1. Flame Retardant Additives for Coatings, Plastics, and Adhesivesby
Walter Conti
BUCKMAN LABORATORIES, INC.
1256 North McLean Blvd.
Memphis, TN

3. 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”

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

5. 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.

6. Fire Flashover

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

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

9. TV/ Low Level Ignition (flame retarded)

10. 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.

11. 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.

12. 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

13. 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

14. 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.

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

16. 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)

17. 3 Things are Needed to Sustain FIRE
Flame
Oxygen
Fuel

18. Phases in the course of a Fire

19. Fire triangle (according to Emmons)

20. Mechanisms of Flame Retardants
Endothermicity
Char former
Vapor phase

21. ENDOTHERMICITY Mode of action - heat absorber Examples
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

22. CHAR FORMER Mode of action - Char former Examples
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)

23. VAPOR PHASE Mode of action - Chemically inhibit flame Inexpensive
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)

24. Major US Producers of Flame Retardant Chemicals
Product Company Tradename
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

25. 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

26. 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

27. 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

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

29. 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

30. 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.

31. 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

32. 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

33. 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.

34. 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.

35. Measuring Flammability/Smoke UL-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

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

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

38. Measuring Flammability/Smoke UL-94 (con't)

39. Measuring Flammability/Smoke UL-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

40. Measuring Flammability/Smoke Oxygen 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.

41. Measuring Flammability/Smoke Oxygen Index (con't)

42. 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.

43. 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.

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

45. 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%

46. 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.

47. 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

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

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

50. PVC Cone Colorimeter Data and Graphs

51. Test Formulation

57. Summary Review of Data
Flamebloc 428/Antimony and the Busan 11-M1/Antimony combination had:
1. Longer times to sustained ignition 2. Lower Heat Release Rates 3. Lower Total Heat Released 4. Lower Total Smoke Generation 5. Better part physical properties
than the control or competitive materials (zinc borate or antimony)
All the above contribute to superior performance for Buckman products in plenum cable applications.

58. Buckman Laboratory Products for Flame and Smoke Reduction
Barium Metaborate Based
BUSAN 11M1
BULAB FLAMEBLOC
BULAB FLAMEBLOC 440
Calcium Metaborate Based
BULAB FLAMEBLOC 381
BULAB FLAMEBLOC 428
BULAB FLAMEBLOC 451

59. Buckman Laboratory Products for Flame and Smoke Suppression
This is a strategic business area for BUCKMAN LABORATORIES, Inc. We are committed to keeping our customers on the cutting edge of FR and SS with new products and technologies.

60. We’re More Than You’d Expect!
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We’re More Than You’d Expect!
1-800-BUCKMAN
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