FLAME RETARDANTS - 101: BASIC DYNAMICS Past Efforts Create Future Opportunities THE FIRE RETARDANT CHEMICALS ASSOCIATION Papers Presented At: BALTIMORE MARRIOTT INNER HARBOR HOTEL BALTIMORE, MARYLAND MARCH 24 - 27, 1996FLAME RETARDANTS - 101: BASIC DYNAMICS Past Efforts Create Future Opportunities 1996 SPRING CONFERENCE THE FIRE RETARDANT CHEMICALS ASSOCIATION “Flame Retardant Markets, Products, Regulations, A Historical Perspective" Louis 0. Racthor Marketing Technical Services, Inc. “Mechanisms for Flame Retardancy and Smoke Suppression = A Review" Joseph Green FNC Corporation “Fire Test Methods for Fire Retardant Polymers" Javier 0. Trevino Omega Point Laboratories, Inc. "Fire Safety Codes and Regulations" Robert S. Strength FRCA Consultant (Product Safety Management, Inc.) "Flame Retardants and Their Market Applications" James D. Innes Flame Retardants Associates Inc "A Review of Phosphorus-Containing Flame Retardants" Joseph Green FMC Corporation "Chlorine Containing Flame Retardants" Ronald L. Markezich Occidental Chemical Corporation “Brominated Flame Retardants" Mary G. Harscher Great Lakes Chemical Corporation "Antimony Flame Retarder Synergists” Irving Touval Touval Associates Inc. "Boron Compounds as Fire Retardants Kelvin K. Shen U.S. Borax Inc, Page 13 31 47 61 71 a9 105 117 137er ee "Mineral Hydroxides-Their Manufacture and Use as Flame Retardants" William E. Horn, Jr. Alcoa Industrial Chemicals "Engineering Thermoplastics"* Ari Hochberg LNP Engineering Plastics, Inc. "HIPS/EPS"* Robert M. Swett Huntsman Chemical Corporation ABS & ABS/PC* Thomas L. Evans General Electric Company “Plame Retarded Vinyl Formulations: Theix Contributions to Fire Safety” A. William Coaker, Ph.D. A Coaker and Associates "Flame Retardant Polyolefins: Key Factors in Developing Engineered Commodity Resin Systems" John Morits The Gitto/Global Corporation “Flammability and Material Trends in the Furnishings Industry” Gordon H. Damant Inter-City Testing and Consulting “Future Flame Retardant Trends /Requirements at Texas Instruments’ Herb Moltzan Texas Instruments "Construction/Federal Requirements - Private Needs"* David Harris National Institute of Building Sciences "Future Trends Involving The Use of Fire Retardant Chemicals in Wire & Cable Applications Doug Terry Furon Company “Pransportation/Amtrak Design § Materials Activities"* James Gourley Ceasar Vergara D. Karan Fire Safety Group/Amtrak * Papers not available at publication time 161 7a 1g1 195 215CHLORINE CONTAINING FLAME RETARDANTS RONALD L. MARKEZICH Occidental Chemical Corporation ‘Technology Center Grand Island, New York 14072 Chlorinated flame retardants can be divided into three groups: aliphatic, aromatic, and cycloaliphatic. ‘The type of organic chlorine compound will determine processing limitations and, to some extent, the application of these flame retardants. Impoctant properties and characteristics of a commercial flame retardant should include: + High molcoular weight: many of the additive flame retardants in this class have molecular weights above 600. High chlorine content: greater than 50 percent. ‘Thermal stability: greater than 270°C for addition to engineering thermoplastics. Nontoxicity. White or light color: many plastics applications require white or light-colored flame retardants ‘compounded into a polymer, it must not bloom during use, even at elevated temperatures. ™ Low volatility: flame-retardant additives must be essentially nonvolatile; they must not vaporize during processing or evaporate from parts during their useful life, Ironically, one property highly desirable for processing--thermal stability--is not desirable for flame retardancy. Restated, if compound is too thermally stable at flame temperatures, it will be a poor flame retardant. Figure | shows the gencral relationship between increasing flame-retardant efficiency and increasing thermal stability for aromatic, alicyclic or cycloaliphatic, and aliphatic flame retardants. Increasing Flame Retardant Efficiency wn Ce cr cl Ol ‘cl 4 x Aromatic Alieyctic Aliphatic z-0-2 Increasing Thermal Stability Figure I. General relationship between flame-retardant efficiency and thermal stability for the three groups of chlorine-containing flame retardants. 89Aliphatic Chlorine Compounds ‘The most efficient class of flame retardants, the aliphatic chlorine compounds, is represented by the chloroparaffins, which are employed as flame-retardant additives fora variety of polymers, including flexible vinyl. PVC is inherently flame retarded by virtue ofa 56 percent chlorine content, and rigid PVC is sometimes blended with other resins for this feature. With plasticizer addition essential for flexible vinyl applications, { however, the inherent flame retardancy is lost and must be restored by flame-retardant additives such as antimony oxide, chloroparaffins, and phosphorus plasticizers. The aliphatic chlorine compounds, which must be processed under 175°C Aromatic Chlorine Compounds ‘The chlorinated bi- and poly-phenyls are the principal members of the chloroaromatic group. The simplest member--decachlorodiphenyl--is shown in Figure 2. These compounds have never - nonas+ a0 RoR+c2 —m RCHOS OH FLAME POISONING er =~ Bee +RCHS > RCH «+ Hor Wars On — Haa+er = Figure 1 The polymer substrate has a temperature at which it will ignite with the application of flame or auto-ignite without direct flame contact. From the above mechanism the brominated flame retardant must release the bromine into the flame front. The most effective flame retardant for a particular organic polymer system will release the bromine early in the fire scenario as the substrate is beginning to burn. If the bromine is released later it will be much less effective. Thermogravimetric analysis (TGA) is one way to represent the temperature range over which the brominated flame retardant decomposes. 107‘Thermogravimetric Analysis 0 100 = 200 300 400 50000700 ‘Temperature (C) 10 Degrees C/min. Ramp Rete Figure 2 The majority of the brominated flame retardants decompose between 200°C and 400°C. This range correlates well for the ignition temperatures of a broad spectrum of organic polymer systems. (8) The selection of flame retardants for an organic polymer system often involves matching the decomposition temperatures. Figure 2 shows the temperature ranges where significant bromine release occurs for five different brominated flame retardants. For a resin system which has a low ignition temperature such as polystyrene or polyolefin, choices might include hexabromocyclododecane (HBCD) or tetrabromcbisphenol A (TBBPA) as potentially the most efficient. Polydibromostyrene (PDBS) would likely be more appropriate for materials with higher ignition temperatures such as nylon. The TGA data in Figure 2 also is a guide for selection of flame retardants where the resin system is thermoprocessed such as in compounding of a thermoplastic or curing of a thermoset. The bromine must not be released from the brominated flame retardant during that processing. 108Therefore one would not use HBCD in a nylon which processes at 240°C - 300°C. PDBS has sufficient thermal stability for nylon processing temperatures. It is a common practice to use synergists in formulations to improve the flammability performance of brominated flame retardants. The most broadly used synergist for brominated flame retardants is antimony trioxide (9). BROMINATED FLAME RETARDANTS One view of brominated flame retardants is that their function is to carry the active component, bromine, into a formulation. Conceptually one would look’ for molecules which might carry the highest weight percent of bromine in a usable form which would be incorporated as an additive. Representatives of this type of family are shown in Figure 3(10). ee pr Decabromodiphenyl oxide Op 6) er aaa Me D095 vA P ccnromosbien on pereenrayeeerye Me ry Con Pontabromodiphony! oxide Be 70.8 Liquid r ry (xey=5) Figure 3 Diphenyl Oxide Pentabromodiphenyl oxide is used in polyurethane systems where a liquid additive is desirable. Octabromodiphenyl oxide is used in acrylonitrile butadiene styrene copolymers (ABS) as it meltblends into the resin giving better physical properties. Decabromodiphenyl oxide is used for polyethylene because of the high bromine content. This family of flame retardants is used in different applications hased on their unique features. 109Another approach is to brominate a reactive building block of the polymer. An example bisphenol A can be brominated to make tetrabromobisphenol A (Figure 4). This is reacted into epoxy resins commonly used in circuit boards or used in ABS systems as an additive flame retardant. It is further converted into families of brominated epoxy oligomers and brominated carbonate oligomers. These are used in a variety of thermoplastics from ABS to polybutylene terephthalate (PBT). Other derivatives include the bis dibromopropyl ether derivative to efficiently flame retard polypropylene (PP). 0 Hs oH Totrabromobisphenol A Brominated Epoxy Oligomers %Br 50-55 Brominated Carbonate Oligomore % Br 52-58 OiCeorsy Tetrabromobisphenot A bis(2,3-dibromopropy! ethos) 2 Br 67.7_MP 90-1006 Figure 4 Bisphenol A Pontabromobenzy! acrylate Br Tetrabromophthalic ‘TBS Anhydride Figure 5 Reactive 110Other reactive flame retardants commercially available are shown in Figure 5. One is tribromophenol which is a reactive building block for a family of flame retardants including an oligomer used in nylon and a phenoxyethane derivative for more UV stable styrenic applications (Figure 6). Poly-dibromophenylene Oxide CO % Br 62.0 MP 210-2406 bis (Tribromophenoxy) othano % Br 70.0 MP 223-2286 Figure 6 Tribromophenol Derivatives Bromostyrenics, dibromostyrene (DBS), and tribromostyrene (TBS), can be copolymerized, homopolymerized, or grafted to various resins. Reactive flame retardants remain the focus of developmental programs for a broad spectrum of polymers and applications. Putting the bromine into the backbone of an organic polymer systems potentially lead to better physical properties, processability and performance. A family of brominated polystyrene flame retardants are used in nylon and other engineering thermoplastics. Pentabromoacrylate is a reactive flame retardant which could be used as a building block for the creation of new flame retardants or copolymerized into a polymer backbone. The homopolymer is proposed for use in thermoplastic polyester and nylon. Tetrabromophthalic anhydride is reacted into the unsaturated polyester by the resin supplier to create a brominated resin system(11). It is also the key building block for additive types shown in Figure 7. 12aof ‘Totrabromophthatate diol SoHcHOCHICHOH Br 46.0 Liquid aT gocregrers oon e 8 ok Br o cH, —N er = or & 0 s = Ethylonobidtetrabromophthalimide % Br 67.2 MP 445-4586 Figure 7 Tetrabromophthalate Derivative: The diol derivative finds significant use in rigid polyurethanes, The bisimide derivative is used in polyolefins, styrenics and PBT where bloom, UV stability or thermal stability are required. There is also a phthalate ester derivative finding use in PVC wire and cable applications. Figure 8 shows two aliphatic materials with significant uses, HBCD and dibromoneopentyl glycol {DBNPG) . Br oo Hexabromocyclododecane eb ome %eBr 74.7 MP 185-197 C he ok er bom, GiizoH Dibromoneopenty! glycol BiG 6 CHO %Br605 MP 109C CHB Figure 8 Aliphatic 112Aliphatic bromine generally releases from the molecule at lower temperatures than aromatic bromine. HBCD is successfully used in expanded polystyrene. Low temperature release in polystyrene foam results in high efficiency. Peroxide synergists can be used as part of the system to hasten the degradation of the polymer. DBNPG is reacted into polyurethanes and unsaturated polyester systems. A monofunctional alcohol, tribromoneopentyl alcohol, TBNPA, is also available. Many of the above materials, whether reacted into the polymer or incorporated into resin systems as additives, are used in combination with other flame retardants. ‘These are often based upon phosphorous, chlorine, boron, and/or anhydrous minerals to meet specific performance needs. The body of formulations knowledge and the changing needs for flammability and properties of the finished goods provide the opportunities for future flame retardants. Brominated flame retardants will continue play a significant role in that future. MANUFACTURERS The list of brominated compounds used as flame retardants grows as new requirements are identified in the marketplace. Table II shows some of the major brominated flame retardant suppliers. Some are vertically integrated back to the extraction of bromine while others see opportunities from their raw materials base or their technology base. Other companies, such as FMC, not included in this list see opportunity in offering in single molecules the combination of bromine and phosphorus. This is the era of globalization where the compounding or formulations development may take place in the same community or in another part of the world. The suppliers are continually challenged to respond to this globalization while remaining responsive to regional requirements. 113Table II 0 TT Brominated Flame Retardant Suppl: Great Lakes Chemical Corporation Albemarle Dead Sea Bromine (Ameribrom) Ferro Bkz0 Elf Atochem Dic DKS Teijin Tosoh (6) Suppliers generally offer formulations recommendations for use of their flame retardants to achieve certain levels of both flammability and other performance criteria. It is from the dialogues among the end-user, the formulators, the regulatory bodies and the flame retardant manufacturers that new opportunities arise. A change in availability of a resin such as polycarbonate or other key raw material such as glass can cause a shift in demand for a specific type of flame retardant. Manufacturers remain alert to these changing demands and continue to participate in this ever changing marketplace. ale1, Jolles, Z.E.,Edt. Bromine And Its Compounds, pp3, Academic Press, New York, 1966. 2. Lyday, P.A., “Bromine Annual Review 1994", ppl, U.S. Department of the Interior Mineral Industry Surveys, Washington, D.C. 1995. 3. Jolles, 2.E.,Edt. Bromine And Its Compounds, pp20, Academic Press, New York, 1966. 4. Bromine, pp719.1000C, Chemical Economics Handbook, SRI International, 1995. 5. Lyday, P.A., "Bromine Annual Review 1994", ppl, U.S. Department of the Interior Mineral Industry Surveys, Washington, D.C. 1995. 6. Bromine, pp719.1000E-H, Chemical Economics Handbook, SRI International, 1995. 7. Lyons, J.W., The Chemistry And Uses Of Fire Retardants, ppl5, Wiley-Interacience, New York, 1970, 8. Cullis, C.F., "Bromine Compounds as Flame Retardants", Procedings International Conference Fire Safety, pp310, 9. Lyons, J.W., The Chemistry And Uses Of Fire Retardants, pplty Wiley- Interscience, New York, 1970,— 10, Nametz, R.C., "Bromine Compounds For Flame Retarding Polymer Compositions Partl: Thermoplastics", Plastics Compounding, pp26-39, July/August, 1984. 11, Nametz, R.C., "Bromine Compounds For Flame Retarding Polymer Compositions PartII: Thermosets", Plastics Compounding, pp54-66, September/October, 1984. 11sBORON COMPOUNDS AS FIRE RETARDANTS K.K. SHEN, Ph.D. and D. J. FERM US. Borax Ine. 20877 Tourney Rd. Valencia, California INTRODUCTION Boron compounds such as borax and boric acid are well known fire retardants for cellulosic products (1,2), However, the use of boron compounds such as zine borate, ammonium pentaborate, boric oxide, and other metallo-borates in the plastics industry has become prominent only since the late 1970's. This paper will review the manufacturing, chemical and physical properties, end-use applications, as well as mode of actions of major inorganic boron compounds as fire retardants THE ORIGIN OF BORON Boron is present in the earth’s crust at a level of only 3pm, but there are areas where it is concentrated as borate salts (salt of oxidized form of elemental boron) in substantial volume for mining, The United States and Turkey supply 90% of global borate demand. U.S. Borax Inc., the largest U.S. borate producer, operates an open pit mine and refinery complex at Boron in the Mojave Desert of California. The principal minerals in the deposit are tincal and kernite (Table I). U.S, Borax produces sodium borate products (borax decahydrate, pentahydrate and anhydrous borax) from tincal ores. Kernite is used to produce borie acid and boric oxide, Etibank, a state-owned Turkish mining and banking group, offers borate minerals (colemanite and ulexite) and refined borates. THE PRODUCTS Table II lists properties and applications for various types of boron-containing fire retardants. 137Borax Pentahydrate (Na;0'2B;05'SH,O )- Commercially borax pentahydrate is produced by conventional extraction and recrystallization from the sodium borate mineral tincal (Na:0-2B;05"10H20 ). Due to its low dehydration temperature and water solubility (4.4%), ithas been used mainly as a fire retardant in cellulosic products (Fig. 1). Its use as a fire retardant in urethane foams was also reported in several patents (3). The anhydrous form of ‘the material ('Na;O*2B.03 ) is also commercially available, but its potential as a fire retardant in plastics has not been fully explored. Boric Acid (B(OH), )- Boric acid is an important precursor of other boron-containing fire retardants. It is produced by reacting a borate mineral such as kernite ('Nax0-2B;03'4H.0 ) or colemanite with sulfuric acid. ‘Na,0-2B05'4H,0 + H;SO,+H,0 —> 4 B(OH); + Na;SO, Due to its low dehydration temperature and water solubility (4.7%), boric acid is mostly used asa fire retardant in cellulosic products such as cellulosic insulation, cotton batting, and medium density fiberboard. Its use in urethane foams has also been reported Boric Oxide ( B:0s )- Boric oxide, also known as anhydrous boric acid, is produced commercially by calcining boric acid. This material has been reported to be an 260 - 300°C 2 B(OH): —————> B,03+ 31:0 effective fire retardant in engineering plastics such as high impact polystyrene, polyetherketone, and polyetherimide (4). More recently, boric oxide, when used in conjunction with red phosphorous, was also reported to be an effective fire retardant in fiberglass reinforced nylon 6,6 (6). Boric oxide softens at about 325 °C. It is, however, hygroscopic and can absorb water and revert back to boric acid but without losing its fire retardant efficacy. Disodium Octaborate Tetrahydrate (Na,0-4B,0;'4H,0 )- This sodium borate is produced from a solution of boric acid and borax. It is an amorphous material and thus can be dissolved into water rapidly (solubility 9.7 wt.% at room temperature). It is used mainly as a fire retardant for cellulosic materials. Ammonium Pentaborate ( (NH.),0-SB:0,'8H,O )- The product can be produced by reacting ammonium hydroxide and boric acid. It has been used as a fire retardant mostly in urethane foam and epoxy, This material releases its water of hydration beginning at about 120°C and releases ammonia beginning at about 220 °C (Fig. 2). Its usage in polymers, however, is limited by its high water solubility (10.9%) and low dehydration temperature. 138Barium Metaborate ( BaO-B:03:H:0 )- It can be produced from borax and barium sulfide, and finds use primarily as a corrosion inhibitor and fungistatic pigment in coatings. This material is also claimed to be a fire retardant in plastics, but its efficacy is not as good as that Of zine borates, Its usage in plastics is also limited by its low dehydration temperature (200 °C). Zinc Borates- This is the most important class of boron compounds used as a fire retardant in the plastics and rubber industries. Zinc borate was the essential ingredient in a US Navy linseed oil-based fire retardant paint specification during World War II, but thereafter this use lapsed until zinc borate of differing composition with a much better thermal stability became commercially available. Zinc borate is commercially produced by reacting either boric acid or sodium borate with zine oxide. Depending on the reaction conditions, a host of zinc borates with different mole ratio of Zn0:B0;:H0 can be produced. In carly 1970, U.S. Borax discovered and patented a unique form of zinc borate with a molecular formula of 2Zn0:3B,053.5H:0 (or 4Zn0°6B,03'7H20) (Fig. 3). In contrast to other commercial zinc borates such as 2Zn0-2B,0;'3H0, it is stable up to 290 °C and is suitable for use even in engineering plastics such as nylons (6-9). 2Zn0 + 6 B(OH); ——+ 2Zn0-3B,0;3.5H;0 + 5.510 Recently U. $. Borax discovered another unique zine borate - 4ZnO-B:0s"H20 - which is stable up to 415 °C and suitable for use in engineering plastics processed at temperature j above 290 °C (10). FIRE RETARDANT MECHANISM OF BORON COMPOUNDS For cellulosic systems, borate fire retardants (such as boric acid, borax pentahydrate, and disodium octaborate tetahydrate) act by endothermic release of water and melting to form sodium borate or boric oxide coating. Chemically, borates also can react with the C6- hydroxyl group of cellulose polymer to give a borate ester and blocking the release of flammable C-6 fragments. In addition, dehydration of alcohols is enhanced by boric acid, which accounts for the larger quantities of char produced when borate treated cellulose is | burned. Boric oxide, or any precursors such as boric acid which can form boric oxide under fire conditions, is well known to reduce afterglow combustions. It is generally believed that boric oxide, a low melting glass, can cover the char and inhibit oxygen permeation, and thus prevent oxidat ion of the char. Another school of thought believes that effectiveness of boricoxide in afterglow suppression is related to its high ionization energy/or electron affinity; active sites for oxygen adsorption on the char surface may be deactivated by boric oxide via electron transfer (11). Ammonium pentaborate, upon thermal decomposition, can evolve large amounts of water, ammonia, and boric oxide which is a glass former. Ammonium pentaborate functions as both an inorganic blowing agent and a glass forming fire retardant. 120-450 °C (NH,),0°5B,03'8H;0 —————> 2NH; + 9H,0 + 5B,03 Zinc borate, in halogenated systems such as flexible PVC, is known to markedly increase the amount of char formed during polymer combustion, whereas the addition of antimony ‘oxide, a vapor phase flame retardant, has little effect on char formation. Analysis of the char shows that about 80-95% of the antimony is volatilized, whereas the majority of boron and zinc from the zinc borate remain in the char (80 and 63%, respectively) (12). The fact that the majority of the boron remains in the condensed phase is in agreement with the fact that boric oxide is a good afterglow suppressant. The zinc species remaining in the condensed phase can alter the pyrolysis chemistry by catalyzing the dehydro-halogenation and promoting cross-linking, resulting in increased char formation and a decrease in both smoke production and flaming combustion, The boric oxide released can promote the formation of a strong, char and, more importantly, can stabilize the char In halogen-free systems, it was reported that zine borate in conjunction with alumina trihydrate promotes the formation of a porous ceramic residue during polymer combustions. This residuc is an important thermal insulator for the underlying substrate or unburned polymer. Both Differential Scanning Calorimetric and Differential Thermogravimetric analyses, as well as char yield analysis suggest that partial replacement of alumina trihydrate with zine borate in a halogen-free polymer such as ethylene-vinyl acetate can favorably alter the oxidative-pyrolysis chemistry of the halogen-free base polymer (7), PRODUCERS AND TRADE NAMES Table III lists major U.S. producers and trade names of boron-based fire retardants. 140REFERENCES Lyons, J.W., The Chemistry and Uses of Fire Retardants, Wiley-Interscience, NY 1970. Sprague, R.W. and K. K. Shen, Journal of Thermal Insulation, 2,161 (April 1979). Ishikawa, Takashi, Japan Kokai, 76, 124, 195, (1975), Lohmeijer, JH., et. al., European Patent Application 0 364 729A1 (1990). Sylvie, Bodrero and Rene Dien, French Patent 93 04093 (1993), Shen, K.K. and T-S. Griffin, ACS Symposium Series 425, “Fire and Polymers” p.157 (1990), Shen, K.K., Plastics Compounding, (Sept /Oct. 1985), Shen, K.K., Plastics Compounding, (Nov-Dec. 1988) 9. Ferm, D.J. and KK. Shen, Proceedings International Conference on Fire Safety, San Francisco, 17, 242 (1992) 10. Schubert, D., U.S. Patent 5,342,533 and 5,472,644 (1994), 11. Rakszawski, IF, and W.E. Parker, Carbon, 2, $3 (1964). 12. Shen, K.K. and RW. Sprague, Journal of Vinyl Technology. No._3,120 (1982). aeee ope eS ‘Table I. Principal Borate Minerals (Ore Name Formula B,0.* Source Tincal Na,0-2B,05+10H,0 36.5 United States, Turkey Colemanite ~ 2Ca0+3B;0s+5H,0 $0.9 Turkey Kernite Na,0*2B,05+4H;0 50.9 United States Ulexite NazO*2Cx0°5B20;"16H20 43.0 Turkey, Chile Hydroboracite CaQ-Mg0*3B;05+6H,0 $0.5 Argentina Szaibetyite 2Mg0'B20;+H,0 414 Russia * Theoretical maximum percent. 141‘Table II. Boron Based Fire Retardant Products Starting Detydration ‘Water Solubility Chemical Name Temperature °C (ovt.% around 20° C) Applications Borax Pentahydrate 6 44 Paper products and wood (Na;0*2B205*5H:0) composite board. Boric Acid nm 47 Paper products, cotton batting (U:B0:) and wood composite board, Boric Oxide ~ 26 Engineering plastics ~ 0s) Disodium Octaborate 40 97 Paper products Tetrahydrate (Na:0+4B,05+4H,0) Ammonium Pentaborate 120 10.9 ‘Urethane, epoxy and other ((NH4),0+5B,05+8H.0) coatings. Barium Metaborate 200 Od Flexible PVC and coatings. (Ba0-B,0;-H1,0) Zinc Borates 290 02 PVC, polyolefins, nylon (2Zn0+3B;03+3.5H,0) silicone, urethane, unsaturated polyesters, and elastomers. (2Zn0+2B;0;3H,0) 190 02 PVC (4Zn0*B,03+H:0) 4is 0.05 Engineering plastics (2Zn0+3B;03) - 02 Engineering plasticsTable IML. Major U.S. Producters of Boron-Based Fire Retardants Trade Name Producer Composition Ammonium Pentaborate US. Borex (NEL)20-5B,05-81,0) Boric Acid US. Borax B(OH); NACC Boric Oxide US. Borax B,0; Bulab Flamebloc Buckman Lab BaO*B,03"H20 Firebrake® ZB US. Borax 2Zn0+3B205+3.SH:0 Firebrake® 415 US. Borax 4ZnO-B,0;1,0 Firebrake® 500 US. Borax 2Zn0+3B03 Neobor® US. Borax NaO*2B203°5 H:O Polybor® US. Borax NazO0+4B,0;¢4 H:0 ZB-467 Anzon 4Zn0-6B,0}+7H:0 28-223 Anzon 2Zn0+2B30y+3H;0 V-Bor ACC Na,0*2B203*5H;0 143bet Weight Loss (%) 90 a0 70 60 50 40 Fig. 1. TGA of Borax Pentahydrate and Boric Acid Borax Pentahydrate (Na,0*2B,03*5H,0 ) Boric Acid (BOH)s) Heating Rate 5°C/min, —_—_——, 169 200 300 400 500 600 Temperature (°C) 700SbT Weight Loss (%) 2. TGA Analysis of Ammonium Pentaborate 100 90 80 . Ammonium Pentaborate ((NH,):0°5B;0;°8H,0 ) 70: 60. 50 Heating Rate 5°C/min 40 ° 100) 200 300 400 500 ‘600 700 Temperature (°C)got 105 100 95 Weight Loss (%) 8 85 80 0 Fig. 3, Thermogravimetric Analysis of Zinc Borates Heating Rate 10°C/min. (2Zn0*3B,0;) (4ZnO*B,05°H,0) (2Zn0*2B.0393H-0) (22n0*3B203*3.5H20) 1 1 1. 1 1 . 100 200 300 400 500 600 700 Temperature (°C)MINERAL HYDROXIDES — THEIR MANUFACTURE, AND USE AS FLAME RETARDANTS WILLIAM E. HORN, JR. AND TERRANCE R. CLEVER Alcoa Industrial Chemicals. Alcoa Technical Center, Alcoa Center, PA and Arkansas Operations, Bauxite, AR INTRODUCTION Mincral hydroxides are an imporiant class of flame retardants, accounting for more than 50% of the volume (by weight) of flame retardants sold in the world (1,2). ‘This is due in part to their relatively low cost, but also because they are easily handled and relatively nontoxic. Mineral hydroxides provide flame retardant formulations that meet the appropriate standard tests for the application (3-5) and produce combustion products of low opacity, toxicity and corrosivity (4-6). When properly compounded (7,8), formulations containing these flame retardants offer a cost effective means to achieve low smoke, flame retardant formulations with a low propensity for nonthermal fire damage (9,10). ‘The two major mineral hydroxide FRs are aluminum trihydroxide and magnesium hydroxide. Smaller amounts of brucite, huntite and hydromagnesite are also sold for this purpose. ALUMINUM TRIHYDROXIDE (ATH) Aluminum trihydroxide, or ATH, is appropriately written as Al(OH)3. Sometimes this ‘material is called alumina trihydrate or hydrated alumina and is written as Al;O3¢3H20. This is erroneous as ATH is neither an alumina nor a hydrate. Aluminum wihydroxide is usually obtained from bauxite ore using an extraction process (11-14). Bauxite ore contains 40-70% aluminum minerals consisting mostly of Gibbsite and Boehmite. Gibbsite is a crystalline form of ATH. Boehmite is aluminum hydroxide oxide, OAIOH. These ores also contain many mineral impurities including silicates, iron and titanium compounds and organic compounds especially humates. The Bayer process, developed by Dr. Karl Joseph Bayer (15), is a low cost procedure widely used to extract caustic soluble aluminum compounds from the bauxite, It involves digesting crushed bauxite ore with concentrated sodium hydroxide solutions at temperatures between 125°-280°C. ‘The chemical reactions involved are: AI(OH)3 + NaOH = AI(OH) 3 +Nat OAIOH + H;0 + NaOH + Al(OH) 3 + Nat 147‘The sodium aluminate solution obtained in the Bayer process is filtered to remove solid impurities, The ATH is precipitated by cooling the stirred solution. The specifics of the process vary among the various manufacturers of ATH. The general process is outlined in Figure I. Figure 1 Bayer Process to Manufacture ATH The product obtained is a coarse Gibbsite with a particle size of 2 50 jum which can be used as is or sold for chemical uses such as the production of alum, ground to produce finer particle sizes of ATH (ground Bayer hydrate) or redissolved and precipitated to produce a more highly purified grade of ATH precipitawe (white hydrate). Ground Bayer hydrate represents the largest volume of ATH sold to the flame retardant market. The ATH can be ground to particle sizes ranging from 1.5 to 35 um depending on the grinding and classification equipment used (14,16,17). Either wet or dry milling is used to produce ground ATH. A wide variety of mills can be used depending on the particle size desired. Classification produces materials with narrower particle size distributions for specific applications. Blending is done to further customize products when necessary. A small percentage of ATH is surface weated to improve Ca(OH); + Mg(OH)2 ‘Ca(OH2) + Mg(OH)2 + MgCl2 >2Mg(OH)2 + CaClr Seawater B Dolime + 1,0 > Saked Dolime ———=—P> M (OND, Slurry Settle Filter M000, Carle Mg(OH), Dry Figure 2 Production of Mg(OH); from Brine or Seawater ‘The Aman process uses a concentrated MgC'lz brine solution as its magnesium source. ‘The solution is hydropyrolyzed to produce a mixture of magnesium oxide and alkali chloride salts. This mixture is treated with water to produce magnesium hydroxide, hydrochloric acid and soluble alkaline salts. The Mg(OH)2 is filtered, washed and dried. The hydrochloric acid is used for other chemical processes. The alkaline salts are returned to the brine source. ‘This process is practiced by Dead Sea Periclasc (22-24). The process is shown in Figure 3. The ‘chemical reactions involved are: MgCl) +H,O > MgO+2HCI ooo'e MgO + H20 — Mg(OH)2 Hydropyrotysis ‘MgC, Brin PS > Crude MgO + HCI + aC igCh, Tan Resa PH Crude MgO + HCI + Ca, K, NaCl hydrolysis Settle Fi M0, << Crude Mg(OH), Figure 3 Production of Mg(OH); by the Aman Process 150‘The Magnifin process uses serpentinite as its magnesium source. The mineral is leached with hydrochloric acid to convert the magnesium into the chloride. The impurities are removed by precipitation and the purified magnesium chloride liquor is roasted to produce MgO which is hydrolyzed to produce purified magnesium hydroxide. The hydrochloric acid is recycled to the process. The process is shown in Figure 4. The reactions involved are: ‘Mg[SiOs](OH)4 + 6HCI — 3MgCl; + SiO2 + SH2O 3MgCh + 3H;0 — 3MgO + 6HCL et 3MgO + 3H;0 — 3Mg(OH)2 Leach Newralie ici + Serpentine —FHE pe Liquor 28022 gc, Satin Preps ° Filter Concentrate Hydropyrolyze Wash Hydro MgOHn, << — Crude MOH), <— Mgo + HCL Dry Figure 4 Production of Mg(OH); from Serpentine ‘The magnesium hydroxide used for flame retardant applications is generally of high purity. Most FR grades are white powders ranging in median particle size from 0.5-5 im. Surface areas can range from 7 to greater than 15 m2/g depending on the particle shape and size. Most magnesium hydroxides sold for flame retardant applications are surface ueated 10 improve dispersion and physical property retention, Like ATH, magnesium hydroxide is used athigh loading levels usually between 50 and 70% (2,22-25,28). Because of their high purity and surface treatment requirements, flame retardant grades of magnesium hydroxide are more expensive than precipitated ATH. ‘Due to their higher decomposition temperature and cost, magnesium hydroxides are generally used in thermoplastic and thermoset resins that are processed above 200°-225°C. They find use in polypropylene and PP blends, polyamides and polyamide blends, ABS and ABS blends, in fluorocarbon polymer blends, in polyphenylene oxide/polystyrene alloys, in polyimides and in the aliphatic polyketone, Carilon® (Carilon is a registered trademark of Shell) (29). End use applications are in wire and cable, appliance housing, construction laminates, piping and electrical components. As with ATH, a wide variety of magnesium hydroxides are commercially available to meet the requirements of the application, OTHER FLAME RETARDANT MINERALS. In addition to ATH and magnesium hydroxide, other minerals are used as flame retardants. ‘These materials are mined, crushed, ground and classified, They may be beneficiated or refined further to improve color or remove unwanted impurities such as iron, They ean be 1sisurface treated to improve polymer compatibility. Such treatments are generally kept to a ‘minimum as these products are aimed at the lower cost applications. Brucite is a naturally occurring form of magnesium hydroxide, Its color and purity vary depending on the quality of the ore. It is usually not as thermally stable as refined magnesium hydroxide because of the impurities present in the mineral. It is also less costly. It is usually used where color is not critical, though high whiteness brucites are available (2,22,23), Hydromagnesite is a mixture of magnesium carbonate and magnesium hydroxide (@MgCO;eMg(OH),¢3H,0). It is a naturally occurring mineral found in Greece. It is sold commercially in combination with huntite, Hydromagnesite decomposes between 220°-240°C, but the mixtures are somewhat more stable (2,30). Huntite is a mixed magnesium calcium carbonate (Mg3Ca(COs)4) which is used for high temperature FR applications. It is stable to 450°C. Being a carbonate, it does not possess the same flame retarding characteristics of a hydroxide but can be used for applications where thermal stability is important, Huntite-hydromagnesite mixtures are commercially available and finding new FR applications. Various blend ratios are available depending on the supplier. Surface treated grades are also available (2,30). Gypsum is hydrated calcium sulfate (CaSO4e2H 0). It is used as a flame retardant in unsaturated polyester tub and shower enclosures (3), FLAME RETARDANT MECHANISM | ‘The mineral hydroxide flame retardants decompose when heated, releasing water into the vapor phase. This elimination of water is endothermic and allows the substrate to remain below its ignition temperature for the duration of the hydrate decomposition. The water is released into the vapor phase along with other gases of decomposition, diluting the amount of fuel available (2,26). ‘The decomposition of the hydrous materials produces an oxide residue which has a relatively high heat capacity, reducing the amount of thermal energy available to } further degrade the substrate (16,26,32). 2AM(OH)3 > AlzO3+3H;0 1500 /g Mg(OH), +MgO+H20 1600 /g ‘The residual oxides form a ceramic-type layer which further protects the substrate (26,32). ‘The oxide also is a good adsorbent and has potential catalytic activity. To achieve good flame retardant response, the mineral hydroxides arc usually used at levels above 50% by weight of the substrate. This also reduces the amount of combustible material available for degradation. The result is an overall net reduction in the mass burning rate of the substrate containing the hydroxides (3-5,33). In addition to inducing flame retardant properties to polymers, the mineral hydroxides also reduce the amount of smoke generation exhibited on buming. Although not thoroughly understood, this phenomenon is associated with the adsorption of carbonaceous materials on the surface of the oxide residue and subsequent oxidation to CO; (26,32), The presence of an increased amount of water vapor in the combustion gases may also play a part in the ‘oxidation of carbon to COs. Because water is the only product of combustion, mineral 152hydroxides do not add significantly to the corrosive nature of the smoke generated during the ‘combustion of polymers containing them (6,9,10).. Because high loadings are required for hydrous minerals to be effective as flame retardants, ‘combinations with other flame retardant materials were examined to assess the potential synergy of the mixtures. ‘The use of small amounts of antimony oxide in combination with hydrous FRs are effective in reducing the amount of loading levels in flexible PVC wire and cable formulations (34). ‘Combinations of ATH and zinc borate are also effective in accomplishing similar reductions 34,35). In general, ton parts of ATH can replace one to two parts of antimony oxide. Adjusting the ratios of the two additives provides the optimal FR/physical property/cost performance. Zinc borate can replace ATH at a similar one to ten part replacement. This general rule is operative for both halogen and non-halogen containing formulations. ATH and magnesium hydroxide give improved performance when used together over a wide range of ratios (28,44). The effect is thought to be due to the increase in the range of ‘endotherm and release of water into the vapor phase. The resulting mixed oxide residue may also play an important role in this synergy. Combinations of hydrous minerals with molybdenum containing compounds reduce smoke emissions and increase flammability resistance, especially in PVC (31,34,35). Similar reports are made for combinations of mineral hydroxides and tin compounds (36,37). ATH and magnesium hydroxide coated with tin compounds are reported to be particularly effective in flexible PVC (37). ATH and red phosphorus offer potential synergy. While red phosphorus is used at low levels (3-5%), the addition of ATH increases the FR performance (38). Combinations of silicon containing compounds and hydrous mineral FRs reduce the amount of additives required to achieve flame retardant formulations (39,40) in a variety of polymeric susbstrates, ‘The mechanism of the interaction is not well understood. MANUFACTURERS OF HYDROXIDE FLAME RETARDANTS ATH The Aluminum Company of America (Alcoa) is the largest manufacturer of ATH in the world. They manufacture both Bayer and white hydrates for internal use and sale to grinders. ‘Alcoa produces precipitated ATH in the 0.25-2 micron particle size range. They grind ATH producing both Bayer and white ground products in the 3-45 micron range. Aleoa operates facilities around the world, Other primary manufacturers of ATH in the United States include Kaiser, LaRoche and Reynolds Chemicals. These producers sell Bayer hydrate to grinders. Alcan Aluminum produces both Bayer and white ATH in Canada and the United Kingdom Primary ATH producers around the world include Martinswerke, VAW, Pechiney, Alusuisse/Lonza, Nabeltec, Showa Denko, Sumitomo and Nippon Light Metal. Most produce precipitated and ground products, J. M, Huber's Engineered Minerals Division is a major grinder of ATH in the United States. Other companies grinding ATH in the U.S. include Aluchem, R. J. Marshall, Georgia Marble, Franklin Minerals, Hitox and Custom Grinders. Incemin is a grinder of 153ATH in Europe. All offer a wide variety of products and most have surface treated grades. Other companies also supply ground ATH. Magnesium Hydroxide ‘The major producers of magnesium hydroxide for flame retardant applications are Kyowa Chemical (Japan), Magnifin (Austria) and Dead Sea Periclase/Dead Sea Bromine Israeli joint venture. Morton International produces magnesium hydroxide and magnesium hydroxycarbonate in the U.S. Martin Marietta now has a line of magnesium hydroxide flame retardants in the U.S. (2). Incemin (Switzerland), Alcan Chemicals Europe and Solem Division of J. M. Huber Engineered Minerals are major grinders of magnesium hydroxide. Smaller companies also offer ground magnesium hydroxide. Other Mineral Flame Retardants i Incemin offers ground brucite, huntite and hydromagnesite/huntite mixtures. Microfine Minerals also grinds a hydromagnesite/huntite blend. The blends produced by Incemin and Microfine Minerals have different compositional ranges and find application in different markets (30). R. McMinerals offers ground brucite in the U.S. Morton International offers magnesium hydroxycarbonate, LATE DEVELOPMENTS Although mineral hydroxides have been used as flame retardants since the 1960s, their use is growing as polymer producers and compounders look for altematives to conventional flame retardants. The demand for improved performance has spurred the development of new grades of existing products, the development of new compositions of matter and an increase in the number of companies offering FR grades of mineral hydroxides. ‘The blending of ATHs to produce materials that develop less viscosity on compounding and the introduction of new surface treatments that offer improved physical property retention and improved processibility are examples of such improvements (18,28). Martin Marietta has introduced their first FR grade of magnesium hydroxide (2,41). Queensland Metals Corp. Ltd. and Mines de Lucette have formed a joint venture to produce and market magnesium hydroxide. Premier Periclase Ltd. has just announced they are entering the same market (2). Anew chemically modified ATH, which is stable to 330°C, has been developed by Alcoa (42,43). All materials are currently being test marketed, CONCLUSIONS Mineral hydroxide flame retardants offer a wide variety of materials for application in almost every market. They can be used in thermosets, thermoplastics, elastomers, engineering resins, paints, caulks, adhesives, backcoating, mastics and paper products. They can be used. 154at processing temperatures of up to 400°C. All are relatively nontoxic. 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