Fluoroplastics, Volume 2

Melt Processible Fluoropolymers - The Definitive User's Guide and Data Book

Sina Ebnesajjad

• Publisher: William Andrew
• Year: 2015
• eBook ISBN: 9781455731985
• Edition: 2
• Topic: Technology & Engineering
• Subtopic: Materials Science
• Index: Technology & Engineering

Fluoroplastics, Volume 2: Melt Processible Fluoropolymers - The Definitive User's Guide and Data Book compiles the working knowledge of the polymer chemistry and physics of melt processible fluoropolymers with detailed descriptions of commercial processing methods, material properties, fabrication and handling information, technologies, and applications, also including history, market statistics, and safety and recycling aspects.Both volumes of Fluoroplastics contain a large amount of specific property data useful for users to readily compare different materials and align material structure with end use applications.Volume Two concentrates on melt-processible fluoropolymers used across a broad range of industries, including automotive, aerospace, electronic, food, beverage, oil/gas, and medical devices.This new edition is a thoroughly updated and significantly expanded revision covering new technologies and applications, and addressing the changes that have taken place in the fluoropolymer markets.- Exceptionally broad and comprehensive coverage of melt processible fluoropolymers processing and applications- Provides a practical approach, written by long-standing authorities in the fluoropolymers industry- Thoroughly updated and significantly expanded revision covering new technologies and applications, and addressing the changes that have taken place in the fluoropolymer markets

1

Introduction to Fluoropolymers

Abstract

A magnificent chapter in the creation and production of polymers involves the discovery of fluoropolymers. Those who may not know that story have most likely heard of Teflon^®, the trademark of fluoropolymers by DuPont. Teflon^® is said to be one of the 10 most known trademarks in the world. The classic story of discovery of fluoropolymers is replete with the magical combination of brilliance and serendipity. The environment and the context in which the discovery occurred, however, often goes overlooked. This chapter attempts to place the invaluable discovery made by Roy Plunkett in the context of its times, events, and the personalities. Plunkett's finding is even more impressive, if at all possible, when viewed through the prism of context.

Keywords

Fluoropolymers; Globalization; Polytetrafluoroethylene; Polyvinyl fluoride; Supercritical carbon dioxide

A magnificent chapter in the creation and production of polymers involves the discovery of fluoropolymers. Those who may not know that story have most likely heard of Teflon^®, the trademark of fluoropolymers by DuPont. Teflon^® is said to be one of the 10 most known trademarks in the world. The classic story of discovery of fluoropolymers is replete with the magical combination of brilliance and serendipity. The environment and the context in which the discovery occurred, however, often goes overlooked. This chapter attempts to place the invaluable discovery made by Roy Plunkett [1] in the context of its times, events, and the personalities. Plunkett's finding is even more impressive, if at all possible, when viewed through the prism of context.

For those who wish to know the ending of the story, let us begin there. By 1938, Roy Plunkett, a young scientist had been employed at DuPont Company for 2 years, researching the new fluorinated refrigerants. This family of chemicals was of interest because they were not only safer than the old gases but also nonflammable, nontoxic, colorless, and odorless. Accidents involving ammonia as refrigerant were commonplace at that time.

Plunkett was attempting to react tetrafluoroethylene with hydrochloric acid (HCl) to synthesize 1,2-dichloro-1,1,2,2-tetrafluoroethane (CClF₂-CHF₂) intended for evaluation as a refrigerant^. [2] As on many other occasions, on the morning of April 6, 1938, Plunkett checked the pressure on a full cylinder of TFE. He found no pressure though the weight of the cylinder was the same as the day before. Plunkett and his technician Jack Rebok removed the valve carefully and shook the cylinder upside down. A small amount of a slippery white substance fell out. They recovered more white powder after cutting open the gas cylinder. The waxy powder was analyzed and found to be polytetrafluoroethylene (PTFE), later trademarked as Teflon^® by the DuPont Company. The rest is, of course, history.

1.1. Coming of Age of Polymer Science

Global economic depression and war in Europe by the decade's end have retrospectively defined the 1930s as a period of tumult and difficulty for most strata of society. Yet these were among the best of times for the emerging field of polymer science. Scientists were driven to find new materials to meet the needs of new technologies, population growth, and to raise living standards through innovation. The giants of polymer science made important strides toward those goals. Many polymer scientists of the period were later recognized for their contributions to the field. The sentiment was somewhat similar to that in the field of genomics in the early twenty-first century.

Working on polymers during the late 1930s must have been an exciting endeavor. Following nearly a century of little technical progress, the field of polymer science was taking shape at academic and industrial centers. Opponents and proponents of various theories on polymers debated heatedly over the finer points of their beliefs at technical meetings. Among the debaters were Herman Mark, Karl Meyer, and Herman Staudinger, who argued passionately about the principles of polymer science. Participants eventually consented to the validity of Staudinger's and Carothers' hypothesis: Polymers are not aggregated collections of small molecules but long chains of small molecules linked by covalent bonding.

Mark, Meyer, and Staudinger's careers flourished. Meyer stated the rubber-like elasticity theory in 1932. Staudinger published his influential book Die hochmolekularen organischen Verbindungen, Kautschak und Cellulose (The high-molecular organic compounds, rubber and cellulose), published by Springer, Berlin, 1932. He received the Nobel Prize for chemistry in 1953. Herman Franz Mark and Karl Heinrich Meyer published Hochpolymere Chemie in 1940 (Natural and Synthetic High Polymers, 1942). You may have heard of Mark–Houwink equation and the pioneering work of Professor Herman Mark at the Polytechnic University in Brooklyn, New York, and elsewhere.

Roy Plunkett's roommate in Manchester College was none other than Paul Flory, who did not do too badly in polymer science. Paul joined DuPont 2 years before Roy in 1934. He worked for Wallace Carothers, the inventor of nylon and neoprene, in the nascent field of synthetic macromolecules when Roy joined DuPont.

Shortly thereafter, the circle of Roy Plunkett's contemporaries scattered as Europe imploded by the events that presaged World War II. Wallace Carothers, the gifted Harvard Chemist who had been wooed to DuPont to partake in pioneering research, died prematurely in 1937. He did not share the 1953 chemistry Nobel Prize with Staudinger because the prize was not awarded posthumously. He not only invented nylon and neoprene but also advanced the field of polymer science with his theories on the structure of polymers.

Roy Plunkett's roommate, Paul Flory, left DuPont in 1938 for the University of Cincinnati and later worked for Exxon Corporation, Goodyear Tire and Rubber Company, Cornell University, Mellon Institute, and Stanford University. Paul Flory, an Illinois native and the son of a clergyman, was awarded the Nobel Prize for chemistry in 1974. His 1953 masterpiece, Principles of Polymer Science, is still consulted by researchers.

1.2. Roy Plunkett's Story

Roy came from a poor farm family in New Carlisle, Ohio. He attended Manchester College in North Manchester, Indiana as the Great Depression began. Roy shared a room with an older student named Paul Flory. Roy graduated with a Bachelor of Arts in chemistry in 1932 and followed Paul to graduate school at the Ohio State University. Roy and Paul both earned masters and PhD degrees from the Ohio State University within 2 years of one another. Roy joined the DuPont Central Research in 1936 where Paul had been working since 1934.

Roy Plunkett was moved to Kinetic Chemical Co., a joint venture that DuPont and General Motors (GM) had set up to produce safe refrigerants. The goal was to replace ammonia and sulfur dioxide gases because of the toxicity and flammability in addition to poor efficiency of those gases. Roy was given a laboratory in DuPont's Jackson Laboratory on the shores of the Delaware River in Deep Water, New Jersey. Roy's laboratory was located across the hall from Charlie, who was a young chemist and had a strong interest in synthesizing new organic compounds. Roy was trying to expand the line of fluorocarbons known as Freon^® in anticipation of the sharp growth of air-conditioned automobile production at GM.

On April 6, 1938, the day Roy Plunkett found the TFE cylinder without pressure, a small commotion erupted in his lab. What was this slippery white powder? How was it formed? He had the opportunity and the cognizance to pause to ask questions; there was no relentless pressure to meet next month's deadline because people understood success in research needed a reasonably low-stress work environment.

Charlie went to Roy's lab when he heard the racket that the occupants were making. He later said, “On another occasion, at Jackson Laboratory, across the Delaware River in New Jersey where I worked, I noticed commotion in the laboratory of Roy Plunkett, which was across the hall from my own. I investigated and witnessed the sawing open of a cylinder from which was obtained the first sample of Teflon^® fluoropolymer.” These words have been taken from Charlie Pederson's 1987 Nobel Lecture. You see Charlie invented new crown ether compounds and was awarded the Nobel Prize for his contribution in 1987.

Roy Plunkett lived in heady times. Before long after his 1938 discovery the world was engulfed in the bloodiest battles ever fought in human history. World War II was loo...

Table of contents

• Cover image
• Title page
• Table of Contents
• Series Page
• Copyright
• Dedication
• Preface to Second Edition
• Acknowledgments to Second Edition
• 1. Introduction to Fluoropolymers
• 2. Production and Market Statistics
• 3. From Fundamentals to Applications
• 4. Fluoropolymers: Properties and Structure
• 5. Operational Classification of Fluoropolymers
• 6. Preparation and Properties of Fluorinated Monomers
• 7. Polymerization Surfactants
• 8. Polymerization and Finishing Melt-Processible Fluoropolymers
• 9. Commercial Grades of Melt-Processible Fluoropolymers
• 10. Injection Molding
• 11. Extrusion
• 12. Rotational Molding and Linings
• 13. Other Molding Techniques
• 14. Fluoropolymer Foams
• 15. Chemical Properties of Fluoropolymers
• 16. Properties of Fluoropolymers
• 17. Surface Treatment of Fluoropolymers for Adhesion
• 18. Fabrication of Fluoropolymers
• 19. Applications in Microelectronics Industry
• 20. Applications of Fluoropolymers
• 21. Safety, Health, Environmental, Disposal, and Recycling
• Glossary
• Index