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Applied Plastics Engineering Handbook: Processing, Materials, and Applications
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Commencer à lireLongueur: 2,331 pages162 heures
- Éditeur:
- Elsevier Science
- Sortie:
- Sep 15, 2016
- ISBN:
- 9780323390415
- Format:
- Livre
Description
Applied Plastics Engineering Handbook: Processing, Materials, and Applications, Second Edition, covers both the polymer basics that are helpful to bring readers quickly up-to-speed if they are not familiar with a particular area of plastics processing and the recent developments that enable practitioners to discover which options best fit their requirements.
New chapters added specifically cover polyamides, polyimides, and polyesters. Hot topics such as 3-D printing and smart plastics are also included, giving plastics engineers the information they need to take these embryonic technologies and deploy them in their own work.
With the increasing demands for lightness and fuel economy in the automotive industry (not least due to CAFÉ standards), plastics will soon be used even further in vehicles. A new chapter has been added to cover the technology trends in this area, and the book has been substantially updated to reflect advancements in technology, regulations, and the commercialization of plastics in various areas.
Recycling of plastics has been thoroughly revised to reflect ongoing developments in sustainability of plastics. Extrusion processing is constantly progressing, as have the elastomeric materials, fillers, and additives which are available.
Throughout the book, the focus is on the engineering aspects of producing and using plastics. The properties of plastics are explained, along with techniques for testing, measuring, enhancing, and analyzing them. Practical introductions to both core topics and new developments make this work equally valuable for newly qualified plastics engineers seeking the practical rules-of-thumb they don't teach you in school and experienced practitioners evaluating new technologies or getting up-to-speed in a new field.
Presents an authoritative source of practical advice for engineers, providing guidance from experts that will lead to cost savings and process improvements Ideal introduction for both new engineers and experienced practitioners entering a new field or evaluating a new technology Updated to include the latest technology, including 3D Printing, smart polymers, and thorough coverage of biopolymers and biodegradable plasticsInformations sur le livre
Applied Plastics Engineering Handbook: Processing, Materials, and Applications
Longueur: 2,331 pages162 heures
Description
Applied Plastics Engineering Handbook: Processing, Materials, and Applications, Second Edition, covers both the polymer basics that are helpful to bring readers quickly up-to-speed if they are not familiar with a particular area of plastics processing and the recent developments that enable practitioners to discover which options best fit their requirements.
New chapters added specifically cover polyamides, polyimides, and polyesters. Hot topics such as 3-D printing and smart plastics are also included, giving plastics engineers the information they need to take these embryonic technologies and deploy them in their own work.
With the increasing demands for lightness and fuel economy in the automotive industry (not least due to CAFÉ standards), plastics will soon be used even further in vehicles. A new chapter has been added to cover the technology trends in this area, and the book has been substantially updated to reflect advancements in technology, regulations, and the commercialization of plastics in various areas.
Recycling of plastics has been thoroughly revised to reflect ongoing developments in sustainability of plastics. Extrusion processing is constantly progressing, as have the elastomeric materials, fillers, and additives which are available.
Throughout the book, the focus is on the engineering aspects of producing and using plastics. The properties of plastics are explained, along with techniques for testing, measuring, enhancing, and analyzing them. Practical introductions to both core topics and new developments make this work equally valuable for newly qualified plastics engineers seeking the practical rules-of-thumb they don't teach you in school and experienced practitioners evaluating new technologies or getting up-to-speed in a new field.
Presents an authoritative source of practical advice for engineers, providing guidance from experts that will lead to cost savings and process improvements Ideal introduction for both new engineers and experienced practitioners entering a new field or evaluating a new technology Updated to include the latest technology, including 3D Printing, smart polymers, and thorough coverage of biopolymers and biodegradable plastics- Éditeur:
- Elsevier Science
- Sortie:
- Sep 15, 2016
- ISBN:
- 9780323390415
- Format:
- Livre
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Applied Plastics Engineering Handbook
Applied Plastics Engineering Handbook
Processing, Materials, and Applications
Second Edition
Edited by
Myer Kutz
Table of Contents
Cover
Title page
Copyright
Dedication
Contributors
About the Editor
Preface to the First Edition
Preface to the Second Edition
Part I: Plastics, elastomeric and biobased materials
1: Engineering Thermoplastics—Materials, Properties, Trends
Abstract
1.1. Introduction
1.2. Aliphatic Polyamides
1.3. Aromatic Polyamides, Aramids
1.4. SemiAromatic Polyamides
1.5. Polyacetals
1.6. Polycarbonates
1.7. Poly (phenylene ether)
1.8. Polysulfones
1.9. High-Temperature Sulfone Polymers (HTS)
1.10. Thermoplastic Polyesters
1.11. Liquid Crystalline Polymers (Polyesters)
1.12. Poly(phenylene sulfide)
1.13. Polyetherimide
1.14. Polyimides
1.15. Polyamide Imides
1.16. Aromatic Polyketones
1.17. Polyarylates
1.18. Aliphatic Polyketones
1.19. Syndiotactic Polystyrene
1.20. Self-Reinforcing Polyphenylene
1.21. Poly(p-xylylene)
1.22. Polybenzimidazole
1.23. Comparison of Physical Properties
1.24. Trends in Engineering Thermoplastics
1.25. Processing
1.26. Conclusions
2: Polyolefins
Abstract
2.1. Industrial Processes for Polyolefin Production
2.2. Classes of Polyolefins
2.3. Catalysts for Olefin Polymerization
2.4. Industrial Reactors
2.5. Polyolefine Properties
2.6. Applications
2.7. Polyolefin Composites
3: Introduction to Fluoropolymers
Abstract
3.1. Introduction
3.2. Fluoropolymer Classification
3.3. Fluoropolymer Products
3.4. Monomer Synthesis
3.5. Monomer Properties
3.6. Polymerization and Finishing
3.7. Structure–Property Relationship of PE to PTFE
3.8. Polymer Properties of PTFE
3.9. Fabrication Techniques
3.10. Applications
3.11. Safety
3.12. Polymerization Surfactant
3.13. Economics
3.14. Summary
4: Poly(Vinyl Chloride)
Abstract
4.1. Introduction [1–3]
4.2. Synthesis of Vinyl Chloride [3,5]
4.3. PVC Resin Synthesis and Characterization [1–3]
4.4. PVC Compounds: Processing and Applications [4,7]
4.5. Recycling PVC [11]
4.6. Vinyl: Sustainability and Energy Efficiency [12]
4.7. Vinyl Chloride and Health
4.8. Dioxin
5: Thermoplastic Elastomers
Abstract
5.1. Introduction
5.2. Classification and Structure
5.3. Production
5.4. Structure–Property Relationships
5.5. Applications
5.6. Economic Aspects and Trade Names
6: Thermoset Elastomers
Abstract
6.1. Introduction
6.2. Some Experimental Details
6.3. Typical Stress–Strain Behavior
6.4. Control of Network Structure
6.5. Networks at Very High Deformations
6.6. Multimodal Chain-Length Distributions
6.7. Other Types of Deformation
6.8. Filler-Reinforced Elastomers and Elastomer-Modified Ceramics
6.9. Current Problems and Future Trends
7: Biodegradable and Biobased Polymers
Abstract
7.1. Introduction
7.2. Naturally Occurring Biodegradable Polymers
7.3. Biodegradable Polymers Derived From Renewable Resources
7.4. Biodegradable Polymers Derived From Petroleum
7.5. Biobased Polymers Derived From Plant Oil
7.6. Concluding Remarks
8: Polymeric Biomaterials
Abstract
8.1. Introduction
8.2. Polymeric Biomaterials in Ophthalmology
8.3. Polymeric Biomaterials in Orthopedics
8.4. Polymeric Biomaterials in Cardiovascular
8.5. Polymeric Biomaterials for Wound Closure
8.6. Polymeric Biomaterials in Extracorporeal Artificial Organs
8.7. Polymeric Biomaterials for Nerve Regeneration
8.8. Conclusions and Future Outlook
Part II: Plastics processing
9: Recycling of Plastics
Abstract
9.1. Introduction
9.2. Technology to Recycle Plastics
9.3. Challenges
9.4. Industries and Industry Organizations
9.5. Products
9.6. Conclusions
Acknowledgment
10: Injection Molding Technology
Abstract
10.1. The Injection Molding Screw
11: Microcellular Injection Molding
Abstract
11.1. Introduction
11.2. Background
11.3. General Discussion of Foam Processing
11.4. General Discussion of Microcellular Processing
11.5. General Discussion of Microcellular Injection Molding
11.6. Process Monitoring and Control Methods for Microcellular Injection Molding
11.7. Equipment Requirements for Microcellular Foam Injection Molding
11.8. Trexel’s MuCell Technology
11.9. Other Physical Foaming Techniques
11.10. Typical Objectives of Microcellular Injection Molding
11.11. Limitations of Microcellular Injection Molding
11.12. Best Target Applications
11.13. More Challenging Situations
11.14. Commercial Examples
11.15. Future Trends
Appendix
12: Extrusion Processes
Abstract
12.1. Introduction
12.2. Single-Screw Extruders
12.3. Single-Screw Extruder Mechanisms
12.4. Twin-Screw Extruder Equipment
12.5. Planetary Roller Extruders: Principle Components and Operating Principles
12.6. Shaping and Drawing and Extrusion Applications
12.7. Extrusion Laminations and Coatings
12.8. Solidification and Cooling
13: Blow Molding
Abstract
13.1. Introduction
13.2. The Process
13.3. Formulas for Blow Molding
13.4. Troubleshooting
Acknowledgments
14: Compression Molding
Abstract
14.1. Basics of Processing by Compression Molding
14.2. Molding Force and Pressure
14.3. Typical Presses
14.4. Compression Molds and Associated Tooling
14.5. Commonly Used Resins
14.6. Resin Charge Characteristics
14.7. Processing Parameters for Granules, Powders, and Preforms
14.8. Resin Matrix Modifiers
14.9. Engineered Fiber-Reinforced Molding Compounds
14.10. Comparisons with Transfer Molding and Injection Molding
14.11. Similar Processes
14.12. Modeling the Fluid Dynamics and Heat Transfer of Mold Filling
14.13. Ensuring Part Quality and Process Efficiency
Acknowledgments
15: Rotational Molding
Abstract
15.1. Introduction
15.2. Rotational Molding Process
15.3. Materials for Rotational Molding
15.4. Molds for Rotational Molding
15.5. Machinery for Rotational Molding
15.6. Design for Rotational Molding
16: Thermoforming
Abstract
16.1. Introduction
16.2. Thermoforming Characteristics
16.3. Thermoformed Product Characteristics
16.4. The Thermoforming Concept
16.5. Thermoforming Machinery
16.6. Thin-Gauge Thermoforming
16.7. Thick-Gauge Thermoforming
16.8. Other Thermoforming Technologies
16.9. Heaters
16.10. Thermoforming Mold Materials
16.11. Plastic Materials
16.12. Product Design
16.13. Operational Aspects of Thermoforming [22]
17: Process Monitoring and Process Control: An Overview
Abstract
17.1. Introduction
17.2. Historical Factors Affecting the Development of Process Monitoring and Controls
17.3. Basic Concepts: Open-Loop and Closed-Loop Controls
17.4. Transducers Used in Plastics Processes
17.5. Data Acquisition Systems
17.6. General Control Strategies: Extrusion Versus Injection Molding
17.7. Process Control Applications Overview: Extrusion
17.8. Process Control Applications Overview: Injection Molding
17.9. Process Development Tools
17.10. Conclusions
18: Polymer Stabilization
Abstract
18.1. Introduction
18.2. Degradation Chemistry
18.3. Stabilizers
18.4. Performance of Stabilizers
18.5. Other Factors Determining the Choice of Stabilizers
Appendix 18.1. Chemical structure, CAS number, and several trade names of several stabilizers
19: Chaotic Advection and Its Application to Extruding Micro- and Nanostructured Plastic Materials
Abstract
19.1. Applicability and Fundamentals
19.2. Machinery and Process Control
19.3. Micro- and Nanolayered Plastics
19.4. Polymer Blends
19.5. Polymer–Solid Composites and Nanocomposites
19.6. Mixtures and Nanodispersions
19.7. Decoration
19.8. Rheology Measurements with Concurrent In Situ Structuring
Part III: Additives, colorants and fillers
20: Surface Modification of Plastics
Abstract
20.1. Introduction: Surface Modification of Plastics: For What Reasons?
20.2. Overview of Surface Modification Techniques
20.3. Surface Modification (Activation) Techniques
20.4. Surface-Coating Deposition Techniques
21: Plastics Additives
Abstract
21.1. Introduction
21.2. Overview
21.3. Thermal Stabilizers
21.4. Nucleating Agents
21.5. Antioxidants
21.6. Flame Retardants
21.7. Color and Colorants
21.8. Fillers
21.9. Reinforcements
21.10. Impact Modifiers and Impact Modification
21.11. Miscellaneous
22: Dispersants and Coupling Agents
Abstract
22.1. Introduction
22.2. Dispersants
22.3. Practical Use Considerations
22.4. Types of Dispersants
22.5. Property Effects
22.6. Coupling Agents
22.7. Conclusions
23: Functional Fillers for Plastics
Abstract
23.1. Introduction
23.2. The Basics
23.3. Thermal and Electrical Properties
23.4. Hardness, Friction, Scratch Resistance, and Wear
23.5. Barrier Properties
23.6. Optical Properties
23.7. Processing
23.8. Extra Phase Effects
23.9. Popular Fillers
23.10. Specialty Fillers
24: Plasticizers
Abstract
24.1. Introduction
24.2. Mechanism of Plasticization
24.3. Types of Plasticizers
24.4. Phthalate Esters
24.5. Terephthalate Esters
24.6. Dibasic Acid Esters
24.7. Epoxy Plasticizers
24.8. Trimellitate Esters
24.9. Benzoate Esters
24.10. Cyclohexanoate Esters
24.11. Polymeric Plasticizers
24.12. Phosphate Esters
24.13. Citrate Esters
24.14. Other Plasticizers
24.15. Plasticizer Characteristics and Performance of Flexible PVC
24.16. Plasticizer Selections for Specific Applications
24.17. Plasticizers for Other Polymers
24.18. Human Health Aspects of Plasticizers
24.19. Future of Plasticizers
25: Adhesion Promoters: Silane Coupling Agents
Abstract
25.1. General Concepts
25.2. Silane Adhesion Promoters
25.3. Adhesion Promoter Mechanism with Silanes
25.4. Optimizing Coupling Agent Performance
25.5. How to Choose a Silane Coupling Agent
25.6. General Applications of Silane Coupling Agents
25.7. Industry and Utility
25.8. Non-Silane Adhesion Promoters
25.9. Sources of Adhesion Promoters
Part IV: Design and applications
26: Plastics Joining
Abstract
26.1. Introduction
26.2. Mechanical Joining
26.3. Adhesive Bonding
26.4. Welding
27: Design of Plastic Parts
Abstract
27.1. Introduction
27.2. Material Selection
27.3. Process Selection
27.4. Structural Design
27.5. Design for Manufacturing and Assembly
27.6. Conclusions
Acknowledgments
28: Three-Dimensional Printing of Plastics
Abstract
28.1. Introduction
28.2. 3D Printing Processes
28.3. Design with 3D Printing
28.4. Manufacturing Strategy
28.5. Future Outlook
28.6. Conclusions
Acknowledgments
29: Plastics in Buildings and Construction
Abstract
29.1. Introduction
29.2. Applications
29.3. Plastic Applications in Green Building Design
29.4. Conclusions
Acknowledgments
30: Automotive Applications of Plastics: Past, Present, and Future
Abstract
30.1. Introduction
30.2. Exterior Components
30.3. Interior Components
30.4. Under-the-Hood Components
30.5. Future Outlook
30.6. Conclusions
31: Infrastructure Applications of Fiber-Reinforced Polymer Composites
Abstract
31.1. Introduction
31.2. Products and Applications
31.3. Durability of Polymer Composites
31.4. Summary
32: The Plastic Piping Industry in North America
Abstract
32.1. Introduction
32.2. Thermoplastic Pipe and Fittings Materials
32.3. Chlorinated Polyvinyl Chloride Materials
32.4. Cross-Linked Polyethylene (PEX) Materials
32.5. Polypropylene Materials
32.6. Polybutylene Materials
32.7. Acrylonitrile Butadiene Styrene Materials
32.8. Nylon (PA) Materials
32.9. Fluoropolymer Materials
32.10. Engineering Plastic Materials
32.11. Multilayer Piping Products
32.12. Composite Piping Products
32.13. Fiberglass-Reinforced Thermoset Piping
32.14. Cured-in-Place Piping
32.15. Pipeline and Piping Rehabilitation Technologies
32.16. Plastic Pipe and Fittings Manufacturing Processes
32.17. Long-Term Strength Testing of Thermoplastic Piping Materials
32.18. Test Methods for Determining Long-Term Hydrostatic Strength
32.19. Validation of Polyethylene Pipe Materials
32.20. Popelar Shift Function Calculations for PE Pipe Materials
32.21. Design of Plastic Piping Systems
32.22. Specifications, Product Standards, Test Methods, and Codes
32.23. Regulatory Matters
32.24. Applications of Thermoplastic Plastic Piping
32.25. Installation Using Thermoplastic Pipe for Pipeline Replacement
32.26. Other Piping Applications
33: PET Use in Blow Molded Rigid Packaging
Abstract
33.1. Introduction
Index
PLASTICS DESIGN LIBRARY (PDL)
PDL HANDBOOK SERIES
Series Editor: Sina Ebnesajjad, PhD(sina@FluoroConsultants.com)
President, FluoroConsultants Group, LLC
Chadds Ford, PA, USA
www.FluoroConsultants.com
The PDL Handbook Series is aimed at a wide range of engineers and other professionals working in the plastics industry, and related sectors using plastics and adhesives.
PDL is a series of data books, reference works and practical guides covering plastics engineering, applications, processing, and manufacturing, and applied aspects of polymer science, elastomers and adhesives.
Recent titles in the series
Biopolymers: Processing and Products, Michael Niaounakis (ISBN: 9780323266987)
Biopolymers: Reuse, Recycling, and Disposal, Michael Niaounakis (ISBN: 9781455731459)
Carbon Nanotube Reinforced Composites, Marcio Loos (ISBN: 9781455731954)
Extrusion, 2e, John Wagner & Eldridge Mount(ISBN: 9781437734812)
Fluoroplastics, Volume 1, 2e, Sina Ebnesajjad (ISBN: 9781455731992)
Handbook of Biopolymers and Biodegradable Plastics, Sina Ebnesajjad (ISBN: 9781455728343)
Handbook of Molded Part Shrinkage and Warpage, Jerry Fischer (ISBN: 9781455725977)
Handbook of Polymer Applications in Medicine and Medical Devices, Kayvon Modjarrad & Sina Ebnesajjad (ISBN: 9780323228053)
Handbook of Thermoplastic Elastomers, Jiri G Drobny (ISBN: 9780323221368)
Handbook of Thermoset Plastics, 2e, Hanna Dodiuk & Sidney Goodman (ISBN: 9781455731077)
High Performance Polymers, 2e, Johannes Karl Fink (ISBN: 9780323312226)
Introduction to Fluoropolymers, Sina Ebnesajjad (ISBN: 9781455774425)
Ionizing Radiation and Polymers, Jiri G Drobny (ISBN: 9781455778812)
Manufacturing Flexible Packaging, Thomas Dunn (ISBN: 9780323264365)
Plastic Films in Food Packaging, Sina Ebnesajjad (ISBN: 9781455731121)
Plastics in Medical Devices, 2e, Vinny Sastri (ISBN: 9781455732012)
Polylactic Acid, Rahmat et. al. (ISBN: 9781437744590)
Polyvinyl Fluoride, Sina Ebnesajjad (ISBN: 9781455778850)
Reactive Polymers, 2e, Johannes Karl Fink (ISBN: 9781455731497)
The Effect of Creep and Other Time Related Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9780323353137)
The Effect of Long Term Thermal Exposure on Plastics and Elastomers, Laurence McKeen (ISBN: 9780323221085)
The Effect of Sterilization on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455725984)
The Effect of Temperature and Other Factors on Plastics andElastomers, 3e, Laurence McKeen (ISBN: 9780323310161)
The Effect of UV Light and Weather on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455728510)
Thermoforming of Single and Multilayer Laminates, Ali Ashter (ISBN: 9781455731725)
Thermoplastics and Thermoplastic Composites, 2e, Michel Biron (ISBN: 9781455778980)
Thermosets and Composites, 2e, Michel Biron (ISBN: 9781455731244)
To submit a new book proposal for the series, or place an order, please contact David Jackson, Acquisitions Editor
david.jackson@elsevier.com
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Dedication
To the memory of Bill Woishnis, colleague and friend
Contributors
Sushant Agarwal, Department of Chemical Engineering, West Virginia University, Morgantown, WV, United States
Samuel L. Belcher†, Formerly Sabel Plastechs, Inc., Moscow, OH, United States
Avraham Benatar, Plastics and Composites Joining Laboratory, Welding Engineering Program, Department of Materials Science and Engineering, Ohio State University, Columbus, OH, United States
Roberto Benson, Department of Materials Science and Engineering, University of Tennessee, Knoxville, TN, United States
Mark Berry, PPD Tech, Bedford, NH, United States
William F. Carroll, Jr., The Vinyl Institute, Alexandria, VA, United States
Ernest A. Coleman, Society of Plastics Engineers, Plastics Engineer & Chemist, C P Technology, PA, United States
Chris DeArmitt, Phantom Plastics LLC, Terrace Park, OH, United States
Sina Ebnesajjad, FluoroConsultants Group, LLC, Chadds Ford, PA, United States
William G. Frizelle, Consultant, St. Louis, MO, United States
Hota GangaRao, Constructed Facilities Center, College of Engineering and Mineral Resources, West Virginia University, Morgantown, WV, United States
Pieter Gijsman, DSM Ahead B.V., Geleen, The Netherlands
Allen D. Godwin, Dwight Look College of Engineering, Texas A&M University, College Station, TX, United States
Rakesh K. Gupta, Department of Chemical Engineering, West Virginia University, Morgantown, WV, United States
Wei He
Department of Materials Science and Engineering
Department of Mechanical, Aerospace, and Biomedical Engineering, University of Tennessee, Knoxville, TN, United States
Geoffrey Holden, Prescott, AZ, United States
Rakesh K. Iyer, Department of Automotive Engineering, Clemson University, Greenville, SC, United States
Long Jiang, Department of Mechanical Engineering, North Dakota State University, ND, United States
Kenth S. Johansson, SP, Technical Research Institute of Sweden, Stockholm, Sweden
Richard W. Johnson, The Vinyl Institute, Alexandria, VA, United States
Hakan Kazan, Department of Automotive Engineering, Clemson University, Greenville, SC, United States
David Kazmer, Department of Plastics Engineering, University of Massachusetts, Lowell, MA, United States
James E. Mark, Department of Chemistry and the Polymer Research Center, University of Cincinnati, Cincinnati, OH, United States
Adrian Merrington, Midland Compounding and Consulting, Midland, MI, United States
Sylvia S. Moore, The Vinyl Institute, Alexandria, VA, United States
Eldridge M. Mount, III, EMMOUNT Technologies, LLC, Canandaigua, NY, United States
Paul Nugent, Paul Nugent, Reading, PA, United States
Peter G. Pape, Peter G. Pape Consulting, Saginaw, MI, United States
Robert A. Paradis, The Vinyl Institute, Alexandria, VA, United States
Edward N. Peters, SABIC, Selkirk, NY, United States
Srikanth Pilla
Department of Automotive Engineering, Clemson University, Greenville
Department of Materials Science and Engineering, Clemson University, Clemson, SC, United States
DI Werner Posch, Material Management, DRÄXLMAIER Group, Braunau, Austria
Sai Aditya Pradeep
Department of Automotive Engineering, Clemson University, Greenville
Department of Materials Science and Engineering, Clemson University, Clemson, SC, United States
Roger Rothon, Manchester Metropolitan University, Chester, United Kingdom
Nick Schott, University of Massachusetts Lowell, Lowell, MA, United States
Robert A. Tatara, Department of Technology, Northern Illinois University, DeKalb, IL, United States
Jim Throne, Dunedin, FL, United States
Thomas Walsh, Walsh Consulting Services, Houston, TX, United States
Dan Weissmann, DW & Associates, Simsbury, CT, United States
Jinwen Zhang, Department of Mechanical Engineering, North Dakota State University, ND, United States
David A. Zumbrunnen, Department of Mechanical Engineering, Clemson University, Clemson, SC, United States
† Deceased
About the Editor
Myer Kutz has headed his own firm, Myer Kutz Associates, Inc., since 1990. For the past several years, he has focused on writing and on developing engineering handbooks on a wide range of technical topics, such as mechanical, materials, biomedical, transportation, and environmentally conscious engineering, for a number of publishers, including Wiley, McGraw-Hill, and Elsevier. Earlier, his firm supplied consulting services to a large client roster, including Fortune 500 companies, scientific societies, and large and small publishers. The firm published two major multiclient studies, The Changing Landscape for College Publishing
and The Developing Worlds of Personalized Information.
Before starting his independent consultancy, Kutz held a number of positions at Wiley, including acquisitions editor, director of electronic publishing, and vice president for scientific and technical publishing. He has been a trustee of the Online Computer Library Center (OCLC) and chaired committees of the American Society of Mechanical Engineers and the Association of American Publishers. He holds engineering degrees from MIT and RPI, served as an officer in the US Army Ordnance Corp, and worked in the aerospace industry on the Apollo project. In addition to his edited reference works, he is the author of nine books, including Temperature Control, published by Wiley, Rockefeller Power, published by Simon & Schuster, the novel, Midtown North, published under the name Mike Curtis, and most recently the independently published novel, In the Grip. He is the editor of the Bulletin of the Professional Scholarly Publishing Division of the Association of American Publishers and writes The Scholarly Publishing Scene column for the magazine Against the Grain. He lives in Delmar, NY, with his wife, Arlene.
Preface to the First Edition
To be sure, there are a great many plastics books on the market. Some have been written by a single author, while others are edited works with multiple contributors. Some are single-volume textbooks or references, others are multivolume works. They vary widely in scope and coverage. Some sweep over a broad swath of the sprawling plastics industry. Others drill deep down into a segment of the industry—a class of materials, for example, or a process. They vary in level and emphasis as well. Some are addressed primarily to students, others to professionals. Some are designed to meet the needs of researchers, others the needs of practitioners in industry. No single source, no matter how extensive, can meet every need in every setting. The industry, in both its academic and business components, is just too massive. In any case, most plastics books are idiosyncratic—their coverage conforms to the predilections or biases of their authors and editors, again not a surprise given the breadth not only of the plastics industry, but also of current and future applications.
Moreover, in trying economic times, with severe pressures on everyone with a demanding job, from professors to engineers, it is difficult to identify potential contributors who can find enough space in their busy professional lives to put together cogent and comprehensive articles or chapters on topics of interest to broad audiences. Nevertheless, it’s still possible to assemble a coherent collection of writings from a diverse group of industrial practitioners and experienced academics, who are willing to impart their hard-won knowledge and expertise to an audience of professionals. As a result of the efforts of the contributors to this volume, I have been able to construct a useful reference for a wide audience, including plastics engineers, polymer scientists, materials engineers and scientists, and mechanical and civil engineers. (As a mechanical engineer myself, of a certain vintage, I would have particularly appreciated a reference such as this one, inasmuch as my materials training focused on metallic materials, which have been supplanted in numerous application by lighter plastics and composites.)
Reviewers of the handbook manuscript agreed with my estimation. Here are summaries of their comments. Reviewer #1 asserted that project engineers for devices using or requiring polymeric materials, as well as researchers in basic polymer chemistry modification, in biomaterials device development, and in applying composite metal/polymer materials for structural applications should find information in the handbook to be useful. Chemical engineers and scientists in related disciplines (chemistry, biology) will also find much useful information in this handbook and turn to it as a first choice, particularly if the user has limited experience in the polymer field.
This reviewer wrote of the handbook that "it appears to be the kind of text to which I would refer to refresh my memory on some subject or to create an understanding for myself of a particular polymer subfield. I would also believe that the text would be invaluable to managers in the field of materials invention or device application who would wish to have the handbook available as a ready, in-depth, reference relative for basic engineering science or manufacturing techniques for polymeric materials. I similarly would think, especially, that applications engineers and managers in consumer products and more complex engineering situations would wish to consult the handbook for initial materials selection and to verify their own understanding of specific polymeric materials’ technology and its applicability to a desired technical result.
The handbook should also be interesting to those students studying or planning a career in chemical processing industries, including those in the medical device and/or applications field. The handbook could be used as a course text though the scope of the book would require two terms for completion.
Reviewer #2 asserted that the encyclopedic approach of this handbook targets a very wide audience—from students (graduate and undergraduate level) to professionals—chemists, designers, technologists, scientists, and engineers and marketing/sales managers in consumer products (appliances, decorative, food and beverage processing); automotive, construction, aeronautics, chemical, electronics industries; and medical device and biopharmaceutical industries.
This handbook, the reviewer continued, could also be helpful for audiences not very familiar with polymer basics looking to find basic introductory articles for plastics processing and applications. More advanced readers will find the book a useful review of more complicated topics, and in this way the handbook will help promote a theoretical basis for plastics industry advancement. This handbook could be recommended as a reference to graduate and undergraduate students with variety of specialties in chemical and polymer engineering—paper and textile chemistry, materials, plastics processing, corrosion protection, coatings, etc., and polymer courses focusing on polymer processing, formulation, and characterization.
According to reviewer #3, the Applied Plastics Engineering Handbook can be used by all professionals who have anything to do with plastics. The handbook has a breadth of coverage that allows it to be useful to those new to the plastics industry as well as to experts. This handbook can be used by a practitioner to learn more about how a polymer can make a product better, to determine how a process can be made faster and more efficient, or just to gain a better understanding of what a polymer or process is all about. One purpose of the handbook is to provide experts with information about materials and processes they may already have had experience with as well as with new insights and additional information that may be useful. This handbook can be used in a wide variety of libraries, from universities to companies that process polymers or make plastic products. It would be very useful for small and start-up companies where they cannot hire experts in every different field of endeavor. This handbook supplies information that can give a well prepared practitioner the ability to venture into a new or parallel market. This handbook can also be useful to government agencies and legislators who need to learn more about a hot topic. This handbook can be a must-have reference in any serious polymer library.
The Applied Plastics Engineering Handbook opens with a brief introductory chapter on the plastics industry. Then the handbook is divided into five sections. The first section presents in-depth discussions of important polymeric materials and is divided into three parts. The first part, on plastics, begins with a brief survey chapter, and then deals with engineering thermoplastics, polyolefins, fluoropolymers, and poly (vinyl chloride); the second part covers thermoplastic and thermoset elastomers; and the third part focuses on nanocomposites.
The handbook’s second major section, Biobased Polymers and Recycling has three chapters, Biodegradable and Biobased Polymers, Polymeric Biomaterials, and Recycling of Plastics.
The book’s third major section presents descriptions of key processes, including blow molding, chaotic advection, and its application to extruding micro- and nanostructured plastic materials, chemical mechanical polishing: role of polymeric additives and composite particles in slurries, compression molding, extrusion, injection molding, microcellular injection molding, rotational molding, and thermoforming. The section closes with an overview of process monitoring and process control.
The book’s fourth major section covers additives, including adhesion promoters, silane coupling agents, coating and colorants, dispersants and coupling agents, functional fillers for plastics, flame retardants, plasticizers, and stabilizers.
The fifth and final section opens with a chapter on design of plastic parts then presents applications: plastics in buildings and construction, infrastructure applications of fiber-reinforced polymer composites, the plastic piping industry in North America, and PET use in blow-molded rigid packaging.
As noted earlier, an editor can develop a handbook like this one only because contributors are willing to participate in the first place and to diligently complete their chapters. Their participation and diligence are tested by the circumstance that I rarely meet them face-to-face. We correspond mainly through email, with occasional telephone calls. That’s how things work in today’s world. I’m able, in all of the projects I work on, to engage with experts around the world. For this handbook, a handful of contributors are based in Europe (Chris DeArmitt, who contributed two additives chapters himself, was instrumental in finding them), although most are located throughout the United States. In total, I was able to secure the participation of several dozen contributors, the majority of whom are employed in, or consult to, industry, while the remainder are professors at a number of diverse institutions. I cannot say often enough how grateful I am for their time and hard work. My thanks also to my wife, Arlene, whose constant support is vital.
Myer Kutz
Delmar, NY
December 2010
Preface to the Second Edition
This new edition of the Applied Plastics Engineering Handbook differs from the first edition, published in 2011, in several major aspects: there are four new chapters; seventeen chapters have been updated; five chapters that were in the first edition have been dropped; and only thirteen chapters are being reprinted without change.
The four new chapters include: Surface Modification of Plastics, Plastics Joining, 3D Printing, and Automotive Applications of Plastics and Elastomers. The addition of these chapters improves the scope of the handbook immeasurably. 3D printing, for example, has been discussed in the popular press in recent years and has captured the public’s imagination. More importantly, with respect to this handbook, practicing engineers will find the chapter very useful. I would like to thank contributor David Kazmer, who also updated his chapter from the first edition on Design of Plastic Parts. I worked hard to include the other three topics in the earlier edition of the handbook but was unsuccessful. Their inclusion in this edition is very gratifying and will be a major benefit to the handbook’s users. I would like to thank Kenth Johansson, Avraham Benatar, and Srikanth Pilla, together with colleagues Sai Aditya Pradeep, Rakesh K Iyer, and Hakan Kazan, for these new chapters.
The seventeen updated chapters include: Engineering Thermoplastics (Edward Peters, contributor), Polyolefins (Werner Posch), Introduction to Fluoropolymers (Sina Ebnesajjad), Thermoplastic Elastomers (Geoffrey Holden), Recycling of Plastics (Adrian Merrington), Injection Molding Technology (William G. Frizelle), Extrusion Processes (Eldridge Mount, III); Compression Molding Robert Tatara); Thermoforming (Jim Throne), Chaotic Advection and Its Application to Extruding Micro- and Nanostructured Plastic Materials (David Zumbrunnen), Dispersants and Coupling Agents (Chris DeArmitt and Roger Rothon), Functional Fillers for Plastics (Chris DeArmitt), Plasticizers; Adhesion Promoters (Allen Godwin): Silane Coupling Agents (Pater Pape), Design of Plastic Parts (David Kazmer), Plastics In Buildings and Construction (Rakesh Gupta and Sushant Agarwal), and The Plastic Piping Industry in North America (Thomas Walsh). Many of these contributors submitted entirely new manuscripts, while a few made targeted changes.
As noted previously, I dropped five chapters that were in the first edition. I did so because space is limited in a handbook’s print format and I determined that the subject matter of the four new chapters is of greater benefit to handbook users than what the five dropped chapters offered.
A majority of contributors are practitioners who work for industrial organizations or are plastics consultants. They and the rest of the roster of contributors, who are principally academics and researchers, lead busy lives. It’s a miracle, I always think, when completed chapters arrive in my email inbox; I am extremely grateful for contributors’ generosity in imparting their hard-won knowledge to a handbook’s audience. I’d like to note that the handbook’s contributor roster is increasingly international, with the addition of Kenth Johansson,.of Sweden; thanks to contributor Chris DeArmitt for recommending him. I must sadly note the passing of contributor Sam Belcher, a giant in the blow molding industry. Finally, I want to recognize my wife, Arlene, whose love and patience sustain me.
Myer Kutz
Delmar, NY
March 2016
Part I
Plastics, elastomeric and biobased materials
1: Engineering Thermoplastics—Materials, Properties, Trends
2: Polyolefins
3: Introduction to Fluoropolymers
4: Poly(Vinyl Chloride)
5: Thermoplastic Elastomers
6: Thermoset Elastomers
7: Biodegradable and Biobased Polymers
8: Polymeric Biomaterials
1
Engineering Thermoplastics—Materials, Properties, Trends
Edward N. Peters SABIC, Selkirk, NY, United States
Abstract
Engineering thermoplastics and advanced engineering thermoplastics or ultrapolymers comprise a special, high-performance segment of synthetic plastic materials that offer premium properties. When properly formulated, ETP may be shaped into mechanically functional, semiprecision parts or structural components. This chapter presents a historical overview of the development of engineering thermoplastics covers the early pioneers in the field up to recent advances in engineering thermoplastics. In addition, it covers a broad range of chemistries, types of polymers, their properties, key performance features, and a brief description of targeted markets.
Keywords
engineering thermoplastics
advanced engineering thermoplastics
ultrapolymers
aliphatic polyamides
aromatic polyamides
semiaromatic polyamides
polyacetals
polyoxymethylene
polycarbonates
poly(phenylene ethers)
polysulfones
polyphenylsulfones
polyethersulfones
high-temperature sulfone polymers (HTS)
thermoplastics polyesters
poly (butylene terephthalate) (PBT)
poly(ethylene naphthalene-2,6-dicarboxylate) (PEN)
poly(butylene naphthalene-2,6-dicarboxylate) (PBN)
liquid crystalline polymers (LCP)
poly(1,4-benzoate)
polyphenylene sulfide
polyetherimide
polyimide
polyamide imides
aromatic polyketones
aliphatic polyketones
syndiotactic polystyrene
polyphenylene
poly(p-xylylene)
parylene
polybenzimidazole
poly[2,2’-(m-phenylene)-5,5’-bibenzimidazole] (PBI)
poly(2,5-benzimidazole)
ab-PBI
physical properties
trends in engineering thermoplastics
copolymers
blends and alloys
additives
processing
1.1. Introduction
Plastics are one of the indispensable materials of modern life that has changed the way we live. Throughout history we have witnessed trends where one material has elevated to replace another for performance, or economic reasons. Advancement in materials has been coeval with the spread of civilization. Early man used available metals in their naturally occurring state. The progress of civilization was literally determined by man’s ability to discover new materials, allowing mankind to induce the properties necessary for increasingly sophisticated tools and implements of destruction. Indeed, societies that learned to exploit new materials developed distinct advantages over their neighbors. This was broadly exemplified in terms of key materials where mankind advanced from the Stone Age, to the Bronze Age, the Iron Age, and the age of steel.
The age of synthetic plastics began in 1909 with the discovery by Leo Baekeland of synthetic phenol-formaldehyde resin. In general, plastic materials are arbitrarily placed into three categories commodity thermoplastic, engineering thermoplastics (ETP), and advanced engineering thermoplastics (AETP), which are also referred to as specialty, advanced, or ultrapolymers. The commodity plastics constitute the highest volume of usage, their consumption exceeding 1 million tons per annum on global scale. ETP comprise a special, high-performance segment of synthetic plastic materials that offer premium properties. When properly formulated, ETP may be shaped into mechanically functional, semiprecision parts or structural components. The term mechanically functional
implies that the parts will continue to function even if they are subjected to factors such as mechanical stress, impact, flexure, vibration, sliding friction, temperature extremes, and hostile environments [1]. The ETP age began 75 years ago.
AETP are distinguished by their unmatched thermal, mechanical, and chemical properties and are at the top position in the plastics performance pyramid. These materials have also been among the fastest growing segment of plastics giving way to new applications driven by innovation.
Innovation in new plastic materials exploded in the 1950s and 1960s. Continuing technological advances have resulted in an even greater impact on our lives and ETP have further penetrated markets dominated by metals.
As substitutes for metal in the construction of mechanical apparatus, ETP offer advantages such as corrosion resistance, transparency, lightness, self-lubrication, and economy in fabrication and decorating. Replacement of metals by plastics is favored as the physical properties and operating temperature ranges of plastics improve and the cost of metals and their fabrication increases [2]. Plastic applications in transportation, a major growth opportunity, have been greatly accelerated by the current awareness of the interplay of vehicle weight and fuel requirements. The ability to replace metals in many areas has resulted in tremendous growth in ETP.
A significant driving force behind the growth in ETP is the continuing expansion of electrical/electronic markets, which demands smaller, lighter components that operate at higher speeds. In addition, the same requirements are driving the automotive market segment. Original Equipment Manufacturers strive toward lower production cost, style flexibility, lower maintenance and more efficient, lower polluting vehicles that utilize better performing materials under the hood and in exterior components.
The global consumption of ETP in 2012 is estimated at 19.6 million metric tons. ETP are the fastest growing segment of the plastics industry. It is estimated that the use of ETP will reach 29.1 million metric tons by 2020. This chapter focuses on the development of ETP during the past 75 years.
1.2. Aliphatic Polyamides
Polyamides, commonly called nylons, were the first commercial thermoplastic engineering polymers. In 1928 Wallace Carothers at DuPont began polymer experiments on polyamide 66. Nylon 66, PA66, is prepared from condensation polymerization of hexamethylene diamine (HMDA) and adipic acid. The structure is shown in Fig. 1.1. PA66 made its commercial debut as a fiber in 1938 with its first use in bristles for toothbrushes and later in women’s hosiery. PA66 was the exemplar for the whole family of polyamides. The first use of nylon as a molding compound was in 1941. In 1953 the 4536 metric tons of PA66 molding compound represented the entire annual volume of ETP [3,4].
Figure 1.1 Structure of polyamide 66.
Polyamides was a new concept in plastics for several reasons. It was semicrystalline polymer that underwent a sharp transition from solid to melt. In addition, it had a relatively high service temperature. The combination of toughness, rigidity, and lubrication-free
performance made PA66 peculiarly suited for mechanical bearing and gear applications. Polyamides acquired the reputation of a quality material by showing that a thermoplastic could be tough, as well as stiff, and perform better than metals in some cases. This performance gave nylon the label an engineering thermoplastic.
PA66 exhibits a glass transition temperature, Tg, of 78°C and a crystalline melting point, Tm, of 269°C. The crystallinity and polarity of the molecule permit dipole association that conveyed to relatively low molecular weight polymers the properties normally associated with much higher molecular weight amorphous polymers. At its Tm, the polymer collapsed into a rather low-viscosity fluid in a manner resembling the melting of paraffin wax. It lacked the typical familiar broad thermal plastic range that is normally encountered in going from a glassy solid to a softer solid to a very viscous taffy stage. This factor led to some complications in molding because very close tolerances were required in mold construction, and very precise temperature and pressure monitoring was necessary to prevent flash or inadvertent leaking of the mobile melt. Early molders of nylon were highly skilled—they had to be because the industry was young.
Nylon based on ω-aminocarboxylic acids, although briefly investigated by Carothers, was commercialized first in Germany around 1939 [4]. Of particular interest to the plastic industry is Nylon 6, PA6, based on caprolactam, which became available in Europe in 1946. Allied Chemical Company initially introduced PA6 to the United States for fiber purposes in 1954. Polycaprolactam is semicrystalline and has been successfully applied as a molding compound. Its Tm of 228°C is lower than PA66. The structure of PA6 appears in Fig. 1.2, Nylon 46, PA46, was developed and commercialized in 1990 by DSM Engineering Plastics to address the need for a polyamide with higher heat and chemical resistance for use in automotive and electrical/electronic applications. PA46 is prepared from 1.4-diaminobutane and adipic acid. PA46 has a Tm of 295°C and has higher crystallinity than PA6 or 6,6 [3].
Figure 1.2 Structure of polyamide 6.
In general, the key features of polyamides are fast crystallization, which means fast molding cycling; high degree of solvent/chemical resistance, toughness, lubricity, fatigue resistance, and excellent flexural-mechanical properties that varies with degree of plasticization by absorbed water. Deficiencies include a tendency to creep under applied load and very high moisture absorption, which will plasticize the polyamide and lower some properties.
Varying the monomer composition has produced many different varieties of polyamides. Variations include PA69, PA610, and PA612 (made from HMDA and the 9-, 10-, and 12-carbon dicarboxylic acids, respectively); and Nylon 11 and Nylon 12 (via the self-condensation of 11-aminoundecanoic acid and lauryl lactam, respectively). These specialty nylons exhibit lower Tms and lower moisture absorption to one-third or one-fourth that of PA6 or PA66.
When unsymmetrical monomers are used, the normal ability of the polymer to crystallize can be disrupted; amorphous (transparent) nylons can then be formed. These amorphous nylons are not as tough as PA6 or 66 but they do offer transparency, good chemical resistance in some environments, and lower moisture absorption.
For example, the polyamide prepared from the condensation of terephthalic acid with a mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamines (PA6-3-T) was developed at W.R. Grace and Company, later produced under license by Dynamit Nobel AG, and currently available from Evonik Industries under the trade name Trogamid TR. This amorphous polyamide exhibits a Tg of 148°C, high clarity, stiffness, toughness, resistance to chemicals, and very good resistance to UV damage. It is used in water filter housings, flow meters, grease containers, and spectacles frames.
Another amorphous nylon is based on aliphatic amines, cycloaliphatic amines, and terephthalic acid. It is marketed under the Grilamid trade name by EMS-Chemie. This amorphous nylon exhibits a Tg of 155°C, high transparency, stiffness, and resistance to chemicals. It is used in viewing glasses, transparent housings, and high-quality spectacle frames.
1.3. Aromatic Polyamides, Aramids
Nylons prepared from aromatic diamines and aromatic dicarboxylic acids can lead to very high-heat aromatic nylons (aramids). Poly (m-phenyleneisophthalamide), MPIA, is made from the condensation polymerization of m-phenylenediamine and isophthaloyl chloride and has a Tg of 280°C. Its structure is shown in Fig. 1.3. W. Sweeny, a scientist at DuPont was responsible for discoveries leading to the commercialization of MPIA and is available under the Nomex trade name. MPIA is used in fibers to make heat-resistant and flame-retardant apparel, electrical insulation, and composites.
Figure 1.3 Structure of MPIA.
Poly (p-phenyleneterephthalamide), PPTA, was invented by S. Kwolek at DuPont in 1965 (first marketed in 1971) [5]. It is made from p-phenylenediamine and terephthaloyl chloride. It exhibits a Tg of 425°C and Tm of >500°C. It was the first commercialized liquid crystalline polymer. Fibers were spun from a lyotropic sulfuric acid solution. Its structure is shown in Fig. 1.4 and is available under the Kevlar trade name. PPTA is used to make highly oriented crystalline fibers derived from liquid-crystalline technology. PPTA fibers exhibit a very high modulus and its uses include composites for sporting goods, bullet resistant apparel, automotive transmission parts, and tires.
Figure 1.4 Structure of PPTA.
1.4. SemiAromatic Polyamides
Several semiaromatic polyamides are based on the reaction of HMDA and terephthalic acid. The structure of poly (hexamethylene terephthalate), PA6T, appears in Fig. 1.5. However, pure PA6T exhibits a Tg of 180°C and a very high Tm of 370°C. The high Tm results in expensive polymerization processes and difficulty in molding. Therefore, modified copolymers based on PA6T have been examined extensively because of use of inexpensive monomers and enhanced properties over aliphatic polyamides. For example, terpolymers using an inexpensive, third monomer such as isophthalic acid, adipic acid, caprolactam, or HMDA have led to the commercialization of semiaromatic polyamides by Amoco, BASF, and DuPont under the trademarks Amodel R, Ultramid T, and Zytel HTN, respectively. These terpolymers exhibit Tgs from 100 to 125°C and Tms from 290 to 320°C and offer enhanced performance over PA66 or 6—such as, higher stiffness, increased strength, greater thermal, and dimensional stability.
Figure 1.5 Structure of polyamide 6T.
Polyamide 9T (PA9T) is a semiaromatic polyamide commercialized under the name of Genestar by Kuraray Co [6]. PA9T uses a long, flexible aliphatic diamine consisting of nine methylene groups in a sequence as part of the polyamide backbone. This melt processible polyamide exhibits a Tg of 125°C and Tm of 300°C. The structure of PA9T appears in Fig. 1.6.
Figure 1.6 Structure of polyamide 9T.
Features include low water absorption, high heat resistance, high chemical resistance, hydrolysis resistance, low friction coefficient, high impact strength good fuel barrier properties, and dimensional precision. It offers an alternative to materials such as PA612 and PA12. Its applications range from friction and wear application, automotive parts to electronic/electrical.
1.5. Polyacetals
After nylon, the next engineering polymers to be commercially introduced were polyacetals [7,8]. Polyacetals are polymerized from formaldehyde and are also referred to as polyoxymethylenes (POM). Staudinger explored the basic polyformaldehyde structure rather thoroughly in the late 1920s and early 1930s, but he was unable to synthesize sufficiently high molecular weight polymer with requisite thermal stability to permit melt processing [9]. Pure formaldehyde could be readily polymerized, but the polymer readily unzips (spontaneously depolymerizes). In 1947, researchers at DuPont began a development program on the polymerization of formaldehyde and stabilization of the polymer. Twelve years later, DuPont brought the unzipping tendency under control with proprietary stabilization technology and commercially announced POM under the Delrin trade name. The key to the stabilization of POM was to cap the terminal hydroxyl groups that participate in, or trigger unzipping reactions. Postetherification or esterification capped or blocked the hydroxyl groups. This material has a Tg of –75°C and Tm of 181°C. The structure of capped POM is depicted in Fig. 1.7.
Figure 1.7 Structure of capped POM.
Celanese joined DuPont in the market with their proprietary polyacetal polymer under the Celcon trademark within a year. Celanese managed to obtain basic patent coverage, despite DuPont’s prior filing. The Celanese POM was a copolymer that resulted in stabilization against thermal depolymerization. POM copolymer has a Tm of 170°C. The structure of POM copolymer is depicted in Fig. 1.8.
Figure 1.8 Structure of POM copolymer.
Both Celanese and DuPont aimed their products directly at metal replacement. Items such as plumbing hardware, pumps, gears, and bearings were immediate targets. In many respects, the acetals resemble nylons. POMs are highly crystalline, rigid, cold-flow resistant, solvent resistant, fatigue resistant, mechanically tough and strong, and self-lubricating. They also tend to absorb less water and are not plasticized by water to the same degree as the polyamides. Rapid crystallization of acetals from the melt contributes to fast mold cycles.
Key areas of use for POMs are industrial and mechanical products that include molded or machined rollers, bearing, gear, conveyor chains, and housings. POMs are widely used in plumbing and irrigation because they resist scale build up, and have excellent thread strength, creep resistance, and torque retention. A deficiency of polyacetals is a tendency to thermally unzip and an essentially unmodifiable flammability.
1.6. Polycarbonates
The aromatic polycarbonates, PC, were the next engineering polymers to be introduced. In 1953, D.W. Fox at General Electric Company and H. Schnell at Bayer AG independently discovered the same unique super tough, heat-resistant, transparent, and amorphous polymer [7,10–13]. When the companies became aware of each other’s activities, agreements were reached that enabled both parties to continue independent commercialization activities without concern for possible subsequent adverse patent findings. General Electric Company (now SABIC) introduced their PC into the United States under the Lexan trademark in 1959 at about the same time as the polyacetals, and a commercial plant was brought on stream in 1960.
PCs of numerous bisphenols have been extensively studied. However, most commercial PCs are derived from bisphenol A (BPA) and is depicted in Fig. 1.9. Both solution and solvent free, melt-transesterification processes are used to manufacturer polycarbonates.
Figure 1.9 Structure of polycarbonate.
In the solvent processes, PC is produced by an interfacial polymerization process [14]. The BPA and 1–3 m% monofunctional phenol, which controls molecular weight, are dissolved or slurried in aqueous sodium hydroxide; methylene chloride is added as a polymer solvent; a tertiary amine is added as a catalyst, and phosgene gas is dispersed in the rapidly stirred mixture. Additional caustic solution is added as needed to maintain basicity. The growing polymer dissolves in the methylene chloride, and the BPA and phenolic content of the aqueous phase diminishes.
In the solvent free, melt-transesterification, diphenyl carbonate reacts with BPA to regenerate phenol for recycle and molten, solvent-free polymer.
BPA based PC is an amorphous polymer with a Tg of 150°C. It offers outstanding impact strength, glass-like transparency, heat resistance, excellent electrical properties, intrinsic flame retardancy, and high dimensional stability up to just below its Tg. This outstanding combination of properties and processing versatility have made PCs the ideal resin for many applications. In addition, transparency gave polycarbonates another dimension and has led to applications in safety glazing, light covers, automotive headlamp lenses, water bottles, compact discs, and ophthalmic applications.
The PCs, like the nylons and acetals, were directed toward metal replacement applications. Glass-fiber filled versions of PCs are available, and this combination is particularly well suited to compete with metal parts. As in the case of other amorphous polymers, glass fibers act as stiffening and strengthening agents but do not raise operating temperatures significantly. In semicrystalline polymers, fillers tend to act as a crutch to bridge the soft, amorphous regions that have Tg-dependent properties, thereby permitting the plastic to maintain structural integrity up to its crystalline melting point. Without filler, crystalline polymers tend to creep under static load at relatively low temperatures because their Tg values are generally comparatively low.
PCs are readily modified via copolymerization with long chain aliphatic dicarboxylic acids to give a resin with improved flow; other bisphenols or phthalates to increase Tg and give PCs with higher heat resistance; and trisphenols to give a branched PC with improved melt strength for blow molding/extrusion. In addition, PC is amenable for the development of many different commercial polyblends [10,15]. Blending PC with other thermoplastics widens the performance window and will be discussed later in this chapter.
Unique high heat PC copolymers have been developed that offers greater thermal resistance than standard PC. These high Tg PCs have been achieved through combining BPA monomer with a high-heat comonomer. The resulting copolymers have a glass transition temperature of 185°C or higher. These copolymers form a family of clear, tough, high heat PCs. In addition, their high flow enables greatly expanded design options for molding thin-wall parts. These materials are offered under the Lexan XHT trademark by SABIC [16,17].
Application opportunities include automotive lighting reflectors and bezels, industrial lighting, protective face shields, heat resistant helmets, heat shields electrical components, residential fuses, landscape lighting, flashlight lenses, and fluorescent lighting covers.
1.7. Poly (phenylene ether)
In 1956, A. Hay of the General Electric Company (now SABIC) discovered a convenient catalytic oxidative coupling route to high molecular weight aromatic ethers [18–20]. Polymers were made by bubbling oxygen through a copper-amine-catalyzed solution of phenolic monomer at ambient temperatures. A wide variety of phenolic compounds were explored, but the cleanest reactions resulted from those that contained small, electron-donor substituents in the two ortho positions. Hence, research focused on the use of 2,6-dimethylphenol. In 1964 General Electric Co. introduced the PPE homopolymer, poly(2,6-dimethyl-1,4-phenylene ether), under the PPO trademark. PPE had excellent hydrolytic resistance and an extremely high Tg of 215°C. The structure is shown in Fig. 1.10.
Figure 1.10 Structure of poly(2,6-dimethyl-1,4-phenylene ether).
The very high Tg, high melt viscosity, and a pronounced tendency for PPE to oxidize at processing temperatures made it very difficult to process. However, in 1965 Westlake Plastics Co. started production of extruded rods, sheets, and tubing of PPE under the Alphalux trademark. Also in 1965 Richardson Co. marketed a miscible blend of PPE with crystal polystyrene, PS. In spite of the PPE/PS miscibility, the single-phase blend was not a commercial success [21].
In mid-1966 GE introduced a family of PPE blends with high impact polystyrene, HIPS, under the Noryl trademark. This combination of total compatibility with PS and the added toughness from the polybutadiene in HIPS were the keys to commercial success. Varying the PPE/HIPS ratio results in a wide range of high temperature, easy to process, tough, dimensionally stable plastics [22].
The first applications were those requiring autoclaving (medical equipment) and outstanding electrical properties at elevated temperatures. As compounding, stabilization, and processing skills improved, markets for PPE blends expanded to include office equipment, electronic components, automotive parts, water distribution systems, and general metal replacement.
PPE-based resins are relatively resistant to burning, and judicious compounding can increase their burn resistance without the use of halogenated flame retardants. In addition, these blends could be modified with glass fiber and mineral fillers. Because of low moisture absorption, dimensional stability, and ability to be used over a wide temperature range, PPE-based resins are especially adaptable to metallization.
After expiration of the original patent on PPE, several manufacturers (e.g., BASF, Huls, Borg-Warner, Asahi, Engineering Plastics Ltd., Mitsubishi) began sales of their own blends based on PPE or its copolymers.
PPE is a versatile material and is used in alloys with PAs to enhance the performance and decrease the moisture absorbance of the PAs. These alloys are described in later in this chapter.
1.8. Polysulfones
Polyarylsulfones are a class of high-use temperature thermoplastics that characteristically exhibit excellent thermal-oxidative resistance, good solvent resistance, hydrolytic stability, and creep resistance [23,24]. Routes to polysulfones were discovered independently and almost simultaneously in the laboratories of Union Carbide Corporation, ICI, and 3M Corporation.
In 1965 A.G. Farnham and R.N. Johnson of Union Carbide (this business was acquired by Amoco Polymers in 1986 and is currently part of Solvay Advanced Polymers) announced the preparation of thermoplastic polysulfones, PSU [25]. The first commercially available polysulfone was prepared by the nucleophilic aromatic displacement of the chlorides on 4,4’-dichlorodiphenyl sulfone, DCDPS, by the anhydrous di-sodium salt of BPA. The reaction is conducted in a dipolar aprotic solvent, such as dimethyl sulfoxide. This polysulfone, PSU, was commercialized in 1966 under the Udel trademark. This amorphous polymer exhibits a Tg of 186°C. The structure of PSU is shown in Fig. 1.11.
Figure 1.11 Structure of polysulfone.
In 1967 3M introduced polybiphenyldisulfones under the Astrel 360 trade name. This polymer was made by the Friedel-Crafts reaction of biphenyl-4,4’-disulfonyl chloride with diphenyl ether and exhibited a very high Tg of 277°C [26]. The structure is shown in Fig. 1.12. The price was very high, it was difficult to melt process, and had limited availability. This resin is no longer commercially available.
Figure 1.12 Structure of polyarylsulfone.
In 1972 ICI started market development of polyethersulfone, PES. This amorphous polymer has a Tg of 225°C. Compared to PSU, it exhibits higher thermal stability, better chemical and solvent resistance, and improved toughness [27]. The structure appears in Fig. 1.13.
Figure 1.13 Structure of polyethersulfone.
In 1976 Union Carbide introduced a second-generation polysulfone resin under the Radel R polyphenylsulfone, PPSU, trade name. This higher performing PPSU was prepared from 4,4’-biphenol and DCDPS [28]. PPSU has a Tg of 225°C. Its structure is shown in Fig. 1.14. The biphenyl moiety imparts enhanced chemical/solvent resistance, outstanding toughness, greater resistance to combustion, and enhanced thermo-oxidative stability.
Figure 1.14 Structure of polyphenylsulfone.
In general, aromatic polysulfones are somewhat polar, aromatic ethers that offer outstanding oxidation resistance, hydrolytic stability and very high thermal endurance in conjunction with a good balance of mechanical properties which are suitable for hot water and food handling equipment, range components, TV applications, alkaline battery cases, and film for hot transparencies. The unmodified products are transparent with a slightly yellow tint. Low flammability and low smoke suit it for aircraft and transportation applications. In addition, it can withstand rigorous handling and repeated steam sterilization cycles and is used in medical application. Thus, polyarylsulfones are used in surgical equipment, laboratory equipment, life support parts, and autoclavable tray systems. Blow molding polyarylsulfones produces suction bottles, tissue culture bottles and surgical hollow shapes.
1.9. High-Temperature Sulfone Polymers (HTS)
There have been several attempts to commercialize high-temperature sulfone polymers, HTS, with performance greater than PES and PPSU. HTS was based on the nucleophilic aromatic displacement of the chlorides on 4,4"-bis (4-chlorophenylsulfonyl) biphenyl with hydroquinone under basic conditions in a dipolar aprotic solvent. In the mid-1970s and again in the mid-1980s, ICI had unsuccessful marketing efforts for polyetherbiphenyldisulfones (Victrex 720P) [29].
In 2004 Solvay Advanced Polymers introduced these HTS under the Supradel trademark. In 2007 the trademark was changed to EpiSpire. The structure appears in Fig. 1.15. HTS is a high-temperature amorphous polymer. The more rigid biphenyldisulfone unit results in polymer with a Tg of 265°C, which is noticeably higher than Tgs other sulfone polymers [30,31]. The structure of HTS appears in Fig. 1.15.
Figure 1.15 Structure of high-temperature sulfone polymer.
HTS is transparent and completely amorphous and can be melt processed by injection molding and extrusion. HTS exhibits high thermal performance capabilities, good strength, stiffness, resistance to hydrolysis by hot water and steam, excellent resistance to acids and bases, and inherent flame resistance. The material’s thermal performance combined with its good strength and stiffness, dimensional stability, and creep resistance suggests opportunities in high-temperature injection molding applications that traditionally have been limited to filled, semicrystalline polymers. Applications for HTS include opportunities in metal and high-performance thermoset resins replacement in a wide range of engineering applications, which includes automotive, aerospace, electrical, electronic, and industrial product applications.
1.10. Thermoplastic Polyesters
In the late 1920s W. Carothers and his research group at DuPont investigated the formation of polyesters from the condensation polymerization of aliphatic dicarboxylic acids with diols. These aliphatic polyesters were found to be inadequate as fiber precursors because of their low melting points. The aliphatic polyesters were bypassed for polyamides with much higher Tms. Semiaromatic thermoplastic polyesters had their beginning in 1941 when J.R. Whinfield and J.T. Dickson at DuPont substituted terephthalic acid for the previously investigated aliphatic dibasic acids and discovered high melting crystalline polymers [7,32,33]. Whinfield and Dickson quickly realized that the polymer poly(ethylene terephthalate), PET, based on ethylene glycol and terephthalic acid was the best suited for fibers. ICI, DuPont, and others developed PET into the familiar polyester fibers and films. PET exhibits a Tg of 70°C and Tm of 265°C. The structure appears in Fig. 1.16.
Figure 1.16 Structure of poly (ethylene terephthalate).
In addition, other semiaromatic polyesters including poly (butylene terephthalate), PBT, were described. PBT prepared by the transesterification reaction of dimethyl terephthalate and butanediol. PBT exhibits a Tg of 45°C and a Tm of 225°C. The structure is shown in Fig. 1.17. Many years later a number of polyester fiber producers became interested in PBT because it resembled nylon.
Figure 1.17 Structure of poly (butylene terephthalate).
While the fiber producers were busily expanding their fiber activities, a number of companies were simultaneously trying to adapt PET as a molding compound. In 1966, the first injection molding grades of PET were introduced; however, these early materials were not very successful. The primary problem was that PET does not crystallize very rapidly. A molded object composed of a crystallizable polymer caught in an amorphous or partially crystallized state would have limited utility. In service, such a part could crystallize further, shrink, distort, crack, or fail. The obvious solution was to use hot molds and hold the parts in the mold until the crystallization process was completed. Postannealing also permits continued crystallization. These approaches, especially with glass fiber incorporation, led to acceptable parts. However, the molding cycles were economically unacceptable. Alternately, some developers tried to use very low molecular weight PET-glass products that crystallized more rapidly. However, because of their low molecular weights, these products lacked essential properties. A very broad search has been conducted for such things as nucleating agents and crystallization accelerators. An improved PET injection-molding compound was introduced by DuPont in 1978 under the trade name Rynite. A number of other companies have followed DuPont into the market. The PET-based molding compounds are gaining acceptance, but actual volume is relatively small.
Other companies look for alternative routes to faster crystallizing polyesters. Celanese researchers focused on PBT and found that it met all the requirements for a molding compound. Compared to PET, PBT had very fast molding cycles even with a cold to moderately heated molds. The basic composition of matter patents had long since expired on PBT when Celanese sampled the market in 1970 with a glass-fiber reinforced PBT product designated X-917. This PBT molding compound was subsequently available under the Celanex trade name. Eastman Kodak followed Celanese early in 1971, and General Electric (now SABIC) followed Eastman Kodak later in the same year with a PBT polyester resin under the Valox trade name. Since that time a dozen or more additional companies around the world have entered the business.
Basically, PBT seems to have a unique and favorable balance of properties between nylons and POM resins. It has relatively low moisture absorption, extremely good self-lubrication, fatigue resistance, solvent resistance, and good maintenance of mechanical properties at elevated temperatures. When PBT was reinforced with glass fiber it has excellent maintenance of properties up to its crystal melting point. Key markets include under-the-hood automotive applications, which require thermal and solvent resistance, electrical and electronic applications, power tools, small and large appliance components, and athletic goods.
Although PET and PBT are widely used, better thermal and mechanical properties are desired for some applications. Higher performance in semiaromatic polyesters was obtained from polyalkene naphthalates. These semicrystalline polyesters are prepared by the condensation polymerization of naphthalene-2,6-dicarboxylic acid and flexible aliphatic diols. The naphthalene moiety imparts stiffness to the linear polymer backbone, leading to improved physical and mechanical, barrier, chemical resistance properties, and UV-ray screening performance. Poly(ethylene naphthalene-2,6-dicarboxylate), PEN, became commercially available from Teijin Ltd. in the early 1970s. PEN has a Tg and Tm of 125 and 268°C, respectively [34]. Its structure appears in Fig. 1.18.
Figure 1.18 Structure of poly(ethylene naphthalene-2,6-dicarboxylate).
PEN is a slow crystallizing polymer. PEN has good transparency, enhanced deflection temperature under load compared to PET, very low gas and water permeation. Targeted applications are in areas that requires transparency, heat resistance, or chemical resistance. These include returnable bottles, cosmetic containers, plastic dinnerware, and health-care product containers. In addition, PEN can be blended with PET to enhance the performance of PET to give a good balance of cost and performance, improved moisture and gas barrier, heat resistance, increased UV-ray absorption.
Poly(butylene naphthalene-2,6-dicarboxylate), PBN, is prepared from naphthalene-2,6-dicarboxylic acid and 1,4-butsnediol. It exhibits a Tg of 78°C and Tm of 243°C [35]. Its structure appears in Fig. 1.19. PBN, like PBT, shows fast crystallization rates compared with other polyesters. The interchain interactions due to the naphthalene rings and the flexibility of the butylene groups can give rise to fast nucleation and spherulitic growth from the melt. PBN exhibits the following unique features: excellent abrasion resistance, excellent in chemical resistance, low gas and water vapor barrier properties, excellent chemical resistance, and good mechanical, thermal and insulating properties.
Figure 1.19 Structure of poly(butylene naphthalene-2,6-dicarboxylate).
PBN exhibits much less abrasion in the Taber test than POM and PPS at room temperature, leading to use in gears and gear-change levers. Its gas-barrier properties have been applied as a back-sheet material for solar battery chargers where back-sheets are normally comprised of multilayer structures. Additional applications include cable encapsulation for mass transportation, where the PBN provides resistance to abrasion between individual cables.
Another class of polyesters are based on cycloaliphatic diols. Eastman Chemical has a broad portfolio of copolyesters where the combination of cycloaliphatic diols, ethylene glycol, iso- and terephthalic moieties are varied. Two will be discussed here. The copolyester poly(1,4-cyclohexylene-dimethylene terephthalate/isophthalate), PCT, is produced from 1,4-cyclohexanedimethanol (CHDM) and a mixture of terephthalic and isophthalic acid. PCT exhibits a Tg of 91°C and Tm of 261°C. The structure of PCT is depicted in
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