TEFLON

Submitted by: Moin

M.Mansoor
M.Sc (Previous)

Submitted to: Madam Suraiya Subject: Toxicology Dated: 26 Nov 2012

Institute of Environmental Science University of Karachi

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TEFLON
HISTORY:
The story of PTFE began April 6, 1938, at DuPont's Jackson Laboratory in New Jersey. DuPont chemist, Dr. Roy J. Plunkett, was working with gases related to Freon refrigerants, another DuPont product. Upon checking a frozen, compressed sample of tetrafluoroethylene, he and his associates discovered that the sample had polymerized spontaneously into a white, waxy solid to form polytetrafluoroethylene (PTFE). The Teflon trademark was coined by DuPont and registered in 1945; the first products were sold commercially under the trademark beginning in 1946. The invention of PTFE has been described as "an example of serendipity, a flash of genius, a lucky accident...even a mixture of all three". Whatever the exact circumstances of the discovery, one thing is certain: PTFE revolutionized the plastics industry and, in turn, gave birth to limitless applications of benefit to mankind.

INTRODUCTION:
Polytetrafluoroethylene (PTFE) is synthetic fluoropolymer of tetrafluoroethylene that finds numerous applications. PTFE is most well known by the DuPont brand name Teflon. PTFE is a fluorocarbon solid, as it is a high-molecular-weight compound consisting wholly of carbon and fluorine. PTFE is hydrophobic.

PROPERTIES:
A trademark used for a waxy, opaque material, polytetrafluoroethylene, employed as a coating on cooking utensils and in industrial applications to prevent sticking. A tough, insoluble polymer used in making nonstick coatings, as for cookware, and in gaskets, bearings, electrical insulators, etc. A plastic that is very smooth and does not react chemically with other substances. It is used in industry and as a surface for cooking pans so that food does not stick to the pan. PTFE is inert to virtually all chemicals and is considered the most slippery material in existence. These properties have made it one of the most valuable and versatile technologies ever invented, contributing to significant advancements in areas such as aerospace, communications, electronics, industrial processes and architecture. PTFE has become a familiar household product, recognized worldwide for the superior non-stick properties associated with its use as a coating on cookware and as a soil and stain repellant for fabrics and textile products.

SOURCES OF TEFLON:
By using nonstick coatings, as for cookware, and in gaskets, bearings, electrical insulators, etc. By using plastic that is very smooth and does not react chemically with other substances. This is used in industry and as a surface for cooking pans so that food does not stick to the pan.

ABSORPTION:
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When PTFE is absorbed through inhalation or ingestion, some of it binds to proteins in the blood, and it can also accumulate in organs such as the Liver and kidneys. PTFE is found in environmental and biological fluids as the anion perfluorooctanoate. PTFE is absorbed from ingestion and can penetrate skin. The oxygens on PTFE are how it binds proteins with fatty acid or hormone substrates such as serum albumin, liver fatty acid-binding protein, and the nuclear receptors and possibly CAR. In animals, PTFE is mainly present in the liver, blood, and kidneys. PTFE does not accumulate in fat tissue, unlike traditional organ halogen persistent organic pollutants. In humans, PTFE has an average elimination half-life of about 3 years. Because of this long half-life, PTFE has the potential to bioaccumulation.

DISTRIBUTION:
Distribution is the process whereby an absorbed PTFE moves away from the site of absorption to other areas of the body. When PTFE is absorbed it passes through cell linings of the absorbing organ (skin, lung, or gastrointestinal tract) into the interstitial fluid (fluid surrounding cells) of that organ. Interstitial fluid represents about 15% of the total body weight. The other body fluids are the intracellular fluid (fluid inside cells), about 40% of the total body weight and blood plasma which accounts for about 8% of the body weight. However, the body fluids are not isolated but represent one large pool. The interstitial and intracellular fluids, in contrast to fast-moving blood, remain in place with certain components (e.g., water and electrolytes) moving slowly into and out of cells. PTFE while immersed in the interstitial fluid is not mechanically transported as it is in blood. PTFE can leave the interstitial fluid by:

entering local tissue cells entering blood capillaries and the blood circulatory system entering the lymphatic system

If PTFE enters into the blood plasma, it travels along with the blood, either in a bound or unbound form. Blood moves rapidly through the body via the cardiovascular circulatory system. In contrast, lymph moves slowly through the lymphatic system. The major distribution of

absorbed PTFE is by blood with only minor distribution by lymph. Since virtually all tissues have a blood supply, all organs and tissues of the body are potentially exposed to the absorbed PTFE.

METABOLISM:
The detoxification process is an elaborate mechanism conducted chiefly by the liver to eliminate both exogenous and endogenous toxins. The liver participates in the detoxification process, largely by the action of two sequential steps referred to as Phase I and Phase II systems. Phase I reactions involve blood filtration, bile excretion, and the interaction of enzymatic processes acting upon the toxin. Bile excretion is most efficient, in regard to the detoxification process, if adequate amounts of dietary fiber are simultaneously available to escort the toxin from the intestines. Ideally, Phase I and Phase II detoxification mechanisms work synergistically. If Phase I detoxification is highly active and Phase II detoxification is lethargic, the individual is referred to as a "pathological detoxifier," a condition which increases sensitivities to environmental poisons.

EXCRETION:
The process of excretion is basically the same as that of absorption, transfer of chemicals across biological membranes according to chemical concentration gradients; the chemicals move from compartments of high concentration to compartments of low concentration. The removal of PTFE from the body is through excretion, and this process is usually accomplished by specific action of the kidney (formation of urine), liver (Formation of bile), and lung (exhalation of volatile compounds).

TEFLON OFFGAS PRODUCTS:

The toxic particles and gases identified as Teflon off gas products, these are described below:

464F - Ultra fine particulate matter: Teflon

produces very small (ultra fine) particles which are very toxic, causing extreme lung damage to rats within 10 minutes of exposure. Longer exposures cause death. At higher temperatures, Teflon also produces toxic gases. Some scientists have found that the particles and gases together are responsible for Teflon's toxicity, perhaps because the gases adsorb to the particles, which because of their small size can lodge deep in the lower respiratory tract.

680F - Tetrafluoroethylene (TFE): The

National Toxicology Program considers tetrafluoroethylene (TFE) to be a "reasonably anticipated" human carcinogen because it is known to cause cancer in laboratory animals, but has not been adequately studied in people. In rats, inhaled TFE causes tumors of the kidney tubules, liver, blood vessels in the liver and one form of leukemia (mononuclear). Mice that breathe TFE develop tumors of the liver and tumors that develop in blood vessels in the liver or white blood cells.

680F - Hexafluoropropene (HFP): In

people, air exposure to fluorocarbons like HFP can lead to eye, nose and throat irritation; heart palpitations, irregular heart rate, headaches, light-headedness, fluid accumulation in the lung (edema) and possibly death. Long-term exposure in workers is associated with decreased motor speed, memory and learning. In mice and rats, inhalation of hexafluoropropene (HFP) causes kidney lesions, decreased numbers of a type of immune cell (lymphocyte) and increased urination. HFP also causes increased numbers of chromosomal abnormalities in hamster ovaries.

680F - Trifluoroacetic acid (TFA):

Very few studies have looked at the toxicity of trifluoroacetic acid (TFA), but those that have found decreased growth of fetal rat boneforming cells (osteoblast) and cartilage cells (chondrocytes), and neural tube defects in rat embryos at high concentrations. A monkey study found the TFA concentration in the fetus was two to six times higher than in the mother's blood following dosing 6

with HCFC-123. The long-term environmental impacts of TFA are unknown, but it is extremely persistent and toxic to plants. TFA is also a breakdown product of many hydro chlorofluorocarbons (HCFCs) and hydro fluorocarbons (HFCs) used as replacement for chlorofluorocarbons (CFCs), which are potent ozone depletes used in refrigeration systems, aerosols and other products. Recently, scientists have suggested that high levels of TFA in the environment could be partly due to heated Teflon and other fluoropolymers because measured environmental levels are higher than predicted, based on breakdown of HCFCs and HFCs alone.

680F - Difluoroacetic acid (DFA): Very

little is known about the toxicity of difluoroacetic acid (DFA), although kidney toxicity has been reported in rats.

680F - Monofluoroacetic acid (MFA, fluoroacetic acid or compound 1080): Monofluoroacetic acid is extremely toxic, doses as low
as 0.7 to 2.1 mg/kg can kill people. Initially, people report nausea, vomiting, numbness, tingling, anxiety, muscle twitching, low blood pressure and blurred vision. If exposure is high enough, people can have irregular heart rate (ventricular fibrillation), heart attacks, and severe convulsions leading to respiratory failure. MFA quickly breaks down into a chemical called fluoroacetate. Sodium fluoroacetate was previously used as a powerful rodent killer (rodenticide). In the body, it breaks down into sodium and fluoroacetate, which is responsible for the toxicity. Sodium fluoroacetate kills rodents, and other animals, by inhibiting the tricarboxylic acid cycle which transforms energy found in food to energy the body uses. Sodium fluoroacetate also causes heart and respiratory failure, central nervous system depression and damage to the testes, including decreased sperm production.

680F Perfluorooctanoic acid (PFOA): Perfluorooctanoic acid (PFOA) has recently come
under significant EPA scrutiny. According to Stephen L. Johnson, Assistant Administrator of EPA's Office of Prevention, Pesticides, and Toxic Substances, the EPA" will be conducting its most extensive scientific assessment ever undertaken on this type of chemical". EPA is concerned about PFOA because it never breaks down in the environment, is found in the blood of over 92 percent of Americans, and is very toxic to rats and 7

monkeys. PFOA causes four types of tumors in rats: liver, pancreas, mammary gland (breast) and testes. PFOA also decreases thyroid hormone levels, a known risk factor for impaired brain development, and delays sexual maturation in laboratory animals. PFOA is especially toxic to the young because it kills young rats at doses that do not kill parental animals. Industry scientists estimate that it takes 4.4 years for people to eliminate just half the amount of PFOA found in their bodies. EPA is taking a close look at PFOA levels found in the blood of people are too close to levels in rat blood that harm the animals.

878F - Silicon tetra fluoride (SiF4):

Silicon tetra fluoride is a highly toxic, corrosive gas. In the lungs, moisture causes the silicon particles to separate, releasing toxic hydrofluoric acid and also coating the lung with silicon particles. Inhaling hydrofluoric acid can cause eye and throat irritation, cough, difficult breathing, bluish skin color caused by lack of oxygen, lung damage and fluid accumulation in the lung (edema). Long term exposure can cause weight loss, decreased numbers of red and white blood cells (anemia and leucopenia), discoloration of the teeth and abnormal thickening of the bone (osteosclerosis).

887F Perfluoroisobutene (PFIB): Perfluoroisobutene (PFIB) is extremely toxic and

inhalation can lead to fluid build up in the lung (edema), a condition that can lead to death. PFIB is listed in the Chemical Weapons Convention as a Schedule 2 compound. PFIB is about ten times more toxic than phosgene, a highly toxic corrosive gas also listed as a chemical weapon. In water, PFIB breaks down into hydrogen fluoride which is also very toxic (see below). Shortterm symptoms of PFIB exposure in people include bad taste in mouth, nausea and weakness. Lung edema occurs about one to four hours after exposure, which is life-threatening in some cases, but in most people clears up in about 3 days.

932F - Carbonyl fluoride (COF2): Breakdown

of Teflon (PTFE) in air is the major source of carbonyl fluoride exposure. Carbonyl fluoride is the fluorine version of phosgene, a chlorinated chemical warfare agent. Carbonyl fluoride fumes can irritate eyes, ears and nose. More serious symptoms of exposure include chest pains, breathing difficulty, and fluid accumulation in the lungs, weakness, liver damage and increased glucose levels. Because carbonyl fluoride breaks down into hydrogen 8

fluoride and carbon dioxide, it causes many of the same toxic effects as hydrogen fluoride (see below).

932F

- Hydrogen fluoride (HF): Hydrogen fluoride (HF) is a toxic corrosive gas, and can cause death to any tissue it comes into contact with, including the lungs. The toxicity of HF is due to the fluoride ion and not the hydrogen ion. Breathing HF can cause severe lung damage, such as fluid buildup in the lungs (edema) and inflammation of lung passages (pneumonia). The fluoride ion (charged particle) is extremely toxic. It is a small ion and weak acid that diffuses quickly and can pass through tissues with relative ease. Fluoride ions inhibit cell respiration, decreasing production of ATP, the major form of chemical energy used by the body. Fluoride attacks cell membranes causing cells to die. The fluoride ion is negatively charged and naturally likes to react with positively charged ions in the body like calcium and magnesium. When fluoride and calcium bind, creating a "precipitate," a life-threatening condition of decreased calcium (hypocalcaemia) can occur. Left untreated, decreases in calcium (and magnesium) can cause abnormal heart rhythm leading to heart attack, muscle spasms and death. Calcium administration is the main treatment for HF poisoning. 1112F - Trifluoroacetic acid fluoride (CF3COF): Trifluoroacetic acid fluoride is toxic, mostly
because it breaks down into hydrogen fluoride, which is very toxic, and trifluoroacetic acid. The few studies that have looked at the toxicity of TFA found decreased growth of fetal rat boneforming cells (osteoblast) and cartilage cells (chondrocytes), and neural tube defects in rat embryos at high concentrations. Other studies show that HCFC-123, a hydro fluorocarbon that breaks down into TFA, causes enlarged liver and decreased levels of glucose, triglyceride and cholesterol in adult animals, but it is unclear whether these effects are due to HCFC123 or a metabolite.

1112F Octafluorocyclobutane (OFCB): Octaflurocyclobutane is a fluorine-containing gas

that is used in the semiconductor industry, sold as Zyron 8020 by DuPont. According to DuPont, inhaling high levels of octafluorocyclobutane can cause heart beat irregularities, unconsciousness and death. People with pre-existing heart conditions may be extra vulnerable. Only a few toxicity studies in

animals are available for octafluorocyclobutane. In one study, rats exposed to a one-time-only inhaled exposure of octafluorocyclobutane lost weight and had abnormal breathing. Dogs that inhaled high concentrations (10-25% air), and were dosed with the stimulant epinephrine, had heart problems.

1112F Name

global warming chemical, perfluorobutane has a long half-life in the upper atmosphere and has over 8,000 times the global warming potential of carbon dioxide. Perfluorobutane is not as acutely toxic as other PTFE off-gases, but has not been tested for longterm effects.

- Perfluorobutane CEA-410): As a

(PFB,

Trade

1202F - Carbon tetra fluoride perfluoromethane): In addition to being a

(CF4,

long-lived fluorinated Teflon "off-gas," perfloromethane is used in the semiconductor industry, is a refrigerant and propellant and a byproduct of aluminum production. The U.S. government is encouraging these industries to decrease emissions of perfluoromethane because it is a potent greenhouse gas, with a global warming potential almost 6000 times higher than carbon dioxide, and can last in the environment for 50,000 years. In the past, perfluoromethane has been used in pesticides as an "inert" ingredient; a label that has nothing to do with toxicity but only means the ingredient is not the main active pesticide. Inhaling fluorinated hydrocarbons like carbon tetra fluoride can cause eye, ear and nose irritation; heart palpitations; irregular heart rate; headaches; confusion; lung irritation, tremors and occasionally coma.

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USES OF TEFLON:
Teflon in a composite sheet form with graphite is used for bearing pads in the George Washington Bridge in New York State to prevent corrosion of the steel plates. Teflon industrial coatings can be used on carbon steel, aluminum, stainless steel, steel alloys, brass and magnesium, as well as non-metallic such as glass, fiberglass, some rubber and plastics. The versatility of these coatings allows almost unlimited application to a wide variety of part sizes and configurations. As a liquid, Teflon repels water and stains for the apparel, home fashions, furniture, and uniform markets. The Teflon forms a molecular shield around each fiber, guarding them from oil and water-based stains, dust and soil. Undetectable by sight, smell or touch, Teflon protects virtually all kinds of fabrics silk, wool, wool-blends, cotton, linen, velvet, heavy woven, micro fibers and both smooth and rugged fabrics without affecting their color, feel or breathe ability. Teflon is used to insulate thousands of miles of data communications cables because of its outstanding properties, heat and chemical resistance. Teflon is used to manufacture socks that reduce friction and blisters. These are especially crucial for diabetics, people with circulatory problems, geriatric needs, obesity and sensitive skin. Teflon is used in many applications for computer chip manufacture because it is very inert and non-reactive. It's used in filters to keep air clean, in chip carriers, and virtually all tubing and piping in the semiconductor industry.

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PROBLEMS WITH THE PRODUCTION OF TEFLON:

By 1984 DuPont was aware of five major problems with the production of Teflon: Chemicals associated with the production of Teflon had been linked to medical problems with workers; including polymer fume fever, leukemia, and liver damage. They had been linked to medical problems with test animals, including leukemia, cancer and reproductive dysfunction. Chemicals associated with the production of Teflon had been linked to birth defects in humans and test animals. Chemicals associated with the production of Teflon had been shown to accumulate in the blood of exposed individuals. Teflon had been shown to off gas free radicals that can form toxic fumes at temperatures much lower than reported by DuPont. Teflon related chemicals were found in drinking water in towns near the DuPont plant.

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PREVENTION:
Paul M. Gibbons, DVM, of the Niles Animal Hospital and Bird Medical Center in Niles, Illinois makes the following recommendations: If you have PTFE-coated drip pans, throw them away. Never boil water in a PTFE-coated pan. Never leave the kitchen when a PTFE-coated pan is in use. Cook at low or medium heat when using PTFE-coated pans. Use a culinary thermometer to determine the temperature at which your PTFE-coated appliances (deep fryers, waffle makers) operate. Never allow anyone to use PTFE-coated cookware in your home, unless instructed of its potential danger. Ensure that your kitchen is properly ventilated, preferably by a hood that vents outdoors. Aerosols from many types of products may contain fluorocarbons and particulates that can be toxic. Avoid the use of hair spray, perfume, spray deodorant, spray-on cooking oil, spray starch, and other aerosols in the same room as, or in close proximity. Burned or scorched plastics can emit toxic fumes. Use care in the kitchen, in the placement of candles, and using wood stoves and fireplaces to avoid the burning, scorching, or igniting of any plastic products. Smoke of any kind, including tobacco smoke, can quickly become toxic to birds, even causing death. Long-term exposure can not only damage the respiratory system, but cause eye and skin problems, as well as increased susceptibility to bacterial infections.

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REFERENCES:
1. www.wikipedia.com 2. www.dictionary.cambridge.org/dictionary/british/teflon 3. www.mindfully.org/plastic/teflon/teflon-historydupont.htm 4. www.tuberose.com/teglon.html 5. www.environmentalchemistry.com/yogi/environmental.html 6. www.peteducation.com 7. www.eoearth.org

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