Introduction to Fluoropolymers: Materials, Technology and Applications

Introduction

The original idea for a series of handbooks about fluoropolymers and fluorocarbons was conceived in the mid-1990s. Two powerful reasons compelled the development of these books. First, there were no definitive sources for the study of fluorinated polymers, particularly the commercial products. A researcher seeking the properties and characteristics of fluorinated plastics did not have a single source to use as a reference. Information available from commercial manufacturers of polymers had long been the sources of choice. Second, waves of the post-war generation (a.k.a. Baby Boomers) were beginning to retire, thus eroding the available reservoirs of knowledge in the industry and in the academia.

A broad scope has been maintained for the series to include as many fluorinated materials as possible. The topics of the books were selected based on the readers’ needs. Inevitably, a number of fluorinated compounds, important in their own right, have been left out of the series usually because the audience was too small to meet the economic hurdles of publishing.

Over the years an added consideration arose which was the need for use of fluoropolymers by many technically trained individuals in diverse fields who are often not fluoropolymer or plastic experts. The generational changes require the training of a new generation of people in plastics including fluoropolymers. The relatively small volume of fluoropolymers has resulted in the engagement of few people in the field thus weakening the continuity of knowledge base.

This book includes a collection of chapters about various fluoropolymers which offer a great deal information about a number of subjects. The book is intended to serve those who wish to begin to learn about fluoropolymers and enter the field. It presents the fluoropolymers history, products and technology without engaging in highly technical coverage or discussing subject matters in great details.

This book is expected to be suitable for beginners and others who wish to learn about the technology, applications and history of fluoropolymers. The history sections are expected to provide lighter reading for the newly graduated individuals as an easy entry point.

I would like to sincerely thank the contributors to this book who are world class experts in their fields: J. Drobny (fluoroelastomers), W. Grot (fluorinated ionomers) and L. W. McKeen (fluorinated finishes and coatings).

I am indebted to Matthew Deans, the Senior Publisher of William Andrew, for his leadership and invaluable support. Thanks to Matthew’s wisdom and guidance Plastics Design Library continues to grow in both the number of titles and the breadth of subject matters it offers. The support provided by Miss Lisa Jones, Production Manager, for the preparation of the manuscript for production and the publication of the book was invaluable and is most appreciated.

Sina Ebnesajjad

April 2013

1

Fluorine, Fluorocarbons, and Fluoropolymers in Human Life

A Day with the Smiths

A review of a day in the life of Mr. and Mrs. Smith who live in Tucson, Arizona, will illustrate the essential role of fluorine, fluorocarbons, and fluoropolymers in society.

Mr. Smith begins the day shaving using a fancy razor, which has a strip of polytetrafluoroethylene (PTFE) fluoropolymer as a part of the safe design of this razor. Taking eggs out of a refrigerator kept cool with a fluorocarbon refrigerant hidden inside its compressor, Mr. Smith makes an omelet for breakfast. He uses a nonstick pan to cook; the pan is nonstick because of the fluoropolymer coating on its surface.

After breakfast, everyone in the family flosses using floss made from PTFE fluoropolymer that does not scar gums. Then everyone brushes using toothpaste that contains fluoride to protect the teeth. Fluorine compounds are added to the toothpaste to help prevent tooth decay. Pain, loss of teeth, gum disease, and disfigurement associated with tooth decay have been reduced since the introduction of fluoridation more than 60 years ago.

Numerous studies since 1945 have illustrated the impact of community water fluoridation in the prevention of tooth decay [1]. For example, in 1993, the results of 113 studies in 23 countries were compiled and analyzed [2]. (Fifty-nine out of the 113 studies analyzed were conducted in the United States.) This review provided effectiveness data for 66 studies in primary teeth and for 86 studies in permanent teeth. Taken together, the most frequently reported decay reductions observed were:

• 40%–49% for primary teeth (or baby teeth)

• 50%–59% for permanent teeth (or adult teeth)

Mrs. Smith is dressing the children. Rain is in the forecast, so to stay dry, the children dress in waterproof coats that have an expanded PTFE fluoropolymer fabric inside them best known as Gore-Tex® (by W.L. Gore and Associates). These coats keep the water out but breathe, keeping the children cool. A similar material is used in modern hospitals.

The couple is pressed for time, so they leave the food spilled on the carpet for cleanup after work because a very thin layer of fluorocarbon protects the carpet. They pick up their cell phones and laptop computers on their way out of the house. Every one of these devices contains coaxial cables that contain insulation made from fluoropolymers and components, which depend on the unique dielectric properties of PTFE. The modern electronics age has depended on fluoropolymers. The silicon chips are made using fluorine-containing gases for etching and chamber cleaning.

Mrs. Smith takes her son’s asthma drug along to school. A fluorinated chemical enables safe delivery-metered doses of the asthma medicine out of the metal container. A thin layer of fluoropolymer coats the inside of the metal container to prevent the drug from sticking to the surface. The metered-dose inhaler, as it is called, allows the drug to be administered in a targeted and precise form. This keeps the child’s exposure limited to the required amount of the asthma drug.

Because of its unique chemical properties, fluorine has been instrumental in the development of novel medicines. Approximately 25% of all marketed drugs contain fluorine, including three of the 10 best-selling drugs in 2011 [3]. Fluorine-enhanced compounds have better pharmaceutical properties, some of which are listed here:

Potency: Improved efficacy and therapeutic window

Selectivity: Fewer side effects

Tissue penetration: Enhanced drug delivery to target

Drug half-life: Less frequent dosing

Metabolism: Reduced drug interactions

Mr. Smith, who is the last to leave the house, turns off the fluorine-containing displays on his desktop computer and television. Last, he sets the thermostat to reduce the air conditioning operation while the house is empty. The central air unit in the house contains a fluorocarbon refrigerant called hydrofluorocarbon (HFC). This material complies with Montreal Protocol by having unique stability and reduced global warming potential. It also helps the air conditioning work efficiently. Tragic events occurred in France in the summer of 2003, when nearly 15,000 people died because of the heat and absence of air conditioning in many homes and buildings. It is well accepted by the medical profession that air conditioning saves lives. Modern hospitals, even in temperate zones, air-condition their facilities.

There are negative environmental impacts resulting from air conditioning, however. Some of these have been corrected, and others will be corrected by additional inventions. The fluorocarbon and fluoropolymer industries have been working for a long time to lower the negative effects of these products on the environment and on global warming.

The Smiths’ house is partially powered by photovoltaic cells that the family installed several years ago. Using these cells is a good deal because after the family paid for the installation of the cells, they have been enjoying free power for some of the family’s electric needs. A special fluoropolymer called polyvinyl fluoride (PVF) plays an important role in photovoltaic units by protecting them from damage and increasing their useful life.

The power plants that supply the rest of the house’s electricity have many fluorocarbon-based components, which help reduce carbon dioxide and other emissions. For example, fluoropolymer-coated bag filters remove harmful particles (fly ash) from the smoke discharged by coal-burning plants. There would be a huge decrease in particulate emissions if every coal-burning plant in the world installed fluoropolymer-coated bag filters.

Before leaving, Mr. Smith looks at the house, admiring the landscaping and the crisp-looking aluminum siding and steel roof that still look as bright and clean as they did 10 years ago. What is great is that he has not had to do a thing to keep the exterior looking good! Both the siding and roof are coated with a paint made with a fluoropolymer called polyvinylidene fluoride (PVDF). This paint endures all the elements of climate, is maintenance free, and is expected to last 30 years.

Later, Mr. Smith will travel on an aircraft that is equipped with fluorocarbon fire extinguishers in its cargo compartment to prevent passive fires started by phantom sparks. The many miles of wires and cables in the aircraft are insulated by fluoropolymers or composite materials that contain fluoropolymers. They allow safe performance of the electrical and signal systems of the aircraft over its lifetime. Mr. Smith may not realize that the interior of the aircraft is surfaced by a composite of fluoropolymer PVF, which is fire safe, durable, and stands up to the harsh cleaning chemicals and disinfectants.

Mrs. Smith’s 76-year-old mother is recovering from an operation in which parts of her arteries were replaced by vascular grafts made from expanded polytetrafluoroethylene (ePTFE) material. She suffered no pain during the operation and had a normal anesthetic experience thanks to the use of a fluorocarbon gas. Mrs. Smith’s mother has been given an excellent prognosis for recovering from the surgery and is adapting well to her new ePTFE veins. She will never know that the anesthesia from which she recovered was a fluorocarbon gas, but she will go on with her active life and enjoy her grandchildren for a long time.

In 1951, Dr. Charles Suckling began attempting to prepare the ideal anesthetic gas, which resulted in the clinical introduction of fluorocarbons with names such as halothane, enflurane, isoflurane, desflurane, sevoflurane, and methoxyflurane. Every year, more than 25 million surgical procedures are performed in the United States, most of which require general inhalation anesthetic. Fluorocarbon compounds such as Sevoflurane® and Isoflurane® have drastically reduced the long-standing anesthesia risk of using anesthesia.

Since the 1990s, decade estimates for the number of deaths attributed to anesthesia have dropped greater than 25-fold from 1 in 10,000 anesthetics to 1 in 200,000 to 1 in 300,000 today [4]. Today, surgeons save lives thanks to safe fluorocarbon anesthetics pioneered by Charles Suckling.

There are many more similar everyday life examples of the use of fluorocarbons that save lives and enhance the quality of human life. More exotic examples include parts in spacecrafts from the early days to the Space Shuttle to the International Space Station. Fluorocarbons, whether chemicals or plastics, are invisible and often go unnoticed. The reason is that they are inside the systems that have enabled today’s societal human standards.

Out of sight, out of mind! This metaphor taken to extreme may narrow the focus to the challenges of fluorocarbons without placing due weight on their critical roles in human life. The fluorocarbon and fluoropolymer industries and governments have been working voluntarily for decades on reducing the negative impact of these products on the environment, on global warming, and on human health. They will continue as they should, but because of the importance of these compounds.

References

1. American Dental Association, Fluoridation Facts. 2005; In: www.ADA.org; 2005.

2. Murray JJ. Efficacy of preventive agents for dental caries. Caries Res. 1993;27(Suppl. Q):2–8.

3. www.Scifluor.com, 2003.

4. American Society of Anesthesiologists, History of Anesthesiology—An Overview. 2003; In: http://asatest.asahq.org/Newsletters/2000/09_00/asaLeadership0900.html; 2003.

2

Fluorine and Fluorocarbons

Chapter Outline

2.1 Uniqueness of Fluorine

2.2 Fluorine Characteristics

2.2.1 Fluorination

2.2.2 Reactivity: An Extreme Element

2.2.3 Preparation of Fluorine

2.2.4 Inorganic Chemistry

2.2.5 Organic Chemistry

2.2.6 Fluorine and Nature

References

What sets fluorine apart from other halogens? Technically speaking, the term halogen provides little descriptive value in scientific and technological discussions. The common characteristic of halogens is that they all have seven electrons in the outer shell of their atomic structure. They all have a valence of –1 in their reactions with hydrogen and metals. The reactivity of halogens decreases from the top (fluorine) to the bottom (astatine) of Group 17 in the Periodic Table of Elements. When fluorine is substituted for any element such as hydrogen in a chemical structure, it will have a profound impact on the compound’s properties, because fluorine is the most reactive of all elements [1]. It has a perfect electronegativity of 4, which is the maximum value of the Pauling scale (0.7–3.98, dimensionless). Even platinum is not immune to fluorine and reacts with F2 gas and forms platinum hexafluoride.

2.1 Uniqueness of Fluorine

Fluorine forms an extremely strong bond with other elements such as carbon because it is the most electronegative of all elements. The carbon–fluorine bond (C–F) is the fundamental reason that polytetrafluoroethylene (PTFE) is one of the most stable and inert plastics known to man. Yet tetrafluoroethylene (TFE) is highly explosive, adding to the diversity of the fluorine effect. A key point is made in the McGraw-Hill Encyclopedia of Chemistry about the stability of halogenated compounds: Organic halogen compounds generally show progressively increased stability in the order iodine, bromine, chlorine and fluorine [2].

It is clear that fluorine is a special element beyond all others. It is relatively easy to substitute fluorine for hydrogen (and other elements) in organic compounds because of its extreme affinity for grabbing electrons. Substituting fluorine for hydrogen in a chemical compound gives rise to a variety of unique and useful effects. Examples include increased polarity, decreased polarity, chemical activity, chemical neutrality, increased biological activity for pharmaceuticals and agro chemicals, greater thermal and oxidative stability, and increased chemical resistance.

An interesting example is fluorination of polyolefin film surface. Slight fluorination renders the neutral surface of a polyolefin film polar. Further increases in the fluorine content of the surface result in total neutrality of the film surface. In practice, slight fluorination of polyolefin surfaces is used to make them adherable. The inside surfaces of plastic pesticide and herbicide bottles are fluorinated extensively to prevent permeation of the agents, which could result in loss of material and unsafe conditions. Sometimes fluorine is mixed with blow molding gas in order to combine the bottle fabrication and fluorination steps.

A number of partially and fully fluorinated polymers have been developed because of the unique effect of fluorine on their properties. Some of the common polymer chemistries include polyolefins, fluorinated elastomers, polymethyl siloxane, acrylic and methacrylic polymers, and perfluorether polymers. The impact of increasing the fluorine content of olefinic polymers on their properties is shown in Table 2.1.

Table 2.1

Effect of Increase in Fluorine Content of Polymers

One can simply conclude that fluorinated compounds have varied and unusual properties, a number of which are quite useful to the development of commercial materials for a broad range of applications including plastics, electronics, agriculture, pharmaceuticals, and medicine.

2.2 Fluorine Characteristics

Fluorine ranks 13th in abundance among the earth’s rocks, present at an average concentration of 0.1% by weight [3]. Fluorine abundance is 0.08% compared to 0.05% in the earth’s lithosphere [4]. Fluorine is considered the most dominant halogen when the whole earth is considered.

The most abundant natural sources of fluorine are fluorspar (CaF2) and cryolith (also called cryolite; Na3AlF6). Teeth enamel is very hard, is mechanically strong, and has long-term durability, mainly because of fluoroapatite [Ca5(PO4)3F or 3Ca3(PO4)2.CaF2], along with hydroxyapatite being its major components. Fluoride is considered a trace element because only small amounts are present in the body (about 2.6 grams in adults), and because the daily requirement for maintaining dental health is only a few milligrams a day. About 95% of the total body fluoride is found in bones and teeth. Fluoride’s primary function in the human body is to strengthen the bone, and it is known to prevent tooth decay. Experts contend that fluoride strengthens the teeth’s enamel by strengthening the mineral composition of the teeth themselves [5, 6].

About 40% of fluorspar [3] is used as metallurgical flux in the steel industry, some of which is recovered as synthetic fluorspar. The highest grade of fluorspar (>97% CaF2) is reacted with sulfuric acid for the production of hydrogen fluoride (HF), which is the starting point of organic fluorinated compounds. Some fluorspar is consumed in uranium processing, petroleum alkylation, and stainless steel pickling [7].