Flame Retardant Additives for Coatings, Plastics, and Adhesives

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
(No Transcript)
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
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 450
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 9.4
• Adhesives 0.2
• Paints and Coatings 4.8
• Other 8.1

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
• 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
• 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
• 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 FRs

• 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 FRs

• 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 FRs

• 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 (cont)

• 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 (cont)

• Does not noticeably degrade final physical
  properties of most finished products
• Heat Stabilization Effect
• Unlike products like Zinc Borate, that
  significantly degrade a polymers final physical
  properties, the Barium and Calcium Metaborates
  act as stabilizers and do not degrade the
  polymers final properties to that degree
• Safer product (MSDS) than many of its competitors

32
Benefits of Flamebloc Flame Retardants/Smoke
Suppressants (cont)

• 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/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
  resins 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/SmokeUL-94 (con't)
37
Measuring Flammability/SmokeUL-94 (con't)
38
Measuring Flammability/SmokeUL-94 (con't)
39
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 Test94VTM-0, or
  94VTM-2
• Horizontal Burning Foamed Materials Test934HBF,
  94HBF-1, or 94HBF-2

40
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.

41
Measuring Flammability/SmokeOxygen Index (con't)
42
Measuring Flammability/Smoke (cont)

• 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 (cont)

• 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 (cont)

• 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
52
(No Transcript)
53
(No Transcript)
54
(No Transcript)
55
(No Transcript)
56
(No Transcript)
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
BUCKMAN!

• Were More Than Youd Expect!
• 1-800-BUCKMAN
• For More Information