Document ymm99K9Xw0QqXJgwBwwrj2nxd

-f\&A6 - 1063 Guide tolde SafeHandling of Fluoropolymer Dispersions r * -.: - :) c di ro ro ro Prepared by the FLUOROPOLYMER MANUFACTURERS GROUP O cto b e r 2001 BZ-101 The Society o f th e Plastics Industry, Inc. I CONTAIN NO OPi This page left intentionally blank. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry. Inc., All Rights Reserved Page 2 NOTE TO USERS This Guide was developed by the Fluoropolymer Manufacturers Group o f The Society o f the Plastics Industry, Inc. and is intended to provide information on general guidelines for safe handling o f fluoropolymer dispersions. The guidelines provided are based on the collective experience o f members o f the industry, but are not intended to be either exhaustive or inclusive o f all pertinent requirements. The information provided in this guide is offered in good faith and believed to be reliable, but is made WITHOUT WARRANTY, EXPRESSED OR IMPLIED, AS TO THE MERCHANTABILITY, FITNESS FOR A PARTICULAR PURPOSE, OR ANY OTHER MATTER. The guidelines provided and the examples included are not intended to be directed to any particular product, nor are they claimed to satisfy all current legal requirements related to control o f processing operations. Following the Guide does not guarantee compliance with any regulation nor safe operation o f processing facilities. Users are cautioned that the information upon which this guide is based is subject to change which may invalidate any or all o f the comments contained herein. The Guide is not intended to provide specific advice, legal or otherwise, on particular products or processes. In designing and operating processing lines, users o f the Guide should consult with their own legal and technical advisors, their suppliers, jjpd other appropriate sources (including but not limited to product or package -labels, technical bulletins, or sales literature) which contain information about known and reasonably foreseeable health and safety risks o f their proprietary products and processes. SPI, its members and contributors do not assume any responsibility for the user's compliance with any applicable laws and regulations, nor for any persons relying on the information contained in this Guide. SPI does not endorse the proprietary products or processes o f any manufacturer or user o f fluoropolymer resins or products. All information about an individual manufacturer's products contained herein has been provided by those manufacturers who are solely responsible for the accuracy and completeness of the data. Copyright 2001 The Society o f the Plastics Industry, Inc. All Rights Reserved SPI Literature Catalogue #: BZ-101 Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 3 This page left intentionally blank. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 4 Table o f Contents NOTE TO USERS ............................................ :....................................................................................................................... 3 INTRODUCTION...................................................................................................................................................................... 7 TYPICAL COMPOSITIONAL INFORMATION................................................................................................................ 8 TOXICOLOGICAL INFORMATION AND POTENTIAL HEALTH EFFECTS ............................................................................................................................................................ 8 Signs and Symptoms O f Exposure 10 Eye Contact 10 Skin Contact 10 Ingestion 10 Inhalation ,1 0 Systemic 10 HANDLING AND STORAGE / EXPOSURE CONTROL .......................................................................................................................................................... 11 FPA PHYSICAL AND CHEMICAL PROPERTIES ........................................................................................................ 13 Thermal Behavior 14 Behavior in Water 14 ECOTOXICOLOGICAL INFORMATION........................................................................................................................ 15 DISPOSAL CONSIDERATIONS ...................................................................................................................................... 15 GLOSSARY............................................................................................................................................................................. 17 REFERENCES......................................................................................................................................................................... 21 Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 5 This page left intentionally blank. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 6 Guide to the Safe Handling of Fluoropolymer Dispersions INTRODUCTION Fluoropolymer dispersions are an aqueous form o f fluoropolymer typically used for coating metal and glass cloth. These dispersions are produced and sold on a global basis by several manufacturers. The purpose o f this guide is to provide safe handling information to dispersion processors, since these products utilize a fluoropolymer polymerization aid (FPA) during their manufacture. Recent studies have revealed the FPAs are persistent in the environment and have exhibited toxicological effects in animals. FPAs are members o f a class o f commercially available perfluoroalkyl carboxylate surfactants (e.g., ammonium and sodium perfluoro-octanoate). FPAs are used to suspend and em ulsify som e fluoropolymers during manufacture or industrial use and are typically used in concentrations less than 0.5%. FPAs may be fqund in other forms o f fluoropolymers, e.g., formulated coatings and som e dry resin products. An eight-carbon member o f this fam ily, ammonium perfluorooctanoate (APFO) is the FPA m ost com m only used in the production o f many fluoropolymers and fluoroelastomers. APFO has several synonyms including C-8 acid, PFOA, FC 143, and perfluoro ammonium octanoate. Similar em ulsifiers include sodium perfluorooctanoate, and the salts o f other perfluorocarboxylic acids, such as perfluorononanoic acid. Because APFO is the best understood FPA in terms o f toxicology and health effects, it is the main focus o f this guide. For purposes o f safe handling o f fluoropolymer dispersions containing FPAs, the other perfluorocarboxylates should be treated sim ilarly to APFO from a chem ical and toxicological viewpoint. APFO is a sublim able solid that is typically supplied to the resin manufacturer in a concentrated aqueous solution. It is then used in a dilute form as a polym erization em ulsifier. Once the polym erization is com plete, the APFO is normally removed during finishing processes that result in dry forms o f fluoropolymer products. Trace amounts o f APFO may be present in finished fluoropolymer resins. Since these finishing steps are not applied to aqueous dispersions, the APFO added during polym erization is usually present in dispersion products as sold. Since APFO is a perfluorinated chemical, it is extremely stable, degrades slow ly, and therefore persists in the environment. APFO also appears to be persistent in humans and has been found in trace amounts in the blood o f workers exposed during manufacturing operations involving its use. Based on health studies covering more than thirty years o f exposure, there have been no adverse human health effects observed in exposed em ployees. For control o f occupational exposure, the American Conference o f Governmental Industrial Hygienists (ACGIH) recommends a Threshold Limit Value (TLV) for APFO o f 0.01 milligram per cubic meter in air as an eight-hour, tim eweighted average (TW A) occupational exposure limit. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, inc., All Rights Reserved Page 7 TYPICAL COMPOSITIONAL INFORMATION The follow ing represents a composition typical o f fluoropolymer dispersions as supplied by fluoropolymer manufacturers. Consult your supplier for specific product information. Ingredient Fluoropolym er Approximate W eight (% wf) 20 - 60 Water 30-70 N on-ionic Surfactant <6 Fluoropolymer Polym erization Aid <1 The fluoropolymer dispersions that contain FPAs may be dispersions o f PTFE, FEP, PFA, PVDF, and THV. FluoroelstdSher dispersions are also available that may contain FPAs. The stabilizing surfactants m ost commonly used in these dispersions are nonionic alkylphenol alkoxylates such as Triton X-100. The pH o f these dispersions w ill vary over the range o f 2 to 10, and their physical appearance is normally a m ilky white liquid. Specific products may vary from one manufacturer to another. Contact your supplier for information on the follow ing topics: fire fighting, first aid and treatment, accidental release measures, stability and reactivity, and regulatory information. TOXICOLOGICAL INFORM ATIONAND POTENTIAL HEALTH EFFECTS Aqueous fluoropolymer dispersion products contain FPAs for which the majority o f the toxicology data and health studies have been conducted on APFO. APFO is a skin, eye, nose, and throat irritant and can be absorbed through the lungs, gastrointestinal tract and skin. APFO has been classified by ACGIH as an animal carcinogen with an A3 rating (ACGIH Threshold Limit Values). A vailable evidence does not suggest that the agent is likely to cause cancer in humans except under uncommon or unlikely routes or levels o f exposure. See ACGIH publication, Threshold Limit Valuesfo r Chemical Substances and Physical Agents and Biological Exposure Indexes (current edition), Appendix A , Carcinogenicity, for further information. The TLV has a "skin" notation, which means that absorption through the skin is a significant potential route o f exposure. ACGIH TLV/TW A 0.01 mg/m3 (skin), A3 Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 8 An OSHA Perm issible Exposure Limit (8-hour time weighted average) has not been established. The results o f acute toxicological tests for APFO are as follows: LC50 4 hr. inhalation - rat LD50 skin absorption - rabbits LD50 oral - rats 980 mg/m3 4278 mg/kg 540 mg/kg These values suggest that APFO is not highly toxic in the short term. APFO is a skin and eye irritant, but is untested for animal sensitization. APFO is not mutagenic in in-vitro mutagenicity assays and did not cause cell transformation in a mammalian cell transformation assay. Tests in anim als demonstrate no developmental toxicity. APFO is not teratogenic in rabbits by oral administration or teratogenic to rats by gavage or inhalation exposures. Tests in m ale rats demonstrated tumorigenic activity based on an increased incidence o f benign testicular, pancreatic, and liver tum ors.. Based on preliminary analysis from a recently com pleted two-generation study in rats, APFO does not affect reproductive processes. Like som e other FPAs, APFO can potentially generate perfluorooctanoate anion either through dissociation or m etabolism . Animal studies conducted on perfluorooctanoate anion indicate effects including liver disturbances, weight loss, loss o f appetite, adrenal and hem atological effects, and benign tumors o f the liver, pancreas and testes o f male rats. There are no known human health effects from anticipated exposure to this perfluorooctanoate anion when used as intended. Epidem iology studies in workers exposed to APFO have demonstrated persistent levels o f organo fluorine in the blood. The presence o f organo fluorochemicals in the blood o f the general population and subpopulations, such as workers, has been published dating back to the 1970's. The major APFO manufacturer's epidem iological study o f its own workers indicates no adverse health effects. Thirty years o f experience has indicated that although APFO is found in trace amounts in exposed workers no abnormalities in liver function or cholesterol have been observed in these exposed em ployees. There has been no increase in any cause o f death amongst the exposed workers. This information in this guide may change, as results o f further studies becom e available. Consult your supplier or SPI for the m ost up-to-date information. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 9 Signs and Symptoms O f Exposure Eye Contact Signs and symptoms associated with eye contact may include irritation w ith discomfort, redness, sw elling, tearing and blurring o f vision. Skin Contact Signs and sym ptom s associated with skin contact may include irritation w ith discomfort, redness, sw elling and itching. APFO may be absorbed through the skin and produce effects similar to those caused by inhalation and/or ingestion. Ingestion Based on results from 4egh-dosage animal testing, signs and symptoms associated with ingestioti may include gastrointestinal tract irritation, abdominal pain, nausea and vom iting, diarrhea, lethargy, abnormal liver function as detected by laboratory tests, abnormal blood form ing system function as detected by laboratory tests; or abnormal blood forming system function w ith anemia. Repeated exposures produced liver, kidney, pancreas and testes changes; anemia and cyanosis. Ingestion studies in animals have shown that repeated doses o f ammonium perfluorooctanoale produce benign tumors in the pancreas, liver and testes. There are no known human health effects from anticipated exposure to APFO when used as intended. Inhalation A single exposure above recommended guidelines may cause irritation to the upper respiratory tract and liver enlargement. Based on results from animal testing, signs and sym ptom s may include soreness o f the nose and throat, irritation o f the upper respiratory passages with coughing, sneezing and discom fort. Prolonged or repeated exposure above recommended guidelines may cause liver effects. Based on results from animal testing, signs and symptoms may include yellow skin (jaundice) and tenderness o f upper abdomen. APFO may be absorbed by inhalation and persist in the body for an extended tim e. Systemic APFO can be absorbed by the body and may be detected in the blood stream follow ing ingestion, inhalation or skin contact. Animal and human experience indicate that this compound has a long halflife in the blood, and may be detected years after exposure. The presence o f organo fluorochem icals in the blood o f the general population and subpopulations, such as workers has been published dating Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 10 back to the 1970's. The major APFO manufacturer's epidem iological study o f its own workers indicates no adverse health effects. Medical conditions potentially aggravated by overexposure include pre-existing diseases, such as those o f the liver and bone m arrow .. Animal studies conducted on perfluorooctanoate anion indicate effects including liver disturbances, weight loss, loss o f appetite, adrenal and hematological effects, and benign tumors o f the liver, pancreas and testes o f m ale rats. There are no known human health effects from anticipated exposure to APFO w hen used as intended. Consult your supplier for specific information on treatment and first aid measures. HANDLING AND STORAGE/ EXPOSURE CONTROL It is important toavoj^L contact when handling products containing FPAs. FPAs are released when dispersions are dried or heated. The primary exposure routes o f FPAs when processing dispersions are through the skin (dermal), ingestion (e.g., by transference from hand to mouth), and via inhalation. FPAs are irritating to the eyes. Based on the high vapor pressure o f some o f these FPAs, it is important to clean up spills and overspray before they dry and allow the FPA to sublime. Dispersion containing waste should also be disposed o f in closed containers. The vapor pressures are high enough that under conditions o f poor ventilation these sources o f FPA may result in exposures that exceed the ACGIH TLV. See the section on physical and chem ical properties for more detail. U se o f engineering controls, good hygienic practices and personal protection equipment (PPE) are critical in reducing em ployee exposure to FPAs when working with fluoropolymer dispersions. A lone, each o f these control methods cannot eliminate potentially hazardous work conditions, but a com bination o f these m ethods, em ployee involvem ent, and company support can control exposure. Wear appropriate gloves and protective eyewear when handling this material. In addition, use one or more o f the follow ing personal protection items as necessary to prevent skin contact: head covering, coveralls, and aprons. D o not allow smoking and/or eating in areas where FPAs or fluoropolymers are used. W ash hands and exposed skin after use, and before handling food or applying cosm etics. There are other health and safety hazards associated with handling, use, and processing o f fluoropolymers, including dispersions. Sm oking cigarettes or tobacco contaminated with dust from fluoropolymer products is associated w ith "Polymer Fume Fever." More information on this subject can be found in SPI's Guide to the Safe Handling o f Fluoropolymers Resins. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 11 The major health hazard associated with handling fluoropolymers is the inhalation o f decom position products. In addition, when handling fluoropolymer dispersions, FPAs are released when coatings are dried or heated. Provide sufficient ventilation to maintain exposures below recommended lim its. If exhaust ventilation is not adequate, use appropriate respiratory protection. APFO is a sublimable solid, meaning that vapors are released directly from the solid. Handling APFO in water lim its the release o f APFO directly into the air. In case o f a release or spill, APFO containing liquids must be cleaned up promptly before the water dries to prevent contamination o f other surfaces in the area. Contain and absorb material onto sawdust, oil-dry or similar inert absorbent. Residuals should be cleaned-up with water and additional absorbent Spilled m aterials should be placed into a covered container for disposal according to applicable local, state and federal regulations. During clean up, caution must be exercised, as the spill area may be extremely slippery. Ventilation and appropriate Personal Protective Equipment (PPE) must be used when cleaning die spill. Contact w ith contaminated surfaces, dispersions, solutions, spray m ist and powder or dust in the air all result in absorption o f FPAs into the body. Exposure to FPAs can occur during dispersion processing operations w hile mixing, transferring, or formulating the coatings, as w ell as w hile applying coatings, drying, sintering or baking. Exposure to FPA may also occur during equipm ent maintenance (e.g. cleaning tanks and spray equipment, fans, spray filters, exhaust ducts, etc.). Because som e FPAs are known to stay in the body for long periods o f tim e, exposure prevention is very important. Engineering controls are the first line o f defense to control exposure. Examples o f engineering controls include both general plant ventilation and local exhaust ventilation for specific, potentially high exposure tasks. A spray paint booth is an example o f a local exhaust system (see the Safe Handling Guide for a description o f local exhaust system s used in fluoropolymer processing). Enclosing processes is an additional type o f engineering controls; automation is another w ay to lim it exposure. Lastly, all heated processing equipment requires a ventilation system to prevent inhalation exposures. A hazard assessm ent o f job tasks w ill help determine what types o f PPE are appropriate and necessary. U sing PPE properly is important. For example, significant exposure can occur from clothing contaminated by improper storage or disposal o f gloves, such as putting them in pockets o f work clothes between uses. In addition, thorough and frequent washing o f hands and any exposed skin w ill reduce potential exposure. Care should be taken to prevent the spread o f material by contaminated clothing and shoes. Contaminated clothing and shoes should be thoroughly cleaned before re-use. Em ployees should not rem ove contaminated clothing from the workplace. Finally, good housekeeping practices also help reduce potential exposure. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 12 For protection from FPAs, gloves should be made from nitrile rubber or neoprene. I f there is a potential for splashing or contact with liquid material, use ANSI Z 87.1 approved chem ical goggles and/or a face shield. In certain applications, using aprons, coveralls, or full body protection, in addition to gloves and face protection, may be appropriate. Consult your supplier for m ore detailed information. Drying or high temperature processing, such as "sintering," may result in the release o f the FPAs and decom position products. The vapors and gases produced in the oven as the product cures may condense as a solid or as a liquid solution in the oven, exhaust duct or stack, or on other cool surfaces. These condensed or solidified fumes can contain hazardous substances. Skin contact with this condensate when cleaning the oven, stack or other equipment must be avoided. Handling concentrated FPA solutions and solids may require the use o f additional PPE such as bodysuits, face shields and respirators. Respiratory protecting may also be required during certain operations, such as spray coating, dispersion processing operations, or sintering. In situations where exposure to sintering fum es, vapors, or dispersion m ists is likely, and ventilation is inadequate to control exposure levels, NIOSH approved respirators must be used and a respiratory protection program m eeting the requirements o f the OSHA respiratory protection standard, 29 C.F.R. 1910.134 must be follow ed. An air-purifying respirator equipped with organic vapor/acid gas cartridges and a high efficiency dust/m ist pre-filter may be appropriate for protection against dust, mist, or fumes as found in cleaning condensate from ovens or exhaust systems. When exposure to FPA or fluoropolymer thermal decom position products is anticipated (as found in firefighting applications), an air-supplied respirator in positive pressure or demand m ode is appropriate. Specific recommendations for respirators should be obtained from product material safety data sheets or your supplier. FPA PHYSICAL AND CHEMICAL PROPERTIES This section discusses som e physical properties o f FPAs as they relate to the safe handling o f fluoropolymer products. The FPAs used commercially are typically mixtures to at least som e degree, and their identity may differ by fluoropolymer producer. Differences can include the m olecular weight o f the FPA, whether branched structures are present in the m olecule, and the identity o f counter-ions present. For relevant physical properties o f an FPA used to make a particular fluoropolymer, the fluoropolymer manufacturer should be contacted. A general treatment o f physical and other properties o f FPAs may be found in Fluorinated Surfactants .' FPAs have certain physical properties that are important for exposure controls. One property is their behavior when warm or hot. FPAs readily get into the air, even when heated as dried solids, such as from a spill in a hot work area. Another property is that FPAs can change into their carboxylic acid form if additional acid is m ixed with dispersion. These carboxylic acids can get into the air more Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 13 easily than the FPAs themselves. Refer to the follow ing section for a m ore detailed discussion o f these topics. Thermal Behavior Perfluorocarboxylic acids are fairly low m elting solids that increase in m elting point w ith increasing chain length and that decrease in melting point with branching.2 The parent acids used to make FPAs typically m elt at less than 100 C. Slight sublimation o f perfluorooctanoic acid has been reported to occur at 40 C.3 W hile it may be expected that conversion to their salts for use as FPAs should reduce their volatility, the salts differ greatly among them selves in their behavior when heated, with som e o f them show ing noticeable volatility. The com m only used ammonium salt, in particular, show s volatility at fairly low temperatures. For example, the vapor pressure o f ammonium perfluorooctanoate (APFO) was reported to be approximately 7 x 10'5m m Hg at 20 C and sublimation was reported to occur at 130 C.4 A study o f w eight loss behavior by thermogravimetric analysis o f various salts o f perfluorooctanoic acid highlighted the differences in their thermal behavior5. For exam ple, the ammonium salt began to show w eight loss in the 50-100 C range (20% weight loss under the conditions used at 167 C), w hile the sodium salt did not show weight loss until about the 200-250 C range (20% w eight loss at 298 C). Due to their thermal response, exposure to FPAs can occur even at room temperature but m ore likely when using heated solutions and solids heated process equipment, and from the vent streams o f such equipm ent. Behavior in Water The solubility behavior o f FPAs is com plex, as expected from surfactants, which can involve the formation o f m icellar solutions and liquid crystal phases. Phase diagrams have been published for ammonium perfluorooctanoate6, and for various salts o f perfluorononanoic acid, including the ammonium salt7. In addition, there are a number o f related references available in the literature. The solubility o f the FPAs varies greatly with chain structure and counter ion. For exam ple, the room temperature solubilities (for isotropic solutions o f surfactant and water) were measured as being about 50% for ammonium perfluorooctanoate, and as being about 18% for ammonium perfluorononanoate. Within the perfluorononanoate family, the parent perfluorononanoic acid showed fairly low room temperature solubility o f less than 0.2%, the sodium salt was about 2%, and the ammonium, as stated above, was about 18%. At higher concentrations, there was liquid crystal formation. Temperature effects can be strong: the solubility o f the sodium salt o f perfluorononanoic acid rose to about 40-50% at 50 C. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., Alt Rights Reserved Page 14 The parent perfluorocarboxylic acids are more acidic than their aliphatic counterparts.8 The acidity constants decrease with chain length beginning with perfluoropentanoic acid,9 but the parent acids o f FPAs still show substantial acidity in comparison to otherwise similar non-fluorinated acids. The pKa o f perfluorooctanoic acid was reported as 2 .5 .10and the pKa o f perfluorononanoic acid w as reported as 2.611. Because o f the acidic character, o f their parent acids, FPAs are likely to be fully ionized unless the pH o f the solution is fairly low, approaching the pKa o f the parent acid, near which point and below , formation o f the undissociated parent acid can be expected. ECOTOXICOLOGICAL INFORMATION D o not discharge dispersions to lakes, streams or waterways. See discussion below for disposal considerations. D isposal to water w ill produce a milky appearance. The fluoropolym er component is not toxic. The stabilizing surfactants have varying ecotoxicity profiles, and users'shfl&ld contact their supplier for more detailed ecotox information for their particular product. FPAs are capable o f generating perfluoroalkyl carboxylate anions that are persistent in the environment. Because these anions do not readily degrade or m etabolize, they have the potential to accum ulate. The ecotoxicology o f APFO is the best studied o f the FPAs. APFO has been determined to be algistatic. It has a 48-hour LC50 value o f 720 mg/L for daphnia. APFO has a 96-hour LC50 o f 740 mg/L for fathead minnows, 634 mg/L for bluegill sunfish and 4001 m g/L for rainbow trout. DISPOSAL CONSIDERATIONS Fluoropolymer dispersions typically have the following waste disposal considerations. Consult your supplier for information on their particular product. Preferred options for disposal are: (1) Separate solids from liquid by precipitation and decanting or filtering. D ispose o f dry solids in a landfill that is permitted, licensed or registered to manage industrial solid waste. Discharge liquid filtrate to a wastewater treatment system . (2) Incinerate only if incinerator is capable o f scrubbing out hydrogen fluoride and other acidic com bustion products. RCRA/US EPA WASTE INFORMATION: Discarded product is not typically a hazardous waste under RCRA 40 CFR 261. Dispose in an authorized landfill site or incinerate under approved Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 15 controlled conditions. This product may be incinerated above 800 C (1472 F) using a scrubber to remove hydrogen fluoride. EMPTY CONTAINER: Empty containers should be punctured or otherwise destroyed before disposal. Empty containers must not be used for home or personal uses. ALL DISPOSAL METHODS: Treatment, storage, transportation, and disposal o f this product and/or container must be in accordance with applicable federal, state/provincial, and local regulations. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry. Inc., All Rights Reserved Page 16 GLOSSARY A3 rating: ACGIH animal carcinogen rating. Confirmed animal carcinogen with unknown relevance to humans: The agent is carcinogenic in experimental animals at a relatively high dose, by routes o f administration at sites, o f histologic types, or by mechanisms that may not be relevant to worker exposure. Available epidem iologic studies do not confirm an increased risk o f cancer to exposed humans. A vailable evidence does not suggest that the agent is likely to cause cancer in humans except under uncommon or unlikely routes or levels o f exposure. Algistatic: A n agent that is active against algae, but does not necessarily destroy algae (i.e. not algicidal). American Conference o f Governmental Industrial Hygienists (ACGIH): A professional organization devoted to the adm inistrative and technical aspects o f occupational and environm ental healths ACGIH is not a governm ent entity. For additional inform ation refer to the current ACG IH TL V s and BEIs book or see w w w .acgih.org. Ammonium Perfluorooctanoate (APFO): Ammonium perfluorooctanoate, or APFO , is the am m onia salt o f perfluorooctanoic acid, having the chem ical form ula C7F 15- C 0 2'N H 4+- APFO is a com m only used FPA. This perfluorochem ical is a powerful surfactant used to em ulsify and stabilize fluoropolym er dispersions. APFO has several synonyms including C-8, PFOA, FC 143, and perfluoro ammonium octanoate. FEP: FEP resin is a polym er o f tetrafluoroethylene and hexafluoropropylene w ith the form ula [(CF(CF3)-C F2)x(CF2 -C F2)y]n. It has a m elting point range o f 473-563F (245-280C ) and is m elt processible. It is supplied in the form o f translucent p ellets, powder, or as an aqueous dispersion. Fluoropolymer dispersions: Fluoropolym er dispersions are an aqueous form o f fluoropolym er consisting o f fin ely divided fluoropolym er particles suspended in water. They are frequently used as ingredients for coating com positions applied to m etal surfaces or fiberglass cloth to create durable, nonstick surfaces. Fluoropolymer Polymerization Aid (FPA): FPAs are members o f a class o f commercially available perfluoroalkyl carboxylate surfactants (e.g., ammonium and sodium perfluoro-octanoate). FPAs are used to suspend and em ulsify some fluoropolymers during manufacture or industrial use and are typically used in concentrations less than 0.5%. Micellar solutions'. Surfactants in water can pack together to form aggregates called m icelles. These aggregates usually have oil soluble surfactant tails bunched together in their interiors, and polar surfactant heads facing the water phase. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 17 M utagenic: A mutagen interferes w ith the proper replication o f genetic m aterial (chrom osom e strands) in exposed ceils. If germ cells are in volved, the effect may be inherited and becom e part o f the gen etic pool passed onto after generations. NIOSH: The N ational Institute for O ccupational Safety and Health is a federal agency. It conducts research on health and safety concerns, tests, certifies respirators, and trains occupational health and safety professionals OSHA: U . S. Occupational Safety and H ealth Administration. Perm issible Exposure Limit (PEL): A term used by OSHA. U nless noted otherw ise, O SH A PELs are TW A concentrations that m ust not b e exceeded during any eight-hour work shift o f a forty-hour w orkweek. These PELs are expressed as eight-hour TW A. A dditional inform ation can be found on the OSHA web site, w w w .osha.gov. Personal Protective*Equipment (PPE): PPE is used to reduce exposures to hazards w hen engineering and adm inistrative controls are not feasible or effective in reducing these exposures to acceptable levels. PFA: PFA resin is a polym er o f tetrafluoroethylene and a perfluorinated vin yl ether having the form ula [(C F(O R f)-C F 2)x(CF2-CF2)y]nwhere ORf represents a perfluoroalkoxy group. PFA m elts at 572F (300C ) minimum and is m elt processible. It is available in the form o f p ellets, pow der, and as an aqueous dispersion. Polymer Fume Fever: A type o f inhalation fever associated w ith the inhalation o f fluoropolym er decom position products (exhaust effluents, fum es, and gases). It is characterized by tem porary flu-like sym ptom s, which may include fever, chills, and / or, cough. Sym ptom s m ay be delayed approxim ately 4-24 hours follow ing exposure. The severity o f effects depends on the extent o f overheating and the quantity inhaled. D ecom position products m ay produce progressive breathing difficulty and later develop into severe pulm onary edem a. Edem a m ay be delayed and unlike polym er fume fever, requires m edical intervention. PTFE: PTFE is a polym er consisting o f recurring tetrafluoroethylene m onom er units w hose form ula is [CF2-CF2]n. PTFE does not m elt to form a liquid and cannot be m elt extruded. On heating the virgin resin, it forms a clear coalescable gel at 630F20 (332C 10). Once processed, the gel point (often referred to as the m elting point) is 20F (10C ) low er than that o f the virgin resin. It is sold as a granular powder, a fine powder, or an aqueous dispersion. PVDF: PV D F is a hom opolym er o f vinylidene fluoride having the form ula [CH2-CF2],, or a copolym er o f vinylidene fluoride and hexafluoropropene having the form ula [(CF(CF3)CF2)x(CH2-C F2)y]n. PVDF polym ers m elt at 273 - 352F (134 - 178C) is m elt processible, and is supplied in the form o f powder, pellets, or as an aqueous dispersion. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 18 RCRA/US EPA WASTE INFORMATION'. The Resource Conservation and R ecovery A ct enacted by Congress in 1976. RCRA's primary goals are to protect human health and the environm ent from the potential hazards o f waste disposal, to conserve energy and natural resources, to reduce the amount o f w aste generated, and to ensure that wastes are managed in an environmentally sound manner. Enabling legislation is U.S.C. title 42, chapter 82, subsections 6901 et seq. Additional information available from the US EPA O ffice o f Solid Waste, or via the URL: "h ttp://w w w .ep a.gov/epaosw er/gen eral/orien tat/". Skin notation: Substances listed with designation "Skin" refer to the potential sign ificant contribution to the overall exposure by the cutaneous route, including m ucous m em branes and the eyes, either by contact w ith vapors or, o f probable greater significance, by direct skin contact w ith the substance. V ehicles present in solutions or m ixtures can also significantly enhance potential skin absorption. It should be noted that w hile som e m aterials are capable o f causing irritation, derm atitisfand sensitization in workers, these properties are not considered relevant when assign in g a skin notation. It should be noted, however, that the developm ent o f a derm atological condition could significantly affect the potential for dermal absorption. U se o f the skin designation is intended to alert the reader that air sam pling alone is in su fficient to accurately quantitate exposure and that measures to prevent significant cutaneous absorption may be required. For additional inform ation refer to the current ACGIH TLVs and BEIs book or see w w w .acgih.org. Systemic: System ic effect refers to an adverse health effect that takes place at a location distant from the body's initial point o f contact and presupposes absorption has taken place. Teratogenic: A teratogen (em bryotoxic or fetotoxic agent) is an agent that interferes w ith normal em bryonic developm ent without causing a lethal effect to the fetus or dam age to the mother. E ffects are not inherited. -T h is contrasts w ith a local effect that refers to an adverse health effect that takes place at the point or area o f contact. The site may be skin, m ucous m em branes, the respiratory tract, gastrointestinal system , eyes, etc. Absorption d o es not necessarily occur. Threshold Limit Value (TL V): Threshold Limit Values (TLVs) refer to airborne concentrations o f substances and represent conditions under which it is believed that nearly all workers may be repeatedly exposed day after day without adverse health effects. Because o f w ide variation in individual susceptibility, however, a small percentage o f workers may experience discom fort from som e substances at concentrations at or below the threshold limit; a smaller percentage may be affected m ore seriously by aggravation o f a pre-existing condition or by developm ent o f an occupational illness. Smoking o f tobacco is harmfiil for several reasons. Smoking m ay act to enhance Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 19 the biological effects o f chemicals encountered in the workplace and may reduce the body's defense mechanisms against toxic substances. The amount and nature o f the information available for establishing a TLV varies from substance to substance; consequently, the precision o f the estim ated TLV is also subject to variation and the latest TLV Documentation should be consulted in order to assess the extent o f the data available for a given substance. THV: TH V is a terpolym er o f tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride, having the formula [(CF2-CF2)x-(CF(CF3)-CF2)y(CH2-CF2) J n. THV is m elt p rocessible w ith m elting points ranging from 240 to 356F (115 to 180C ) depending on grade. It is available in p ellet, agglom erate or as an aqueous dispersion. Threshold Limit Value / Time Weighted Average (TLV-TWA): The tim e-w eighted average concentration for a conventional 8-hour workday and a 40-hour w orkw eek, to w hich it is b elieved that nearly all workers m ay be repeatedly exposed, day after day, w ithout adverse effect. - Tumorigenic: Tumors (benign and cancerous) are formed as sw ellin gs or abnormal grow th o f tissues. The probability that tumors w ill occur depends on the sp ecies, sex , strain, and age o f the anim al, as w ell as the dose, route and length o f exposures to a substance. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry. Inc., All Rights Reserved Page 20 REFERENCES 1K issa, Erik Fluorinated Surfactants-, Marcel Dekker: N ew York, 1994. 2Bem ett, Marianne K. and Zisman, W. A . J. Phys. Chem. 1967, 71,2075-82 3Nakayama, Haruo Bull. Chem. Soc. Jpn. 1967,4 0 ,1592-95. 4Griffith, F. D. and Long, J. E. Am. Ind ffyg. Assoc. J. 1980,4 1 ,576-83. 5Lines, D. and Sutcliffe, H. J. Fluorine Chem. 1984,25(4), 505-12. s Tiddy, G. J. T. J. Chem. Soc., Faraday Trans. 1 1 972,6 8 ,608-12. 7Fontell, Krister and Lindman, Bjm J Phys. Chem. 1 9 8 3 ,8 7 ,3289-97. *K issa, Erik Fluorinated Surfactants-, Marcel Dekker: N ew York, 1994. 9M oroi, Yoshikiyo; Yano, Hiroaki; Shibata, Osamu; Yonemitsu, Tadashi Bull. Chem. Soc. Jpn. 2001, 74(4), 667-72. 10Y linen, Markku; Kojo, Annell; Hanhijrvi, Hannu; Peura, Pekka Bull. Environ. Contam. Toxicol. 1 9 9 0 ,4 4 ,46-53. 11M oroi, Yoshikiyo; Yano, Hiroaki; Shibata, Osamu; Yonemitsu, Tadashi Bull. Chem. Soc. Jpn. 2001, 74(4), 667-72. Guide to the Safe Handling of Fluoropolymer Dispersions Copyright 2001 The Society of the Plastics Industry, Inc., All Rights Reserved Page 21