Table Of Content(cid:1)(cid:2)(cid:3)(cid:4)(cid:5)(cid:4)(cid:6)(cid:4)(cid:2)(cid:7)(cid:8)(cid:9)(cid:5)(cid:10)
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in
Chemical Processing Industries
The Definitive User’s Guide and Databook
Sina Ebnesajjad, Ph.D.
DuPont Fluoroproducts
Wilmington, Delaware
Pradip R. Khaladkar
DuPont Engineering Technology
Wilmington, Delaware
Copyright © 2005 by William Andrew, Inc.
No part of this book may be reproduced or utilized in any form or by any means, electronic or mechanical,
including photocopying, recording, or by any information storage and retrieval system, without permission in
writing from the Publisher.
Plastics Design Library and its logo are owned by William Andrew, Inc.
ISBN: 0-8155-1502-2
Library of Congress Cataloging-in-Publication Data
Ebnesajjad, Sina.
Fluoropolymers applications in chemical processing industries : the
definitive user’s guide and databook / Sina Ebnesajjad and Pradip R.
Khaladkar.
p. cm.
Includes bibliographical references and index.
ISBN 0-8155-1502-2 (alk. paper)
1. Fluoropolymers--Industrial applications. I. Khaladkar, Pradip R. II. Title.
TP1180.F6E34 2005
668.4'238--dc22
2004016616
Printed in the United States of America.
This book is printed on acid-free paper.
10 9 8 7 6 5 4 3 2 1
Published in the United States by
William Andrew, Inc.
13 Eaton Avenue
Norwich, NY 13815
1-800-932-7045
www.williamandrew.com
NOTICE
To the best of our knowledge the information in this publication is accurate; however the Publisher does not
assume any responsibility or liability for the accuracy or completeness of, or consequences arising from, such
information. This book is intended for informational purposes only. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use by the Publisher. Final determination of
the suitability of any information or product for any use, and the manner of that use, is the sole responsibility of
the user. Anyone intending to rely upon any recommendation of materials or procedures mentioned in this
publication should be independently satisfied as to such suitability, and must meet all applicable safety and
health standards.
William Andrew, Inc., 13 Eaton Avenue, Norwich, NY 13815 Tel: 607/337/5080 Fax: 607/337/5090
Dedicated to
Ghazale and Shaila
Series Editor’s Preface
This is the latest book in the PDL (Plastics Design series. In each class, the size of its audience was
Library) Fluorocarbon Series. The original idea for simply too small to meet the economic requirements
the Fluorocarbon Series was conceived in the mid- of publishing.
1990s. Two important rationales precipitated the The first two books of the series cover
development of the collection. First, there were no commercial fluoropolymers (ethylinic); the third book
definitive sources for the study of fluorinated focuses on their applications in the chemical
polymers that included the commercial products. A processing industries. The fourth book deals with
researcher seeking the properties and characteristics fluoroelastomers, the fifth with fluorinated coatings
of fluorinated plastics did not have a book that could and finishes, and the sixth book is about fluorinated
serve as a single-source reference. Information put ionomers such as Nafion®.
out by commercial manufacturers of polymers has The authors of these handbooks are leaders in
long been the source of choice. Second, the post-war their fields who have devoted their professional
generation (a.k.a., baby boomers) were beginning to careers to acquiring substantial expertise. Each book
retire, thus reducing the available knowledge in the is a product of decades of the author’s experience
industry and academia. and several years of research into the available body
The selection of the topics for the books has been of knowledge.
made based on the importance of the practical Our hope is that these books will meet the needs
applications of fluorinated polymers. Inevitably, a of the people who work with fluorinated polymers
number of fluorinated macromolecule classes that are for any reason. Future revisions are planned to keep
important in their own right had to be left out of the this series abreast of progress in these fields.
Sina Ebnesajjad July 2004
Authors’ Preface
The first two books in this series dealt with that come in contact with chemicals in factories.
fluoropolymers manufacturing, properties, and Chapters 3 and 4 elaborate on the properties of
fabrication technologies. The aim of the present book fluoropolymers and their selection for various parts.
is to build upon the information in the first two books Chapters 5 and 6 describe processes to convert
to address the use of fluoropolymers in the chemical fluoropolymers into shapes and parts. Chapter 7
processing industry (CPI) and other allied industries. covers the fabrication techniques used to finish the
They include food, pharmaceutical, semiconductor, fluoropolymer shapes/parts. Chapter 8 reviews design
and pulp and paper industries. This book is both a and construction of the basic process components of
reference and a source for learning the basics for those a chemical handling plant. Chapter 9 describes the
involved in the entire product value chains related to operation and maintenance of vessels and tanks.
the chemical industries, from fluoropolymer Chapter 10 provides an approach and material on
producers all the way to the end-users. The reader laboratory techniques that can be applied to determine
will be able to read about how the unique the cause of failure of parts. Chapter 11 offers a
characteristics of fluoroplastics are utilized in the modeling methodology to predict and analyze failure
design and construction of equipment exposed to of fluoropolymer parts, thus allowing design
harsh chemical environments. This book offers improvement. Chapters 12–14 are devoted to the cost
information helpful to engineers, maintenance analysis, safety considerations, and future trends of
personnel, students, material managers, and all others fluoropolymers. The “Glossary,” “Appendixes,”
involved in the chemical processing industries. “Trademarks,” and “Index” sections provide
This book emphasizes the practical over the additional information and tools to facilitate finding
theoretical. There are numerous sources for in-depth information in the book.
study of topics including polymerization and the We have tried to present the data in SI units in
polymer science of fluoropolymers. Some of these most of the book. A large number of parts are,
references have been listed at the end of pertinent however, still specified in English units. In such cases,
chapters, serving as both bibliography and additional conversion factors have been listed in footnotes to
reading sources. Review papers are particularly allow the reader to convert to metric units.
helpful as a starting point for finding additional None of the views or information presented in
sources for concentrated reading in a selected area. this book reflects the opinions of any of the companies
The chapters of this book have been written to or individuals that have contributed to the book. If
allow sequential and independent reference to them. there are errors, they are oversights on the part of the
Chapters 1 and 2 introduce the reader to authors. A note to the publisher indicating the specific
fluoropolymers, fluoroelastomers, and the other error, for the purpose of correcting future editions,
materials of construction used to manufacture parts would be much appreciated.
Sina Ebnesajjad July 2004
Pradip R. Khaladkar
Acknowledgments
We owe the majority of our learning and from Exponent, Inc., for their generosity in
experience in the field of fluoropolymers to our contributing Chapter 11 to this book. This is a better
employment at the DuPont Company. DuPont book because of the contribution of these colleagues
Fluoroproducts and DuPont Engineering Technology who are at the forefront of the science and technology.
have generously contributed to this volume by We have made a great deal of use of data
providing a great deal of the data and research developed and organized by our colleagues and
material, and by supporting literature searches, friends in the DuPont Company, S. A., in Geneva,
securing reference material, and the preparation of Switzerland. We would like to specially acknowledge
the manuscript. We thank the companies that have Dr. Theodore Schroots for data, figures, and tables
provided us with information, photographs, and that he has developed over the last three decades.
illustrations; they have been cited usually in the Mr. Tom Johns from DuPont Information and
captions, and in some cases in the bibliography Computing Technology conducted the literature
section at the end of the chapter. search for this book; we thank Tom and his colleagues
A number of companies have furnished the for the reference material, including articles, books,
authors with information, which has been cited in and patents.
the bibliography section at the end of each chapter. Our sincere thanks go to Mrs. Jeanne Roussel
The following corporations have provided the authors and the Write One staff for converting the raw
with the data in their commercial information manuscript into a real book with care and patience.
bulletins: DuPont, Solexis, Daikin, Dyneon, Asahi Editorial suggestions and support by Ms. Millicent
Glass America, Atofina, Crane Resistoflex, Edlon, Treloar, William Andrew Publishing, have greatly
Dualam, RMB Co., Xomox, RL Industries, upgraded the organization and the text. It would have
Electrochemical Engineering and Manufacturing been impossible for us to complete this project
Company, and Wisconsin Protective Coatings Co. We without the many helpful suggestions and moral
sincerely appreciate the contribution that the data support of William Woishnis, CEO of Plastics Design
supplied by each company have made to this book. Library, at William Andrew Publishing.
Special thanks go to our friend Dr. Lawrence Finally, there are not enough words for the
McKeen, DuPont Fluoropolymer Solutions, for authors to thank their life partners, Ghazale Dastghaib
contributing the powder coating technology section and Shaila Khaladkar, who have provided unlimited
included in Chapter 8. We would like to sincerely encouragement throughout this project.
thank Dr. Jörgen Bergström and Dr. Stewart Brown
Trademarks
Trademark Property of Trademark Property of
Aclar® Allied Signal Corp. Isopar® Exxon Mobile Corp.
Acrysol® Brenntag, N.V. Kalrez® DuPont Co.
Adiprene® Crompton Uniroyal Chemical Kapton® DuPont Co.
Aflas® AGC Chemicals Kevlar® DuPont Co.
Aflon® PFA Asahi Glass Co. Kynar® Atofina Chemicals, Inc.
Aflon® COP Asahi Glass Co. Kynar 500® Atofina Chemicals, Inc
Algoflon® Ausimont Corp. Kynar Flex® Atofina Chemicals, Inc
Autograph® DuPont Co. Mylar® DuPont Co.
Bakelite® Bakelite Corp. Natrosol® Hercules Corp.
Bernex® Bernex Co. Neoflon® Daikin Corp.
Capran® Honeywell Inc. Nomex® DuPont Co.
Cellosolve® Dow Chemical Corp. Nordel® DuPont Co.
Dykor® Whitford Corp. Nucrel® DuPont Co.
Dykor® 800 Whitford Corp. Plastite® Textron Fastening Systems
Polyflon® Daikin Corp.
Dyneon® Dyneon
Polymist® Solexis
EMAWELD® Ashland Specialty
Quantanium® Whitford Corp.
Chemical Co.
Excalibur® Whitfrod Corp. Scotch-Weld® 3M Corp.
Fluon® Asahi Glass Co. Selar® DuPont Co.
Silverstone® DuPont Co.
Fluorocomp® Teleflex Corp.
Silverstone Select® DuPont Co.
Fluoro Etch® Acton Tech.
Silverstone SUPRA® DuPont Co.
Fluorinert® 3M Corp.
Silverstone Xtra® DuPont Co.
Fluoromelt® Asahi Glass Co.
Solef® Solvay Polymers, Inc.
ForaFlon® Atofina Corp.
Stelite® DuPont Co.
Freon® DuPont Co.
Tedlar® DuPont Co.
Freon® 113 DuPont Co.
Teflon® DuPont Co.
Frekote® Frekote Co.
Tefzel® DuPont Co.
Genetron® Allied Signal Corp.
Tetra-Etch® W. L. Gore & Assoc.
Gore-Tex® W. L. Gore & Assoc.
Torlon® Solvay Advanced Polymers
Gore-Tex GR® W. L. Gore & Assoc.
Triton® Dow Chemical Corp.
Gylon® B.F. Goodrich Corp.
Tyvek® DuPont Co.
Halar® Ausimont Corp.
Vespel® DuPont Co.
Hostaflon® Dyneon Corp.
Viton® DuPont Co.
Hyflon® Ausimont Corp.
Whitcon TL® Asahi Glass Co.
Hylar® Ausimont Corp.
Xylan® Whitford Corp.
Hylar 500® Ausimont Corp.
Xylan Plus® Whitford Corp.
Hypalon® DuPont Co.
Table of Contents
1 Introduction to Fluoropolymers..................................................................................................1
1.1 Introduction .............................................................................................................................1
1.2 What are Fluoropolymers?............................................................................................................1
1.3 Fundamental Properties of Fluoropolymers .................................................................................2
1.4 Developmental History of Fluoropolymers..................................................................................3
1.5 Examples of Uses of Fluoropolymers...........................................................................................5
References................................................................................................................................................6
2 Materials of Construction............................................................................................................7
2.1 Introduction .............................................................................................................................7
2.2 Historical Background ..................................................................................................................7
2.3 Definition of Polymer-based Materials ........................................................................................8
2.4 Comparison Between Polymer-based Materials and Metals........................................................8
2.4.1 Position of Fluoropolymers in the Materials Spectrum..................................................10
2.5 Applications of Polymer-based Materials for Corrosion Control..............................................10
2.5.1 Applications of Fluoropolymers for Corrosion Control .................................................10
References..............................................................................................................................................14
3 Properties of Neat (Unfilled) and Filled Fluoropolymers .......................................................15
3.1 Introduction ...........................................................................................................................15
3.2 Influence of Processing on Fluoroplastics..................................................................................15
3.3 Chemical Compatibility of Fluoropolymers...............................................................................15
3.3.1 Chemical Compatibility of Perfluoropolymers...............................................................15
3.3.1.1 Effect of Ozone on Fluoropolymers..................................................................16
3.3.1.2 Oxygen Compatibility of PTFE.........................................................................17
3.3.2 Chemical Compatibility of Partially Fluorinated Fluoropolymers.................................17
3.3.3 Chemical Compatibility of Polychlorotrifluoroethylene ................................................18
3.4 Permeation Fundamentals...........................................................................................................18
3.4.1 Permeation Measurement and Data.................................................................................20
3.5 Environmental Stress Cracking...................................................................................................21
3.6 Properties and Characteristics of PTFE......................................................................................23
3.6.1 Introduction to Filled PTFE Compounds........................................................................23
3.6.1.1 Granular-based Compounds ..............................................................................23
3.6.1.2 Fine Powder-based Compounds........................................................................25
3.6.1.3 Compounding with Engineering Polymers........................................................25
3.6.1.4 Reinforced Gasketing Material..........................................................................26
3.6.1.5 Co-Coagulated Compounds...............................................................................26
3.6.1.6 Fabrication of Parts from Compounds ..............................................................26
3.6.1.7 Typical Properties of Filled Fluoropolymers ....................................................27
3.6.2 Mechanical Properties of PTFE ......................................................................................28
3.6.2.1 Deformation Under Load (Creep) and Cold Flow ............................................35
3.6.2.2 Fatigue Properties..............................................................................................36
3.6.2.3 Impact Strength..................................................................................................36
3.6.2.4 Hardness ............................................................................................................36
3.6.2.5 Friction...............................................................................................................36
xii CONTENTS
3.6.2.6 PV Limit ............................................................................................................47
3.6.2.7 Abrasion and Wear ............................................................................................47
3.6.3 Electrical Properties of PTFE..........................................................................................47
3.6.4 Thermal Behavior of PTFE.............................................................................................47
3.6.4.1 Thermal Stability...............................................................................................47
3.6.4.2 Thermal Expansion............................................................................................51
3.6.4.3 Thermal Conductivity and Heat Capacity.........................................................51
3.6.4.4 Heat Deflection Temperature ............................................................................51
3.6.5 Irradiation Resistance of PTFE .......................................................................................51
3.6.6 Standard Measurement Methods for PTFE.....................................................................52
3.7 Properties and Characteristics of Melt-processible Fluoroplastics............................................55
3.7.1 Mechanical and Dynamic Properties...............................................................................55
3.7.1.1 Tensile Properties ..............................................................................................55
3.7.1.2 Moduli................................................................................................................55
3.7.1.3 Deformation Under Load (Creep) .....................................................................69
3.7.1.4 Poisson’s Ratio ..................................................................................................69
3.7.1.5 Flex Fatigue Properties......................................................................................69
3.7.1.6 Impact Strength..................................................................................................70
3.7.1.7 Hardness ............................................................................................................82
3.7.1.8 Friction, Wear, and Abrasion.............................................................................82
3.7.2 Thermal Properties of Melt-processible Fluoropolymers...............................................86
3.7.2.1 Thermal Stability...............................................................................................86
3.7.2.2 Temperature-related Properties .........................................................................89
3.7.2.3 Thermal Aging...................................................................................................89
3.7.3 Weatherability of Melt-processible Fluoroplastics.........................................................94
3.7.4 Electrical Properties of Melt-processible Fluoroplastics................................................96
3.7.4.1 Perfluoroalkoxy Polymers.................................................................................96
3.7.4.2 FEP.....................................................................................................................98
3.7.4.3 PVDF.................................................................................................................98
3.7.4.4 ETFE................................................................................................................100
3.7.4.5 ECTFE.............................................................................................................100
3.7.5 Optical and Spectral Properties of Melt-processible Fluoroplastics ............................100
3.7.6 Radiation Effect on Melt-processible Fluoroplastics....................................................100
3.7.7 Flammability of Melt-processible Fluoroplastics .........................................................110
3.7.8 Biofilm Formation of Melt-processible Fluoroplastics.................................................110
References............................................................................................................................................112
4 Selecting Fluoropolymers for Corrosion Control..................................................................117
4.1 Introduction .........................................................................................................................117
4.1.1 Corrosion of Metals.......................................................................................................117
4.1.2 Corrosion of Polymer Materials....................................................................................117
4.1.3 Approaches to Selection................................................................................................117
4.2 Economics of Selecting Fluoropolymers..................................................................................118
4.3 Preparing to Determine Compatibility......................................................................................118
4.4 Current Technology for Determining Compatibility................................................................118
4.4.1 Experience .....................................................................................................................118
4.4.2 Manufacturers’ Literature .............................................................................................119
4.4.3 Testing .........................................................................................................................149
4.4.3.1 Coupon Testing................................................................................................149
CONTENTS xiii
4.4.3.2 Simulated Testing ............................................................................................150
4.4.3.3 Special Testing.................................................................................................154
4.4.4 Fabrication Considerations in Materials Selection.......................................................154
4.4.5 Inspection and Maintenance Aspects of Materials Selection .......................................157
References............................................................................................................................................157
5 Manufacturing of Parts from Polytetrafluoroethylene Polymers ........................................161
5.1 Granular Resin Processing........................................................................................................161
5.1.1 Resin Selection..............................................................................................................161
5.1.2 Compression Molding ...................................................................................................162
5.1.2.1 Equipment........................................................................................................162
5.1.2.2 Densification and Sintering Mechanism .........................................................163
5.1.2.3 Billet Molding..................................................................................................164
5.1.3 Automatic Molding........................................................................................................167
5.1.4 Isostatic Molding...........................................................................................................168
5.1.4.1 Introduction to Isostatic Molding....................................................................168
5.1.4.2 Comparison of Isostatic with Other Fabrication Techniques..........................169
5.1.4.3 Wet- and Dry-Bag Isostatic Molding...............................................................170
5.1.5 Ram Extrusion...............................................................................................................170
5.1.5.1 Introduction to Ram Extrusion........................................................................170
5.1.5.2 Ram Extrusion: Basic Technology..................................................................170
5.2 Fine Powder Resin Processing..................................................................................................174
5.2.1 Resin Handling and Storage..........................................................................................174
5.2.2 Paste Extrusion Fundamentals.......................................................................................175
5.2.3 Extrusion Aid or Lubricant............................................................................................176
5.2.4 Wire Coating..................................................................................................................176
5.2.4.1 Blending the Resin with Lubricant..................................................................176
5.2.4.2 Preforming.......................................................................................................176
5.2.4.3 Extrusion Equipment and Process...................................................................177
5.2.5 Extrusion of Tubing.......................................................................................................178
5.2.5.1 Spaghetti Tubing..............................................................................................178
5.2.6 Pressure Hoses...............................................................................................................178
5.2.6.1 Blending Lubricant and Pigment and Preforming...........................................183
5.2.6.2 Extrusion Process for Pressure Hoses.............................................................183
5.2.6.3 Quality Control of Pressure Hoses..................................................................183
5.2.7 Unsintered Tape.............................................................................................................185
5.3 Fluoropolymer Dispersion Processing......................................................................................185
5.3.1 Dispersion Applications ................................................................................................186
5.3.2 Storage and Handling of Dispersions............................................................................186
5.3.3 Dispersion Formulation and Characteristics.................................................................187
5.3.3.1 Formulation......................................................................................................188
5.3.4 Glass Cloth Coating by Dispersion...............................................................................188
5.3.4.1 Equipment........................................................................................................189
5.3.4.2 Processing........................................................................................................189
5.3.5 Dispersion Impregnation of Flax and Polyaramide.......................................................191
5.3.5.1 Processing........................................................................................................191
5.3.6 Coating Metal and Hard Surfaces with Dispersion.......................................................191
References............................................................................................................................................192
