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Flame Retardant Additives for Coatings, Plastics, and Adhesives

Flame Retardant Additives for Coatings, Plastics, and Adhesives. by Walter Conti BUCKMAN LABORATORIES, INC. 1256 North McLean Blvd. Memphis, TN 38108-1241 1-800-282-5626. Mission.

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Flame Retardant Additives for Coatings, Plastics, and Adhesives

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  1. Flame Retardant Additives for Coatings, Plastics, and Adhesives by Walter Conti BUCKMAN LABORATORIES, INC. 1256 North McLean Blvd. Memphis, TN 38108-1241 1-800-282-5626

  2. Mission • “We, the associates of Buckman Laboratories, will excel in providing measurable, cost-effective improvements in output and quality for our customers by delivering customer-specific services and products, and the creative application of knowledge”

  3. Flame Retardant Additives for Coatings, Plastics, and Adhesives Buckman Laboratories

  4. Definition of FIRE • Fire is one of the 4 Elements: EARTH, AIR, FIRE and WATER. • By Webster, Fire is defined as: • A Rapid, persistent chemical reaction that releases heat and light, esp. the exothermic combustion of a combustible substance with oxygen.

  5. Fire Flashover

  6. Upholstered Chair Fire (elapsed time 4:50 min/sec)

  7. TV/ Low Level Ignition (not flame retarded)

  8. TV/ Low Level Ignition (flame retarded)

  9. Introduction • Almost anything will burn. • The objective of flame retarding is to increase the resistance of a product to ignition and to reduce flame spread. Thus, the use of a flame retardant may prevent a small fire from becoming a major catastrophe.

  10. Introduction (con't.) • A National Bureau of Standards (U.S.) study comparing fire retarded and non-fire retarded products concluded that fire retardant additives decreased the overall fire hazard of their host products.

  11. FIRE Statistics • US has one of the highest fire death rates in the industrialized world • More than 2 million fires reported each year / cost of 8.1 billion dollars • Where fires occur in the home: • Kitchen 29% • Bedroom 13% • Living Room/Den 8% • Chimney 8% • Laundry Area 4% • Top causes of residential fires: • Careless Smoking • Arson • Alternative heaters • Cooking

  12. Determining the Fire Hazard of a Product • Factors needed to be considered in determining the fire hazard of a product are • Ignitability • Flammability • Heat released when burned • Heat release rate • Smoke obscuration • Toxicity of the smoke generated

  13. Flame Retardant Market • The overall market for flame retardant chemicals is controlled by government regulations, insurance underwriters, national or local building codes, special regulations and compliance with existing and anticipated standards. • Without these regulatory actions or mandatory standards, flame retardant chemicals probably would not be used to an appreciable extent.

  14. Flame Retardant Market (con't.) • Fire Retardant additives in • Plastics 9.4% • Adhesives 0.2% • Paints and Coatings 4.8% • Other 8.1%

  15. Desired Properties of a Flame Retardant • High Decomposition Temperature • Low volatility • Non-blooming or plate-out • Minimal effect on final physical properties • Low toxicity • (no single additive meets all these requirements)

  16. 3 Things are Needed to SustainFIRE • Flame • Oxygen • Fuel

  17. Phases in the course of a Fire

  18. Fire triangle (according to Emmons)

  19. Mechanisms of Flame Retardants • Endothermicity • Char former • Vapor phase

  20. ENDOTHERMICITY • Mode of action - heat absorber • Primarily utilize evaporative cooling provided by chemically bound water and diluting the oxygen in the gas-phase reaction • Examples • Alumina trihydrate and magnesium hydroxide • They are relatively inefficient • High use levels required comprimise products physical properties

  21. CHAR FORMER • Mode of action - Char former • As the material is broken down a char or carbon layer is formed. This char acts as a physical barrier excluding oxygen and fuel for the fire. • Examples • Barium/Calcium metaborates, phosphorus compounds, zinc borate. These products work best with a halogen donor of some sort (chlorinated resin, chlorinated wax, other synergistic flame retardant)

  22. VAPOR PHASE • Mode of action - Chemically inhibit flame • Free radicals generated during combustion are scavenged by halogens (which compete with oxygen - no oxygen, no flame) stopping the chain reaction of combustion. • Inexpensive • Examples • Halogenated materials (deca-brome type, chlorinated paraffin wax, phosphate esters, antimony tri and pentoxide)

  23. Major US Producers of Flame Retardant Chemicals ProductCompanyTradename • Alumina Trihydrate Alcoa FlameGaurd LaRoche Chemical Reynolds Metals Solem • Antimony Oxide Albermarle Anzon Cookson Laurel Fireshield, Thermogaurd • Boron Compounds Buckman Laboratories Flamebloc Climax US Borax Firebrake • Brominated Phosphates Ameribrom / Dead Sea Bromine Albermarle Saytex Ferro Great Lakes Chemical Firemaster, Smokebloc FMC • Chlorinated Cmpds Ferro Dover Chemical Occidental Pearsall • Chlorinated Phosphates Akzo Albright and Wilson • Molybdenum Cmpds AMAX Sherwin William • Phosphate Esters Akzo Monsanto

  24. Characteristics of Other Most Widely Used FR’s • Antimony Tri/Pentoxide (Sb2O3)- • Pros • Inexpensive Commodity (large price swings $1 - $3) • Fine particle size • Track Record in many materials and applications • Cons • May Cause “Antimony Measles” in workers • Halogen needed for optimal performance • High loading levels, possibly decreased physical properties • Higher product density • Most supply is imported (commodity, large price swings) • See Technical Data Sheet Example

  25. Characteristics of Other Most Widely Used FR’s • Zinc Borate (ZnBO3) - • Pros • Inexpensive • Similar RI of most thermoplastics (lower pigment levels) • Track Record in many materials and applications • Cons • High loading levels, possibly decreasing final physical properties • Halogen needed for optimal performance • High product density • Water of hydration

  26. Characteristics of Other Most Widely Used FR’s • Brominated Flame Retardant (BFR's) - • Pros • Cost Effective • Track Record in many materials and applications • Cons • Halogen (Bromine) • Brominated materials under scrutiny in Europe, US may follow • Not readily biodegradable - environmental issues

  27. Primary Industries Where Flame Retardants are Used • Wire and cable (electronic and other) • Appliances • Textiles • Coatings • Adhesives • Carpet Backing • Other

  28. Successes with Flamebloc Products in Plastics/Coatings • PVC (wire and jacketing) • Chlorinated Polyethylene (riser cable) • Nylon other engineering resins (part of FR package) • Polyester Pultrusion • Coatings / Intumesent coatings

  29. Benefits of Flamebloc Flame Retardants/Smoke Suppressants (con’t) • Flame Retardant / Smoke Suppressor • Data has shown that the smoke suppressant effectiveness can be as great as 50% or better (see data) • Four particle sizes to choose from • The theory is that you will get better dispersion in your polymer with a smaller particle size and more uniform distribution curve. Also, the increased surface area helps create more char.

  30. Benefits of Flamebloc Flame Retardants/Smoke Suppressants(con’t) • Does not noticeably degrade final physical properties of most finished products • Heat Stabilization Effect • Unlike products like Zinc Borate, that significantly degrade a polymer’s final physical properties, the Barium and Calcium Metaborates act as stabilizers and do not degrade the polymer’s final properties to that degree • Safer product (MSDS) than many of its competitors

  31. Benefits of Flamebloc Flame Retardants/Smoke Suppressants(con’t) • Reduced toxic smoke emissions and total smoke • The Flamebloc products keep the Peak Rate of Heat Release and Total Heat Release (cone calorimeter) low thus creating less combustibles and less smoke. Also the byproducts of BMB and CMB are less toxic than some of its counterparts. • Non-halogen

  32. Test Methods • There are many different tests for determining the degree of flame retardancy of materials. • The correlation of performance between test methods is poor. Therefore, a system that passes one test, might not pass or may need modification in order to pass a different test. • Following is a list of some of the more common test.

  33. Measuring Flammability/Smoke • The two most popular laboratory methods of measuring flammability are • UL -94 • Limited Oxygen Tests • While such small scale tests are useful for comparative studies, they do not predict the level of hazard in an actual room fire.

  34. Measuring Flammability/SmokeUL-94 • The UL-94 requirements cover tests for flammability of plastic materials used to manufacture parts in devices and appliances. They are intended to provide an indication of a resin’s flammability , and therefore acceptability for a particular application. • Tests: • Horizontal Burning Test; 94HB 20MM • Vertical Burning Test; 94V-0, 94V-1, or 94V-2

  35. Measuring Flammability/SmokeUL-94 (con't)

  36. Measuring Flammability/SmokeUL-94 (con't)

  37. Measuring Flammability/SmokeUL-94 (con't)

  38. Measuring Flammability/SmokeUL-94 (con't) • Tests: • Horizontal Burning Test; 94HB • 20 MW Vertical Burning Test; 94V-0, 94V-1, or 94V-2 • 500 MW Vertical Burning Test; 94-5VA or 94-5VB • Thin Material Vertical Burning Test;94VTM-0, or 94VTM-2… • Horizontal Burning Foamed Materials Test;934HBF, 94HBF-1, or 94HBF-2

  39. Measuring Flammability/SmokeOxygen Index • Oxygen index is the consumption of oxygen of a fire system related to a numerical value. The higher the value the better the flame retardant system may be. • Buckman Laboratories has this apparatus available in the lab.

  40. Measuring Flammability/SmokeOxygen Index (con't)

  41. Measuring Flammability/Smoke(con’t) • Methods for measuring smoke • Cone colorimeter • UL Steiner Tunnel Test (larger scale) • Although toxic gases are the major cause of fire deaths, it has been suggested that heat release rate is the single most important variable in characterizing flammability.

  42. Measuring Flammability/Smoke Cone Calorimeter • The cone calorimeter is an apparatus that measures the rate of heat release using the ‘oxygen consumption principle’, ignitability and smoke production.

  43. Measuring Flammability/Smoke UL Steiner Tunnel Test • This test analyzes the smoke produced by the burning of a material.

  44. Flame Retardant Chemicals Market • Projected Growth is 4% per year over the next five years • Flame retardants in the electronics market segment will grow the fastest at about 7.5%

  45. Current and Future Trends • Europe has moved to ban or curtail the use of brominated diphenyl oxide flame retardants because of the potential formation of highly toxic brominated furans and dioxins during combustion. • Reformulation to replace halogenated flame retardants with non-halogenated flame retardants.

  46. Current and Future Trends (con’t) • New co-polymerization of engineering thermoplastics • More rigid flame retardant requirements have been established for the upholstered furniture industry • Better flame and smoke reduction using non-halogen chemistry in the polyolefin arena

  47. Current and Future Trends (con’t) • Flame retardant blends (synergism's between different FR mechanism products) • i.e. Flamebloc products and antimony oxide

  48. Data Review Buckman Laboratories Cone Calorimeter Data on Plenum Wire and Cable Formulation

  49. PVC Cone Colorimeter Data and Graphs

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