by blow moulding. For example, with PET bottles, EVOH can be used as a barrier layer to keep the carbonated contents fizzy. Another commonly used barrier layer is PVDC, however, the use of these materials as packaging materials is generally declining due to environmental issues. Therefore other materials such as EVOH, PVAL, coated PP films, Nylon resins called MXD6, and PET films which are silica- or alumina-coated are becoming more popular for gas-barrier purposes.

Recently, various types of oxygen scavengers have been developed and applied as active packaging materials. In fact, PET bottles having oxygen barrier or scavenging properties are now used in the production of plastic beer bottles in Europe and the United States.

Because of the environmental interest in the problems of plastic waste disposal and the inherent solubility and biodegradable nature of PVAL, interest in this material has heightened for these processes which are capable of high production rates.

9. Packaging

Biodegradable packaging is a direct response to the problem of waste packaging and disposal using petroleum-based synthetic plastics. Material performance and cost are the main barriers to increased biodegradable market share as consumer acceptance

of these materials is growing. Legislative demands for sustainability and biodegradable disposal such as composting are also drivers towards the use of biodegradable materials (see Section 15). The major problem with waste packaging here has to do with product life cycles. Packaging materials have expected lifetimes which are very short – days or weeks. A plastic used in construction on the other hand, such as PVC window frames are expected to last for decades. Therefore, discarded packaging makes up a considerable proportion of the plastic waste stream. This is therefore an ideal outlet for biodegradable plastics which can be used for packaging items such as food films, single use food containers, disposable plates and cutlery and bottles. These products can be mass produced through processes such as injection moulding, blow moulding and film blowing if cost effective and reliable supplies of biodegradable materials are available. However, this is not always the case.

9.1 Active Packaging

Active packaging is where a packaging system actually does more than simply package food. One such example would be to transfer antimicrobal agents from a carrier film and into the food to maintain a predetermined and useful concentration to help with food safety or food preservation for example. For such purposes, properties such as diffusion, polymer swelling and dissolution are important. The properties of PVAL make it a polymer of interest for such new applications. Antimicrobotic release systems described here have until now mainly been used in medical and pharmaceutical applications.

10. PVAL in Medicine: Hydrogels

Hydrogels are 3-dimensional crosslinked hydrophilic polymer networks which do not dissolve in water

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at body temperatures but swell when exposed to an aqueous medium (a.5).

PVAL is one of the most well known hydrogel materials and can be caused to crosslink as required. PVAL has good biocompatilbility and this has meant it has found application in a variety of medical applications including contact lenses, implants, drug delivery systems, medical implants and also wound dressing.

Hydrogels in wound dressings can incorporate useful features such as pain control, ease of changing, transparency to allow monitoring of healing, absorbtion and prevention of fluid loss, bacterial barriers, good oxygen permeability, and good handling or control of drug dosage. Hydrogels provide an interesting comparison to the field of active packaging whereby the packaging is also incorporating useful features.

As a biocompatible material PVAL is also of interest for surgical grafts and implants as well as medical devices.

11. Biopolymers

Biopolymers is short for biological polymers. These are polymers which occur in nature produced by microorganisms, plants and animals.

In the 1970s, the first impacts of the energy crisis began to focus the development of alternatives to traditionally employed materials. The response was to begin active research in the area of biopolymers. As early as the 1980s, the main advantage for using biopolymers became their capacity to decompose under natural

conditions. Continued apprehensions regarding the increased cost of crude oil due to the uncertainty of global supply is compounded by the ongoing concerns regarding the current political climate. These drivers have forced manufacturers and government to consider alternative solutions to reduce dependence upon oil. Bio-based alternatives to fossil fuel feedstocks are growing across the globe, and the growth in biopolymer development is finding increased favour within many industrial sectors. Improvements in economies of scale and sales growth of between 20-30% per year would indicate that biopolymers may soon be competing with commodity polymers (a.17).

Therefore, biopolymer itself is a term which can be used to describe a wide range of materials. There are two categories into which a material can fall in order to be classified as such:

material or

Carbohydrates, proteins and polyesters (which are produced by microorganisms) are all found abundantly in nature. Not surprisingly, these materials are all naturally biodegradable. Common examples of each is shown in Table 7.

There are a large variety of materials which can be categorised as a biopolymer. These often take on other names such as low environmental impact polymers, or green polymers, but for the purposes of this report, the term biopolymer shall be used. Within the category of polymers which are produced from bio-feedstocks, there are three types of biopolymer - those which are

Table 7 Examples of polymers in nature

 

Biopolymer

Plants sources

Examples

Animal source

Example

Carbohydrates

Polysaccharide

Cellulose

Glycosaminoglycans

Hyaluronan

Starch

Chitin

Proteins

Amino acids

Soy protein

Amino acids

Collagen

Wheat gluten

Casein

Keratin

Polyesters

Produced by bacteria Lactic acid – found in microorganisms and animals

PHA Polymerisation of lactic acid makes poly(lactic acid) (PLA)

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naturally occurring within the environment (including those from polysaccharides, polypeptides and lipids), those which are manufactured synthetically - i.e., they are man made biopolymers in an attempt to address the problems and issues which are currently being faced, and then hybrid, composite materials which are beyond the scope of this review. There are opportunities to employ petrochemical based materials in order to develop a hybrid composite which can extend product ranges and enhanced competitiveness.

Increase in the production, and subsequent use of biopolymers could be attributed partly to the increasing awareness of the damage to the environment caused through the use of fossil resources, which are widely recognised as being a finite feedstock (a.18). Security of supply, particularly within the current political and economic climate is another significant factor.

Some natural polymers can also be extracted and chemically modified to produce thermoplastics. For example, Polymerisation of lactic acid makes poly(lactic acid) (PLA).

With the exception of poly(lactic acid) (PLA) these polymers are all naturally produced by nature. In the case of PLA, a monomer from nature, lactic acid, is polymerised by man to produce PLA. So it could be argued that this is a type of synthetic material however, it retains its biodegradability and has a renewable source. It is therefore generally considered to be a biopolymer. Therefore this section also includes polymers from renewable resources that can be polymerised to create biopolymers that are biodegradable and may be naturally produced or synthetically produced.

Biopolymers may be synthetic or naturally occurring in origin, but in order for them to be of significant benefit to the manufacturing sector they have to be competitive on financial, performance and also availability criteria.

To switch from a biopolymer to a bioplastic it is necessary to add additives, just like conventional polymer to plastic processes. Therefore, bioplastics are plastics manufactured using biopolymers with other additives, however, they do not necessarily retain the biodegradability properties of the biopolymer.

The major advantage of using biodegradable materials is that they can be naturally diposed of through processes such as composting. But the biodegradability of raw materials does not necessarily mean that the product or package made from them (e.g., coated paper) is itself compostable.

However, there is widespread interest for biopolymers and bioplastics among consumers. The public perception is that conventional plastics are environmentally unfriendly. The brand of ‘sustainability’ can provide an image benefit. However, for manufacturers the environmental benefits of biodegradable packaging must be reflected in cost advantages, if large scale applications are to become feasible. Therefore, in the short term, it may be preferable to communicate the functional advantages of biodegradable packaging rather than its compostability.

Biopolymers can have advantages for waste processing. Coated paper (with for example, polyethylene) is a major problem product for composting. Although such materials are usually banned from inclusion in organic waste under separate collection schemes, some of them usually end up in the mix. The paper decomposes but small scraps of plastic are left over in the compost. The adoption of biopolymers for this purpose would solve the problem.

Whether the use of a bioplastics will contribute to a more sustainable society is a question that will have to be studied by a representative life cycle analysis (LCA) of each application and by comparison with existing applications. Representative LCA are needed at material and product levels; they must make allowance for future developments in biopolymers and take account of all relevant environmental impacts associated with the complete product life cycle, including the depletion of raw materials, the agricultural use of fertilisers and pesticides, transportation, utilisation and waste disposal. Biopolymers can be categorised as either:

Naturally occurring

Naturally occurring biopolymers are those which are formed organically by the earth's natural resources, with the most common natural biopolymers being derived from starches and celluloses. Starch is found in corn, potatoes and wheat and is therefore offers a potential opportunity for farmers wishing to develop non-food crops. Cellulose is the most plentiful carbohydrate in the world. Natural biodegradable polymers are generally produced in nature by all living organisms and as a class, they represent truly renewable resources since they are predominantly biodegradable, even if this process is slow as they are produced in nature (a.20). The synthesis of these materials involves enzyme- catalysed, chain growth polymerisation reactions of activated monomers, which are typically formed

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within cells by complex metabolic processes (a.19). Predominantly these polymers are formed from one of the three following categories:

These protein materials tend not to be soluble, so they are more often employed in their natural form. Prime examples of these include wool, silks and collagens. Gelatin, however, is a water-soluble biopolymer and as such has significant implications for use within a number of industries, particularly pharmaceutical and medical applications.

celluloses, etc)

Polysaccharides include the biopolymers which can be categorised as starch, cellulose and chitin based. Cellulose and starch based biopolymers have attracted the most interest due to their wide availability and relative low cost, but other complex carbohydrates are also of interest.

Starch is the primary carbohydrate reserve in both plant tubers and seed endosperm. The largest source of starch worldwide is from maize, but other contributors to the starch stocks include wheat, potato and rice. It is an attractive proposition to biopolymer developers due to its abundant stock and subsequent low cost. Starch films have been employed particularly within packaging films, and the biopolymer Mater-Bi, manufactured by Novamont is predominantly starch-based. Corn starch is the raw material from which poly(lactic) acids (PLA) are derived. Thermoplastic starch and starch blends such as with PVAL and aliphatic polyesters are available.

Naturally produced polyesters including PVB, polyhydroxy butyrate (PHB) and poly(hydroxybutyrate- co-hydroxylvaleratevalerate) (PHBV).

Celluloses are also well represented within nature in amongst other forms, wood and paper. Cellulose is a polysaccharide as it is derived from sugars - it is repeated units of the monomer glucose. Cellulose biopolymers have been used for packaging particularly for confectionery and cigarettes.

Chitin is a naturally occurring material found in the animal kingdom, in the shells of crustaceans and insects. In its original form, chitin is not soluble, but chitosan (partly deacetylated chitin) is. Both materials have found favour in the cosmetic industry due to their water-retaining and moisturising properties.

These materials constitute those derived from oils and

fats. Triglycerides are extracted from sunflowers, rape and soya oils. Cashew nut shell liquid is also employed from this classification. The development of rape and soya oils has lead to an increased volume production for use within non-food alternatives and this has had

a subsequent impact upon the overall material cost through an increase in global demand (a.19).

Synthetic

Synthetic biopolymers are those which are not found naturally occurring and as a result are artificially manufactured by man. Generally these are derived from fossil fuel materials, much in the same way as traditional commodity polymers. These materials include polycaprolactone (PCL), PVAL and EVOH.

Polycaprolactone (PCL) have been available in differing forms since the mid 1970s, but whilst the low melting point of the material makes thermally accelerated degradation an increasingly attractive proposition, it means that the material cannot be used in applications that will generate some heat. Current uses for PCL include orthopaedic casts and adhesive mould agents. Other aliphatic polyesters include polybutylene succinate (PBS). Aliphatic-aromatic copolyesters and hydro-biodegradable polyesters such as modified PET are also available.

12. Blends

A blend is a combination of two or more materials whose objective is to achieve a superior performance from the composite than is available from the separate constituents. Natural polymers have been introduced in

different kinds of blends as both polymers and as fillers

in order to improve biodegradability. Starch has been

used widely for this reason due to its low cost and large

availability in the market.

Blend materials are produced by processing of starch with biodegradable polymers such as PVAL, PLA, PCL and PHB plastics (PHBV) to mention but a few. Other natural polymers blended with biodegradable polymers to produce biodegradable composites materials include: cellulose, pectin, chitosan, lignin, soy protein and wheat gluten.

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13. Blends of PVAL

13.1 PVAL-Starch Blends

PVAL can be blended with thermoplastic, water- soluble starch, (e.g., potato starch) to produce readily biodegradable plastics. The blends show only one melting point, which is lower than those reported for either blend component. This suggests a miscibility between the two components. Some PVAL-starch blends commercially available are shown in Table 8.

Degradation occurs via hydrolysis and biodegradation

of the sugar molecules. Water, plasticisers (such as

glycerol and sorbitol) and other processing aids are used

to

prepare the blends which allow a reduction in the cost

of

the material but with many of the useful properties

of

the PVAL retained. As both materials are available

individually, manufacturers are able to produce their own custom blends.

These materials have found applications in packaging. For example, a water-soluble starch/PVAL compound including silicate nanoclay is used in Australia for thermoformed candy trays (a.10).

A further application for this material is in loose fill

packaging materials. These are expanded products with densities ranging from 0.01 to 0.1 g/cm 3 . Water

solubility can be achieved in under three minutes.

Table 8 Starch-PVAL Blends Commercially Available

Polymer Type

Tradename

Origin

Starch-PVAL blends

Novon

Japan

Novon

USA

Mater-bi

Italy

Thermoplastic starch (TPS) cannot be drawn into a film by itself as it is too sticky. However, in combination with PVAL, thin film (less than 200 μm) is easier to process than with PVAL alone. This is because the TPS improves the melt strength and elongation properties. These blends also show improved moisture absorption in humid conditions and offer considerable more resistance to some chemicals than basic PVAL film formulations.

Whilst the TPS improves the viscosity characteristic for film blowing, it is offset by a drop in tensile strength and puncture strength. Also the water solubility time is increased as the wet strength decreases. This can be seen in Table 9.

These materials are suitable for many mainstream PVAL water soluble applications such as hospital and medical disposal bags, dissolvable packaging for detergents and other cleaning items (toilet blocks, tablets detergents) and others already listed in this review. However, these blends are cheaper to produce.

 

Table 9 Properties of PVAL and TPS

 

Property

Test Method

PVAL 1

PVAL 2

PVAL/TPS 1

PVAL/TPS

TPS content (%)

 

0

0

50

50

Film thickness

 

50

40

50

40

(μm)

Tensile strength

ASTM D882

40

75

25

35

Dry (MPa)

(a.11)

Tensile strength

ASTM D882

 

15

 

0.5

Wet (MPa)

(a.11)

Elmendorf tear,

ASTM D1004

3.0

0.45

1.50

1.00

kg (N)

(a.12)

Solubility

ASTM D5226

60/10

70/65

100/10

185/65

Properties

(a.13)

–dissolution time

(s/˚C)

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13.2 Other Blends

Whilst PVAL-starch blends are sold commercially there are other blends of interest being developed. Blending has long been done with conventional plastic materials and the benefits are clear, by varying specific amount of the components a number of varying and tailor made properties can be produced.

Therefore blending a biodegradable but synthetic material with a biopolymer is therefore a new avenue for polymer manufactures to explore. A whole range of polymers and copolymers have been examined by academia. It has been found cellulose and PVAL form compatible blends whilst starch, gelatine and lignocellulosic materials produce incompatible PVAL blends.

13.2.1 PVAL/Gelatin Blends

Gelatin has a natural polymer source (amino acid) and is actually denatured collagen.

Gelatin is obtained from animal skin and bones and waste gelatine disposal is an issue in its own right. Diversion of waste gelatine into other applications is therefore advantageous. Like PVAL, gelatine possess film forming properties and is used in a variety of applications where this property can be utilised, such as sausage casings, thickening agent (food industries), as an adhesive in book making and as drug capsules (pharmaceutical). The combination of the two materials is therefore of interest. Two different areas of research with the materials are outlined next, one in agriculture and one in medical applications.

PVAL alone can act as a soil conditioner, gelatine alone can act as a nitrogen fertiliser. The combination of the two could provide self-fertilising films (a.14). It would also increase water permeability of films but keep their mechanical integrity. The components are immiscible on a macromolecular level but regardless of this, the film properties of a cast solution are improved by material combination if PVAL levels are kept at 80% or more. However, it appears that the more biodegradable gelatine is rendered less active by the addition of PVAL whose own biodegradability remains relatively unchanged by the addition of gelatin.

When combined in solution and cast as a film, PVAL- gelatin forms a hydrogel membrane. One potential application for this material has been identified by researchers as a moist wound dressing (temporary

artificial skin) (a.15). The resultant membrane showed interesting properties: being superabsorbent and compatible with human blood and further research is ongoing in this area.

14. Degradability

The issue of degradability and biodegradability of

plastics and biomaterials can be confusing. There are

a number of materials that can be degraded but not

biodegraded. Therefore it is worth clarifying what these terms actually mean:

Degradation of plastic: a change in the chemical structure resulting in failure of physical properties or appearance.

Degradable plastic: a plastic which undergoes degradation at specific environmental conditions. This

is determined by a standard test method and specified

change over time of the property measure (such as physical property or appearance). Examples of this type

of degradation could for example be photodegradation,

biodegradation or composting.

Photodegradable plastic: where degradation is the result of daylight.

Biodegradable plastic: one which degrades over time, through the action of nature. In the correct conditions, naturally occurring organisms such as bacteria, algae and fungi can metabolise the material to biomass. However, those materials derived from fossil fuels can also result in carbon dioxide being released into the environment during the degradation process.

Compostable plastic: where degradation occurs during composting by biological processes at a suitable rate and leaves no visible or toxic residues. The resultant degradation products are biomass, carbon dioxide and water.

Oxidatively degradable plastic: is a plastic in which the degradation results from the action of oxidation.

Hydrolytically degradable plastic: a plastic in which the degradation results from hydrolysis.

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According to the American Society for Testing and Materials (ASTM), polymers are biodegradable

if degradation results from the action of naturally

occurring micro-organisms such as bacteria, fungi, and algae. As we have seen, biodegradable polymers can

be produced from natural materials such as starch and

cellulose, as well as from polymers that are derived

from petrochemical feedstocks.

Biopolymers like polyester and starch-based polymers are being pushed as an environmentally friendly alternative to petroleum-based polymers, which may take hundreds of years to naturally biodegrade. Biopolymers can be produced without toxic by-products and biodegrade quickly, leaving a minimal human

footprint on the environment. However, like the issue

of degradability there is often confusion over the terms

biopolymer, bioplastics and biodegradability.

A bioplastic is made from a renewable natural

biological polymer source (plant, animal or microorganism), however, materials are also available in the marketplace that have both bio-origin and petroleum based materials. Equally, materials may mix biopolymers with non-bioadditives. So while some materials may be 100% fully fledged biological plastic (including all the additives and the polymer), others may be a combination.

A further confusion comes with the fact that just because

a bioplastic has components of a biopolymer, it does not necessarily biodegrade as the original source material did. On the other hand a petroleum-based plastic such

as PVAL is water soluble, but does not have the ‘green’

credentials often credited to bioplastics. Biopolymers can be made into any number of material types, such as thermoplastics, thermosets, elastomers, just like their oil-based counterparts. Therefore biopolymer, bioplastic and biodegradable are not the same thing and it should

not be assumed (although mainly it does) that one

necessarily follows from the other. PE can be produced from oil feedstocks, however, it can also be produced

by using sugar. PE which has been produced by the

sugar route is a biopolymer, that produced by oil is not. However, neither are biodegradable, though they can be

made to degrade over time through the use of additives. This sort of controlled degradation of synthetic polymer

is well known, especially for PE films.

A biodegradable plastic is one which degrades through

the action of nature. That is through naturally occurring

organisms such as bacteria, algae and fungi. This mechanism could occur through mechanisms such as composting, soil burial, anaerobic digestion, marine and freshwater environments or exposed to the environment

as litter.

The final option of the disposal of litter through biodegradation is attractive. The persistence of plastic products discarded in the environment is a major problem. The majority of these wastes come

in the form of packaging which has a short life cycle.

Therefore, biodegradable materials, especially in the packaging industry are becoming an important strategy for the future removal of plastic waste from our environment.

There are currently three different types of biodegradable materials that can be readily identified

in the marketplace:

polyethylene oxide).

as maize, corn and starch which are biodegradable. (These will be discussed in more depths in Section 14.1).

14.1 Biodegradable Plastics

A biodegradable plastic has been defined in Section

14 as when the degradation is the result of naturally occurring microorganisms (e.g., algae, bacteria or fungi) and a compostable plastic as one in which the degradation also occurs by biological processes but in a specified composting environment (a.10, a.16).

A number of different definitions of biodegradable

plastics have been published by different organisations.

However, most of the definitions of biodegradation are based on the same concept: the action of micro- organisms on the material and its conversion into carbon dioxide or methane and water.

For example, under EN 13432 (a.17) the scope of testing for packaging includes assessment of four factors. These are:

Biodegradability, disintegration during biological treatment, the effect on the biological treatment process and the effect on the quality of the resultant compost.

Some of the factors considered include:

Before assessment materials must be characterised by their constituent parts including the presence of any heavy metals, volatile solids and the organic carbon content amongst others.

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Disintegration in a biological waste treatment process can be either aerobic or anaerobic but must occur without any detrimental affects on the process itself.

For anaerobic biodegradation testing the maximum testing time can be 2 months, for an aerobic biodegrading test the maximum degradation exposure time is 6 months.

After degradation has occurred the compost would

be sieved for residues and not more than 10% of the

original dry weight of the material shall fail to pass through a < 2mm sieve fraction for an acceptable disintegration to have occurred.

Composting plastics are required to leave no toxic residues, biodegradation is generally less specific. It is therefore important to consider degradation in light of the specific standards and test methods for the materials being considered.

14.2 Oil-Based Naturally Degradable Polymers

As we have seen it is not only biopolymers than can degrade in the environment. Synthetic materials can be made to degrade by the use of additives or by being soluble in water. There are two main types of polymers in this category, PVAL and EVOH. Like PVAL, EVOH is also a water-soluble synthetic plastic and is commonly used in multilayer film packaging (film and blow moulding) in conjunction with cheaper

materials as an oxygen barrier layer. It is a high cost material whose pricing presents a considerable barrier

to

expansion into the degradable plastic market.

14.3 Photo-degradable Plastics

A

is

photodegradability, The ultraviolet (UV) radiation present in daylight can be used to photodegrade synthetic polymers which contain suitable formulations. This type of degradation can therefore be triggered in polymers such as PE. By incorporating light sensitive materials into plastic formulations either through the use of copolymers or additives it is possible to induce bond breakage of the carbon backbone. Plastics left exposed to UV light, therefore, breakdown becoming increasingly weak and brittle as the bonding breaks down. This also makes the residual components more likely to degrade further from other environmental

through the use of daylight. This is called

further type of the way plastics can be degraded

effects such as abrasion or mechanical impact. Since their effectiveness to degrade is effected by the intensity of the UV exposure, factors such as weather conditions and location are major factors in the process. Photodegradable plastics remain most useful in applications that remain problematic to littering an obvious example being plastic bags.

However, it should be noted that while most synthetics do not naturally degrade in the environment at useful timescales, they can be made to be degrade much faster if this is required. Controlling this rate is another issue and one which is beyond the scope of this review. However photodegradation is an example of controlled degradation in action.

15. Plastics and Biodegradable Plastics Disposal

Much of European environmental policy on plastics and biodegradable materials has come from European Union legislation. Environmental Action Programmes (EAP) have been in place for over 30 years now. There have been six versions which have developed increasingly as our understanding of environmental protection has advanced. Therefore from the first through to the current sixth EAP, increasing legislative requirements have been developed for the benefit of EU citizens.

However, a midterm report on the sixth EAP published in April 2006 stated that ‘the EU was still not yet on the path towards genuine sustainable development’. Therefore further legislation is still likely in waste management. In the context of this review, areas of interest to future markets of PVAL derive from tougher legislation in the areas of The Landfill Directive and Sustainable Development, both objectives in EAP 6.

For sustainable development the key themes is to promote both sustainable production and consumption. This should encourage the growth of environmental degradation as a waste disposal option. The EU intends to support research and encourage further adoption of Integrated Product Policy (IPP) programmes which are aimed at reducing environmental impact associated with particular products and services. Therefore, manufacturers in member states will be encouraged to reduce impact throughout the life cycle of their products. The EU has already adopted IPP philosophy is legislation which can be seen in both the End-of- Life (ELV) Vehicle Directive (a.18) and even more obviously in the WEEE Directive (a.8), however, these

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are sectors in which PVAL is not expected to have great impact in the foreseeable future. (Though given advances in material technology, applications such as PVAL mobile phone cases may one day be seen.)

The 1999 EU Landfill Directive (Directive 1993/31/EC) which took a further three years to become transposed into English law, will have widescale implications for how plastic waste is disposed of in future, certainly within the UK which has been heavily reliant on this form of waste disposal. Biodegradable municipal waste going to landfill must be drastically reduced, dropping to just 35% of that produced in 1995 by 2020. Whilst this legislation is not aimed at just plastics but all materials, it is clear that disposal by other means, i.e., composting facilities, are being encouraged by such legislation.

The waste management hierarchy is:

1. Prevention

2. Re-use

3. Recycling

4. Recovery (including energy recovery)

5. Safe disposal

Therefore the sensible approach in dealing with plastic waste is to reduce the amount of waste at source. For waste already generated, control should be exercised over the life cycle from design, production and usage. For bioplastics, re-use and recycling will be less of an option as the preferred disposal would be for biomass production. However, this also throws up issues of energy usage as a durable oil-based plastic once produced may be recycled several times before being recovered for energy via incineration. A one use biopolymer would be made, used, and then discarded. These are issues which must be considered in adoption of these materials. Is it worth putting all that energy into making them to immediately discard them and turn them back to biomass?

The type of biodegradable plastic employed for any application should dictate the disposal route. This may be by standard plastic reprocessing, landfill or open environments. A compostable material needs composting facilities and water soluable and/or water degradable materials need water or waste water treatments. Contamination of conventional plastics recycling routes could be a significant risk in future as biopolymers become more established in the market place.

Consider the effect of a photodegradable HDPE on HDPE recyclate. It would remain undetected in feedstock and be recycled with non-degradable plastics.

However, once these materials are reused for example as containers, they would retain the potential to degrade and disintegrate under daylight. Consumers would not be too happy if their water butts or compost bins disintegrated. Therefore, widescale use of degradable plastics has the potential to undermine the growing confidence in recycled plastics. Effective methods for control of sorting degradable and non-degradable plastics will be necessary to ensure this does not happen if there is a significant change in degradable plastic usage. Labelling to inform consumers of where to dispose of their plastics is one such method,

There are several identifiable environmental benefits that may potentially be derived from the use of biodegradable plastics compared to non-degradable plastics. These are:

such as PVAL increases the soil organic content as well as water and nutrient retention, while reducing chemical inputs and suppressing plant disease.

environmental benefits in many cases: the use of potentially sustainable resources and reduced greenhouse gas emissions.

However, it should be remembered that there is potential for adverse environmental risks with biodegradable plastics. Despite their nature, they still require time in order to decompose completely. There are significant concerns that with current low levels of consumer education, biodegradable plastics may be seen as being suitable for disposal through any means available, and in

some cases predictions are that littering will even rise as a result of their use and subsequent incorrect disposal. However, there are specific requirements regarding degradation, and indeed, in many cases the contamination

of traditionally employed polymer waste streams with

biomaterials is another considerable problem to be overcome. One potential method of resolving this issue is the development and implementation of some form

of labeling or decoration to ensure consumers are aware

of the correct disposal routes.

A further consideration is that biodegradable

plastics which end up in landfills may also prove problematic as they are unlikely to degrade under such highly packed conditions and could prove as persistent as standard plastics wastes in landfill sites. Furthermore, there is potential for methane to be released during the degradation process with some biopolymers which would clearly exacerbate global environmental issues.

Polyvinyl Alcohol: Materials, Processing and Applications

European legislation promoting sustainability will continue to be an important market driver. However, high costs relative to conventional plastics, concern about performance of biodegradable plastics, and limited production capacity have restricted market expansion to less than 1%. However, certainly in Europe, bioplastics are viewed as a large potential market for starch-based crops like corn, wheat, potatoes and peas. Currently, bioplastics applications account for only a few, serving mostly the low end loose fill packaging and high end surgical/medical devices and cosmetic packaging markets. However, if mandatory biodegradable regulations are enacted, the European markets could expand quickly.

Consumer education on sustainability, recycling and degradability should be encouraged allowing the public to have a clear picture of the options available rather than the limited viewpoints that are expressed by national newspapers for instance.

This will allow for a clearer determination of appropriate waste disposal methods such as composting, incineration and landfilling.

15.1 Composting

Compost is the natural, aerobic (oxygen using) and exothermic (heat producing) process which occurs with the breakdown of organic matter derived from animals and plants. Bacteria, fungi, insects and animals which inhabit soil break down the material and as a result biomass/humus, carbon dioxide (or methane) and water are formed. The resulting biomass can then be used to facilitate further plant growth with the use of the soil like residues, which contain significant levels of useful bacteria and nutrients and the volume of organic waste sent to landfill is also reduced.

For composting to become a major part of our waste disposal infrastructure a large number of commercial composting facilities will be required. Under waste management regulations these, like landfill sites, are likely to require licenses to ensure correct environmental standards are adhered to. It will also need a shift in the way waste is sorted. However, putting our plastic waste onto the compost heaps in our gardens may be some time away.

15.2 Incineration

Incineration, whilst not used as a major waste disposal option in the UK is the primary waste disposal route for a number of countries. Japan for example, where landfill space is limited, disposes of over 90% of its waste in this manner. Scandinavian countries also strongly favour this method of waste disposal over landfill.

The reason is that the content of municipal waste including plastic wastes, are a good source of fuel. Plastics are made from oil reserves after all. Further, the energy created by incineration can be used to generate electricity and therefore this method of disposal is often termed energy recovery. Whole cities can be powered by burning wastes by this method. However, countries who favour land filling such as the UK, do not currently have the incinerator capacity available to make widescale switches in their waste disposal strategy.

Modern technology ensures problems of emissions are minimised but often incinerators are of concern to the residents living nearby for fear of air pollution and new installations often therefore attract strong protests. Incineration does not eliminate all waste but substantially reduces it. The residues still need to be disposed of, usually by landfilling.

Plastics disposed of by incineration leave no residue. However, the use of fillers and additives may reduce the energy produced as the polymer percentage is reduced. Western Europe generates around 100 million tonnes of solid waste annually of which around 7% is plastics. However new technologies for disposal are emerging for plastic materials with heat generation, most notably methods of pyrolysis which have been developed to recover chemical fractions of the plastics which can be used as fuels or chemical feedstocks. Reinforcements where present such as glass and carbon fibre can also be collected by similar methods. At present there are technologies for collecting the polymer and technologies for collecting the fibre but not as yet, a single combined solution. However, research is ongoing in this area of materials recovery. For thermoset materials, which cannot be recycled, this could be the most appropriate method of future waste disposal. The strength and durability of thermoset composite materials makes them highly unlikely to be replaced by biopolymer composites in the near future.

Polyvinyl Alcohol: Materials, Processing and Applications

15.3 Landfilling

In the UK landfilling has been the principal means in which waste has been handled (over 80% of our waste goes to landfill), this is in contrast to some other European countries that favour incineration (with energy recovery) to dispose of their waste. However, following EU legislation, namely the EU Landfill Directive, strategies for diverting biodegradable municipal waste from landfill must be implemented.

Because of the reliance on landfilling in the UK, they were given four years longer to implement the targets (an offer extended to all EU Member States land filling at levels over 80%).

Waste considered hazardous, non hazardous and inert must be separated by landfill operators and a single site can only be licensed to accept one type of waste. Landfill operators are also, as of October 2007, required to treat non-hazardous waste. This can include any biological, chemical, physical or thermal process which reduces volume or hazard. This can include sorting, to encourage recycling or energy recovery.

The underlying principles of landfill operation remain the same: to prevent or reduce negative effects of land filling which threaten either the environment or human health.

16. Conclusion

PVAL is unique among synthetic polymers. Although made from oil-based feedstock, this polymer has an inherent ability to be biodegraded. With properties once regarded as a scientific curiosity and a niche market which utilises its inherent water solubility and with biocompatibility and biodegradable credentials, this material is likely to expand further into markets in which biopolymers and biodegradable materials (namely short life consumer products and medical applications) are likely to dominate in future.

With biodegradable plastics materials likely to become more valuable as land fill operations seek to divert such waste, it is unclear how this may affect the prospects for biodegradable plastics in the marketplace unless prices become more commercially comparable with traditional commodity plastics. Blending of materials may provide one method to limit the cost penalties but the wide scale implications for waste disposal and expanding recycling

capacity if such materials are used is also uncertain. However with increasing pressure for sustainability to be bought to bare from the EU, significant shifts both in the marketplace and disposal infrastructure will have to occur to meet the waste targets.

References

a.1

BS EN ISO 15023-1, Plastics - Poly(vinyl alcohol) PVAL Materials - Part 1: Designation System and Basis for Specification, 2006.

a.2

DIN 53015, Viscometry - Measurement of viscosity by means of the rolling ball viscometer by Hoppler, 2001.

a.3

Japan Chemical Week, 2006, 47, No.2385, 8.

a.4

N. Preston, Flexible, 2006, 4, 5, 40.

a.5

M. Kokabi, M. Sirousazar and Z.M. Hassan, European Polymer Journal, 2007, 43, 3, 773.

a.6

F.F. Nord, Naturwiss 1936, 24, 763.

a.7

E. Chiellini, A. Corti, S. D’Antone and R. Solaro, Progress in Polymer Science, 2003, 28, 963.

a.8

The European Directive on WEEE (Directive

2002/96/EC)

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Plastics Technology, 2004, 50, 10, 32.

a.10

Plastics Technology, 2007, 53, 2, 60.

a.11

ASTM D882, Test Method for Tensile Properties of Thin Plastic Sheeting, 2002.

a.12

ASTM D1004, Test Methods for Tear Resistance (Graves Tear) of Plastic Film and Sheeting, 2008.

a.13

ASTM D5226, Practice for Dissolving Polymer Materials, 2003.

a.14

E.R. Kenaway P. Cinelli A. Corti S. Miertus and E. Chiellini, Macromolecular Symposia, 1999; 144, 351.

a.15

K. Pal, A.K. Banthia and D.K. Majumdar, AAPS PharmSciTech, 2007, 8, 1, Article 21.

a.16

A. Srivastava, Popular Plastics and Packaging, 2004, 49, 1, 87.

a.17

EN13432, Packaging - Requirements for Packaging Recoverable Through Composting

Polyvinyl Alcohol: Materials, Processing and Applications

and Biodegradation - Test Scheme and Evaluation Criteria for the Final Acceptance of Packaging, 2005.

a.17

G. Scott, Polymer Degradation and Stability, 2000, 68, 1.

a.18

End-of-Life Vehicle (ELV) Directive [Directive

2000/53/EC]

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M. Heyde, Polymer Degradation and Stability, 1998, 59, 1-3, 3.

a.19

R.Chandra and R. Rustgi, Progress in Polymer Science, 1998, 23, 1273.

a.20

P. Nayak, Review of Macromolecular Chemistry

and Physics, 1999, 39, 3, 481.

Abbreviations and Acronyms

ASTM

American Society of Testing and Materials

CRT

Cathode ray tube(s)

EAP

Environmental Action Programme(s)

ELV

End-of-life vehicle

EU

European Union

EVOH

Ethylene vinyl alcohol

HDPE High-density polyethylene

IPP Integrated product policy

LCA

Life cycle analysis(es)

LCD

Liquid crystal display(s)

LDPE Low-density polyethylene LLDPE Linear low-density polyethylene

OPP

Orientated polypropylene

PA

Polyamide

PBS

Polybutylene succinate

PCL Poly- -caprolactone

PDP

Plasma display panel(s)

PE

Polyethylene

PET

Polyethylene terephthalate

PHA Polyhydroxyalkonoates

PHB Polyhydroxybutyrate

PHBV

Poly(hydroxybutyrate-co-

PLA

hydroxylvaleratevalerate) Poly(lactic acid)

PP

Polypropylene

PVAc

Polyvinyl acetate

PVAL

Poly(vinyl alcohol)

PVB

Poly(vinyl butyral)

PVC

Polyvinyl chloride

PVDC

Poly(vinylidene chloride)

TPS Thermoplastic starch

UV

Ultraviolet

References and Abstracts

Abstracts from the Polymer Library Database

Item 1 Advanced Functional Materials 18, No.19, 2008, p.2946 SURFACTANT-FREE SELF-ASSEMBLED PVA-IRON OXIDE/SILICA CORE-SHELL NANOCARRIERS FOR HIGHLY SENSITIVE MAGNETICALLY CONTROLLED DRUG RELEASE AND ULTRAHIGH CANCER CELL UPTAKE EFFICIENCY Hu S-H; Liu D-M; Tung W-L; Liao C-F; Chen S-Y

The synthesis of surfactant-free self-assembled poly(vinyl alcohol)(PVA)-iron oxide/silica core-shell nanocarriers by encapsulation of monodispersed magnetic iron oxide particles derived by high temperature decomposition of ferric acetylacetonate and a model hydrophobic drug such as ibuprofen using PVA as binder followed by coating with a thin shell of silica by hydrolysis and condensation

of tetraethyl orthosilicate is described. The products were

characterised by FE-SEM TEM SQUID magnetometry and XRD and their controlled drug release properties under an

external magnetic field were investigated by UV-visible spectroscopy. 28 refs.

Taiwan National Chiao Tung University

TAIWAN

Accession no. 1030215

Item 2 Advanced Functional Materials 18, No.19, 2008, p.2855 A NOVEL CROSS-LINKED POLY(VINYL ALCOHOL) (PVA) FOR VASCULAR GRAFTS Chaouat M; Le Visage C; Baille W E; Escoubet B; Chaubet F; Mateescu M A; Letourneur D

The fabrication of crosslinked poly(vinyl alcohol)(PVA) films by aqueous solution casting in the presence of sodium trimetaphosphate as crosslinking agent and their

characterisation by DMA and by biocompatibility via cell culture studies is described. The fabrication of small diameter tubes based on the crosslinked PVA films via

a gluing procedure with cyanoacrylate adhesive was

investigated and their evaluation as potential vascular

grafts by in-vitro and in-vivo testing is discussed in terms

of mechanical properties such as compliance elasticity and

resistance to mechanical stress compatible with circulatory blood flow. 31 refs.

INSERM; Montreal University; Paris VII Universite; Paris XIII Universite

CANADA; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE

Accession no. 1030209

Item 3 Polymer 49, No.21, 2008, p.4740 TRANSITION OF HYDRATION STATES OF POLY(VINYL ALCOHOL) IN AQUEOUS SOLUTION Wenbo Li; Yun Zheng; Rongshi Cheng

A straightforward method for determination of the

hydration number of polymer in aqueous solution based on ice-melting technique of DSC is proposed. The simple yet precise method has been applied to determine the hydration

number of poly(vinyl alcohol) (PVA) in aqueous solution covering a wide range of concentrations from 0.005 to 0.3 g(solute)/g(solution) for three samples with different molar masses. The hydration number of PVA maintains a constant lower value of 2.5 when the concentration exceeds 0.2 g(solute)/g(solution). It increases to a value

of 7 when the concentration decreases to the overlap

concentration C*of the polymer where C*was estimated

as the reciprocal of its intrinsic viscosity. For solutions of C<C* the hydration number keeps constant again at the value of 7. This behaviour evidently demonstrates that PVA

has two hydration states one occurs at the dilute regime and

the other occurs at concentrated regime. The concentration

dependent transition from one state to another is treated mathematically by a quantitative formula which involves two parameters: one denotes the transition concentration and the other denotes the width of the transition region. The transition concentration decreases linearly with increasing molar mass resembling the behaviour of molar mass dependence of overlap concentration. The structural features for the two states of hydrated PVA are briefly discussed. 19 refs. Copyright (c) 2008 Elsevier Ltd.

Nanjing University; South China University of Technology

CHINA

Accession no. 1029966

Item 4 Polymer Preprints 2008, 49, No.2, p.343 SYNTHESIS OF POLY(VINYLACETYLENE) BLOCK COPOLYMERS AS PRECURSORS FOR NANOCARBON MATERIALS Aimi J; McCullough L A; McGann J; Kowalewski T; Matyjaszewski K

Poly(vinylacetylene) (PVA)-containing block copolymers were synthesised via activators regenerated by electron transfer (ARGET) atom transfer radical polymerisation (ATRP). The active acetylenic hydrogen atom in vinylacetylene was substituted by the trimethylsilyl group in order to prevent 14-polymerisation. In the homopolymerisation of trimethylsilyl-protected

References and Abstracts

vinylacetylene (VA-TMS) it was found that a lower temperature prevented side reactions and gave a well- controlled polymer with low polydispersity. The desilylated homopolymer of PVA-TMS was easily crosslinked to give an insoluble polymer. A block copolymer of PMMA-b- PVA was also synthesised by ATRP. This block copolymer seemed miscible thus block copolymerisation overcame the insolubility of the deprotected homopolymer. Nanocarbon materials could be prepared by pyrolysis of PVA-containing block copolymers. 7 refs. Carnegie-Mellon University; Washington D.C

USA

Accession no. 1029567

Item 5 Journal of Applied Polymer Science 110, No.3, 2008, p.1784 KINETIC STUDY OF THE FREE-RADICAL POLYMERIZATION OF VINYL ACETATE IN THE PRESENCE OF DEUTERATED CHLOROFORM BY 1 H-NMR SPECTROSCOPY Semsarzadeh M A; Abdollahi M

Real time nuclear magnetic resonance spectroscopy was used to study the kinetics of the free radical polymerisation of vinyl acetate using deuterated chloroform as chain transfer agent and azobisisobutyronitrile as initiator. Effects of the concentrations of initiator and solvent on reaction kinetics were evaluated and kinetic parameters such as rate and transfer constants and initiator efficiency were calculated. It was shown that both temperature and solvent concentration affect initiator dissociation rate constant but initiator concentration does not. The solvent concentration was found to have an effect on both initiator efficiency and termination rate constant. 60 refs. Tarbiat Modarres University

IRAN

Accession no. 1029333

Item 6 Journal of Applied Polymer Science 110, No.3, 2008, p.1632 INFLUENCE OF HIGH PRESSURE GASES ON POLYMER-SOLVENT THERMODYNAMIC AND TRANSPORT BEHAVIOR Jones A T; Danner R P; Duda J L

The use of soluble gases as co-solvent in the devolatilisation process for removal of residual solvents and monomers in the polymerisation process was investigated using either carbon dioxide or ethylene with polystyrene or polyvinyl acetate. The introduction of the gas was found to reduce polymer solubility and increase solvent diffusivity and ethylene was found to have the most effect. Gas chromatography was used in the analysis of solvent removal and the work demonstrated the potential for increasing production rates in polymerisation process by exchanging the

normal non-interacting gases such as nitrogen or air by

a soluble gas. 18 refs.

Pennsylvania State University

USA

Accession no. 1029314

Item 7 Polymer Reprints 49, No.2, 2008 PHOTOINDUCED LIVING RADICAL POLYMERIZATION WITH HIGHLY ACTIVE MANGANESE COMPLEX Koumura K; Satoh K; Kamigaito M

Efficient controlled radical polymerisation of vinyl acetate (VAc) methyl acrylate (MA) or styrene (St) occurred in the presence of a system comprising ethyl iodoacetate or ethyl 2-iodo-2-methylpropanoate and dimanganese dodecacarbonyl under visible light irradiation. The polymerisation of VAc was rapid and efficient and gave

a polymer with a controlled molecular weight even at a

low concentration of Mn 2 (CO) 10 . The polymerisations of MA and St also gave polymers with controlled molecular weights. 4 refs.

Nagoya University; Washington D.C.

JAPAN; USA

Accession no. 1029046

Item 8 Pharmaceutical Technology Europe 20, No.10, 2008, p.32 PVA COPOLYMER: THE NEW COATING AGENT FUJII T; NOAMI M; TOMITA K; FURUYA Y

The commercial development of a copolymer of vinyl alcohol with acrylic acid and methyl methacrylate as a sprayable film coating agent for tablets and microparticles is described. The copolymer was characterised by solubility and viscosity in water DSC oxygen permeability the strength of film adhesion to the tablet core drug dissolution properties and impact strength and the results are discussed in comparison with those for hydroxypropyl methylcellulose as control in terms of pharmaceutical applications. 10 refs. Shionogi and Co.Ltd.

JAPAN

Accession no. 1028318

Item 9 Journal of Materials Science 43, No.17, 2008, p.5898 TWO-STEP SYNTHESIS OF POLYACRYLAMIDE/ POLY(VINYL ALCOHOL)/POLYACRYLAMIDE/ GRAPHITE INTERPENETRATING NETWORK HYDROGEL AND ITS SWELLING CONDUCTING AND MECHANICAL PROPERTIES Fan S; Tang Q; Wu J; Hu D; Sun H; Lin J

References and Abstracts

The two-step synthesis of poly(acrylamide)/poly(vinyl alcohol)(PVA)/polyacrylamide/graphite interpenetrating network hydrogels by initial radical polymerisation of acrylamide in the presence of PVA and graphite micropowder with potassium persulphate as initiator followed by a subsequent radical polymerisation of acrylamide and NN'-methylene bisacrylamide as crosslinking agent is described. The hydrogels were characterised by FTIR TGA electrical conductivity and tensile properties and the effects of PVA graphite and crosslinking agent contents on swelling properties of the hydrogels are discussed. 39 refs. Huaqiao University

CHINA

Accession no. 1028239

Item 10 FujianKey Laboratory of Polymer Materials Composites Part A 39, No.10, 2008, p.1638 CELLULOSE NANOFIBER REINFORCED POLY(VINYL ALCOHOL) COMPOSITE FILM WITH HIGH VISIBLE LIGHT TRANSMITTANCE Chunyi Tang; Haiqing Liu

In this paper we presented the fabrication and characterisation of poly(vinyl alcohol) (PVA) composite film reinforced with high volume of electrospun cellulose nanofibrous mat (CNM). Its visible light transmittance and mechanical properties were examined in relation to fibre content in the composite. Optimal CNM content in the composite was found to be 40wt% in terms of its overall properties. This composite film exhibited visible light transmittance of 75% and its mechanical strength and Young's modulus were increased by 50% and 600% respectively as compared to neat PVA film. 22 refs. Fujian Normal University

CHINA

Accession no. 1028058

Item 11 Materials Letters 62, No.28, 2008, p.4380 MECHANICAL STRENGTH IMPROVEMENT OF POLYPROPYLENE THREADS MODIFIED BY PVA/CNT COMPOSITE COATINGS Bo Zhao; Jing Wang; Zijiong Li; Ping Liu; Da Chen; Yafei Zhang

Poly (vinyl alcohol)/carbon nanotube (PVA/CNT) composite was coated on the surface of polypropylene thread for toughness enhancement. Multiwall carbon nanotubes (MWNTs) were treated in acid and alkali to get water-soluble nanotubes and then embedded into poly (vinyl alcohol) (PVA) matrix resulting in polymer-carbon composite with homogeneous nanotube dispersion. The stress-strain measurements show that the tensile strength and toughness of the PVA/CNT coated thread increased by