Fire Retardant Polyester Resin Bruce Curry

October 1-3, 2003

Formulations
ABSTRACT
combustion. Additionally, metal hydrates such as
The original fire retardant polyester resin formula-
ATH absorb heat from the combustion zone, which
tions incorporated bromine and chlorine (halogens)
reduces the prospect of continued burning. Finally,
into the polymer. The disadvantages to these for-
ATH will produce a char during burning that results
mulations were excessive toxic products and smoke
in further flame retardant protection and less smoke
given off on exposure to a flame. Alumina trihydrate
generation.
(ATH) has successfully been added to non-
halogenated polyester resins to resolve the toxicity
Another fire retardant filler is ammonium polyphos-
and smoke issues.
phate, which has been used for many years but not
extensively in fiber reinforced composites. It is a
Unfortunately the high concentration of AHT detri-
fine grained non-toxic white powder that uses the
mentally affects the mechanical properties of com-
intumescent effect for flame retardancy in fire re-
posites. Ammonium polyphosphate (APP) is an
sistant coatings. It will foam on exposure to heat or
intumescent filler that is widely used in coatings for
flames. The carbon foam layer protects the compo-
fire resistance. Other papers have been presented
site through its heat-insulating effect and reduces
that describe the benefits of using filler blends of
further oxygen access. An APP supplier is suggest-
ATH and APP in composites. This paper describes
ing that lower viscosities and improved fire re-
the development of fire retardant formulations with
sistance properties can be achieved by decreasing
emphasis on non- halogenated filled systems with
the ATH content and substituting part of the re-
varying amounts of ATH and APP. Neat and filled
moved ATH will APP. The focus of this paper is to
viscosities, cast resin mechanical properties are
confirm this suggestion.
reviewed. Also included in this paper are flammabil-
ity test results on composites tested according to
One significant disadvantage of using ATH as the
BSS 7239 toxicity test, ASTM E 84, ASTM E 162,
only filler is that high loadings were required to
ASTM E 662, and ASTM E 1354.
meet specific fire retardant requirements such as
ASTM E 84 class I ratings. Other disadvantages are
INTRODUCTION
that ATH does settle, reinforcements are harder to
Originally fire retardant polyester resins were made
wet out and finished parts were more brittle.
with halogenated raw materials such as tetrabro-
mophthalic anhydride, tetrachlorophthalic an-
Five different test methods were used to evaluate
hydydide or chlorendic acid or anhydride. These
these new blends. ASTM E 84 “Surface Burning
products performed well until toxicity issues be-
Characteristics of Building Materials” is a standard
came important. In order to satisfy the needs for low
test for general fire resistance and is widely recog-
toxicity products, non-halogenated general purpose
nized. Three tests that are often specified for mass
unsaturated polyester resins were introduced that
transit applications are ASTM E 162 “Surface Flam-
were filled with products such as alumina trihydrate
mability of Material Using a Radiant Heat Energy
(ATH). This filler was the key component in meeting
Source,” ASTM E 662 “Specific Optical Density of
the fire retardant and toxicity requirements.
Smoke Generated by Solid Materials” and Boeing
Support Standard (BSS 7239) toxicity test. A test
ATH products provide effective flame redundancy
that is being recognized increasingly as a more re-
by several routes. First, they dilute the amount of
producible fire retardant test is ASTM E 1354 “Heat
fuel available to sustain combustion during fire by
and Visible Smoke Release Rates for Materials and
replacing part of the resin. Secondly, ATH contains
Products Using an Oxygen Consumption Calorime-
34.6% bound water that is released at high temper-
ter.”
atures [beginning at 230°C (446°F)] providing a
blanket effect, which limits the oxygen available for
 Fire Retardant Polyester Resin Formulations, continued
Bruce Curry, October 1-3, 2003

A summary of these tests follows: bility of materials using a radiant heat energy source),
ASTM E 662 (specific optical density of smoke generat-
a) ASTM E 84- Laminates that are a minimum of 45.7 ed by solid materials) and the BSS 7239 toxic gas gen-
cm (18 inches) wide by 7.3 meters (24 feet) long are eration tests were run because they are often specified
compared in burning characteristics to a mineral for mass transport applications. ASTM E 1354 (heat
fiber cement board, which is rated 0, and a red oak and visible smoke release rates for materials and prod-
board that is rated 100. To meet an ASTM E 84 ucts using an oxygen consumption calorimeter) was run
class I rating, the laminate in question must have an because it is becoming more recognized as one of the
ASTM E 84 rating of 25 or less. most reproducible fire tests. It is also an excellent
b) ASTM E 162- This test measures surface flamma- screening test since a minimum amount of composite is
bility employing a radiant heat source rather than a required to run the test.
flame.
c) ASTM E 662- This test measures the optical density Liquid properties were tested with standard equipment
of smoke using a radiant energy source. The smoke and methods that are typically used in the industry. The
is measured in a flaming mode and a non-flaming casting preparation is found in Figure A. Fire testing was
mode. In order to obtain the flaming mode, a row of run on composites only.
equidistant flamelets is placed across the lower
edge of the specimen. RESULTS
d) BSS 7239- This test is a Boeing Support Standard 1. Resin liquid properties of Firepel® K133-AAA-00
that measures the amount of toxic gases that are with different ratios of ATH/APP fillers are found in
generated from a burning laminate in a controlled Figure B.
environment. 2. The neat casting of Firepel® K133-AAA-00 was test-
e) ASTM E 1354- 100 mm square coupons are burned ed for mechanical properties and those values are in
while being subjected to an external heat flux that is Figure C.
set from 0-100 kW/m2. Time to ignition, heat re- 3. Composite mechanical test results of neat resin ver-
lease, smoke obscuration and mass loss are rec- sus 60% ATH filled laminate values are in Figure D.
orded. This paper compares the fire/smoke proper- 4. Fire Test Results (Firepel® K133-AAA-00 compo-
ties of three filled resin systems utilizing ATH and sites with different ratios of ATH/APP fillers)
blends of ATH/APP. a) ASTM E 84 (surface burning characteristics of
building materials) results are in Figure E.
EXPERIMENTAL b) ASTM E 162 (surface flammability of materials
A non-halogenated general purpose unsaturated poly- using a radiant heat energy source) results are
ester resin Firepel® K133-AAA-00 containing both sty- in Figure F.
rene and methyl methacrylate (MMA) was chosen. In c) ASTM E 662 (specific optical density of smoke
order to minimize the number of variables, three types generated by solid materials) results are in Fig-
of composites were prepared keeping the total filler con- ure G.
tent constant. A standard formula that required a 40/60 d) BSS 7239 (toxic gas generation) results are in
ratio of resin/ATH was chosen as a control. Ammonium Figure H.
polyphosphate replaced 12.5% and 25% of the ATH in e) ASTM E 1354 (heat and visible smoke release
two different composites. rates for materials and products using an oxy-
gen consumption calorimeter) is in Figure I.
Liquid resin properties both neat and filled, cast neat
mechanical values, and the fire tests are provided in DISCUSSION
ables. The resin made with 12.5% ammonium poly- 1. The cast neat mechanical properties of a non-
phosphate and 47.5% ATH are coded APP12.5/ATH halogenated general purpose polyester resin are
47.5. The resin made with 25% ammonium polyphos- typical of properties that are required in the FRP in-
phate and 35% ATH are coded APP25/ATH 35. The dustry.
resin was promoted with 0.6% cobalt 6%, 0.2% N, N- 2. A filled composite is more rigid as expected. The
Dimethyl aniline (DMA) and 1.5% methyl ethyl ketone strength values are lower due to not being able to
peroxide (MEKP). Composites were made by wetting achieve as high of glass content.
one layer of 450 grams per square meter (1.5 oz) 3. The 60% ATH and the APP25/ATH 35 met ASTM E
chopped strand mat. 84 class I flame spread and smoke spread rating but
the APP12.5/ATH 47.5 did not; however, ASTM E
The ASTM E 84 tunnel test (surface burning character- 84 is an inconsistent test. It is interesting to note that
istics of building materials) was run since it is one of the the smoke rating was higher with increasing
most standard tests. The ASTM E 162 (surface flamma- amounts of APP.

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 Fire Retardant Polyester Resin Formulations, continued
Bruce Curry, October 1-3, 2003

4. The ASTM E 162 time to ignition, heat evolved Generally the tests with APP were disappointing. In
and time to specific distances indicated that the discussions with our APP supplier, indications are that
composite was progressively less fire resistant too much ATH was used, making it difficult for the
with increasing quantities of APP. APP to exfoliate properly. High performance flame-
5. The maximum smoke ratings, according to the retardants like APP rely on the presence of charable
ASTM E 662 results, were progressively higher substrate (carbon based polymer) to create an intu-
in values as the quantity of APP increased. The mescent foam.
smoke density results at the 1.5 and 4.0 minute
intervals varied significantly. CONCLUSION
6. Based on the BSS 7239 test results, the 60% 1. With increasing concentration of APP, the viscosi-
ATH composite was the best performer. ty increased which is a negative factor.
7. ASTM E 1354 data was difficult to analyze for 2. APP did not improve the fire and smoke properties
conclusions. The APP12.5/ATH 47.5 composite of a non-halogenated general purpose polyester
had the best result for the time to sustained igni- resin where the total filler content was kept at
tion. The best average peak heat release was 60%.
APP25/ATH 35 and the best smoke rating was 3. Since desired results were not obtained in this
with 60% ATH. series of testing, it is suggested that a formula
containing APP be repeated using less ATH. If
positive results were obtained, the use of APP in
composites could be an important raw material in
fiberglass reinforced composites.

Figure A.

CASTING PREPARATION

Catalyst and Cure Schedule Quantity and Time

Benzoyl Peroxide (BPO), % 1.0
Cure Schedule
60°C (160°F), hours 4
93°C (200°F), hours 1
116°C (240°F), hours 1
138°C (280°F), hours 2

Figure B.

RESIN LIQUID PROPERTIES

Property Firepel® K133-AAA-00

NEAT Firepel®
60% ATH APP12.5/ATH 47.5 APP 25/ATH 35
K133-AAA-00
C Brookfield Viscosity Spindle #1 @
0.018 (18) 0.1 (100) 0.12 (120) 0.185 (185)
50 rpm, al second (cps)

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 Fire Retardant Polyester Resin Formulations, continued
Bruce Curry, October 1-3, 2003

Figure C.

CAST MECHANICAL PROPERTIES

Property NEAT Firepel® K133-AAA-00

Tensile Strength, Mpa/psi 68 / 9,900
Tensile Modulus, Gpa/psi 3.4 / 490,000
Elongation, % 2.4
Flexural Strength, Mpa/psi 106 / 15,400
Flexural Modulus, Gpa/psi 3.8 / 550,000
Heat Distortion, °C/°F 85 / 185
Barcol Hardness (934) 45

Figure D.

GLASS FIBER COMPOSITE MECHANICAL PROPERTIES

Property Firepel® K133-AAA-00

NEAT* 60% ATH*
Tensile Strength, Mpa/psi 107 / 15,600 7.9 / 11,500
Tensile Modulus, Gpa/psi 90 / 1,300,000 137 / 2,000,000
Elongation, % 1.4 1.3
Flexural Strength, Mpa/psi 165 / 24,000 134 / 19,500
Flexural Modulus, Gpa/psi 7.6 / 1,100,000 11.7 / 1,700,000
Barcol Hardness (934) 45 62
Glass Content, % 30 16
* Composite made with 1 ply of 450 grams per square meter mat (1.5 ounce per
square foot)

Figure E.
ASTM E 84 RESULTS
SURFACE BURNING CHARACTERISTICS OF BUILDING MATERIALS USING
NON HALOGENATED GENERAL PURPOSE POLYESTER RESIN COMPOSITE
(# OF SAMPLES—1)
TEST RESULTS
Firepel® K133-AAA-00
60% ATH APP 12.5/ATH 47.5 APP 25/ATH 35
Flame Spread 25 40 25
Smoke Development 65 160 250

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 Fire Retardant Polyester Resin Formulations, continued
Bruce Curry, October 1-3, 2003

Figure F.
ASTM E 162 RESULTS
SURFACE FLAMMABILITY OF MATERIALS USING A RADIANT ENERGY
SOURCE USING NON HALOGENATED GENERAL PURPOSE POLYESTER
RESIN COMPOSITE (# OF SAMPLES—4)
TEST RESULTS
Firepel® K133-AAA-00
60% ATH APP 12.5/ATH 47.5 APP 25/ATH 35
Time to ignition, seconds 71 51 44
% Standard deviation 14 4.8 7.9
Baseline temperature, °C 190 185 185
Maximum temperature, °C 245 276 291
% Standard deviation 1.6 3.2 4.8
Temperature Rise, °C 55 91 106
% Standard deviation 7.4 9.8 13
Time to 7.6 cm (3 inches), minutes 2.7 2.0 2.0
% Standard deviation 30 8.2 5.7
Time to 15.2 cm(6 inches), minutes 4.7 2.9 3
% Standard deviation 32 8.8 4.3
Time to 22.8 cm (9 inches), minutes 8.3 4.5 5.0
% Standard deviation 24 3.0 3.8
Heat evolution factor, Q 8.8 14.4 17
% Standard deviation 8 9.8 13
Flame spread factor, Fs 2.2 3.0 3.0
% Standard deviation 18 4.9 5.2

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 Fire Retardant Polyester Resin Formulations, continued
Bruce Curry, October 1-3, 2003

Figure G.
ASTM E 662 RESULTS
SPECIFIC OPTICAL DENSITY OF SMOKE GENERATED USING NON
HALOGENATED GENERAL PURPOSE POLYESTER RESIN COMPOSITE
(# OF SAMPLES—3)
TEST RESULTS
Firepel® K133-AAA-00
60% ATH APP 12.5/ATH 47.5 APP 25/ATH 35
NON FLAMING EXPOSURE
Maximum smoke density 40 89 134
% Standard deviation 17 85 6.5
Smoke density after 1.5 minutes 0.2 0.14 0.03
% Standard deviation 60 82 173
Smoke density after 4.0 minutes 2.0 0.47 1.0
% Standard deviation 40 84 120
FLAMING EXPOSURE
Maximum smoke density 61 106 163
% Standard deviation 28 18 20
Smoke density after 1.5 minutes 1.3 0.43 2.6
% Standard deviation 18 97 91
Smoke density after 4.0 minutes 16 8.5 23
% Standard deviation 41 37 10

Figure H.

TOXIC GAS GENERATION BSS 7239 FLAMING MODE RESULTS USING NON
HALOGENATED GENERAL PURPOSE POLYESTER RESIN COMPOSITE
(# OF SAMPLES—1)

TEST RESULTS
Firepel® K133-AAA-00
60% ATH APP 12.5/ATH 47.5 APP 25/ATH 35
Hydrogen Cyanide (HCN),
<2 4 7
ppm
Carbon Monoxide, (CO),
67 275 290
ppm
Nitrous Oxides, (NOx),
<2 35 60
ppm
Sulfur Dioxide, (SO2),
<1 ND ND
ppm

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 Fire Retardant Polyester Resin Formulations, continued
Bruce Curry, October 1-3, 2003

Figure I.

ASTM E 1354 RESULTS

OXYGEN CONSUMPTION CALORIMETER USING NON HALOGENATED GENERAL PUR-
POSE POLYESTER RESIN COMPOSITE
TEST RESULTS
Firepel® K133-AAA-00
60% ATH APP 12.5/ATH 47.5 APP 25/ATH 35
Time to sustained ignition, seconds 63 76 59
% Standard deviation 5 11 3.9
2
Average peak heat release rate, kw/m 341 358 314
% Standard deviation 6.7 12 2.9
2
Average heat release rate after 60 seconds, kw/m 235 258 262
% Standard deviation 11 3.0 2.5
2
Average heat release rate after 180 seconds, kw/m 138 143 171
% Standard deviation 3.4 3.7 3.5
2
Average heat release rate after 300 seconds, kw/m 104 113 126
% Standard deviation 2.7 3.8 5.1
2
Total heat release, mj/m 27 27 33
% Standard deviation 5.2 5.0 3.9
Average effective heat of combustion, mj/kg 17 17 21
% Standard deviation 4.7 8.8 1.8
2
Smoke obscuration, average specific extinction area, m /kg 433 498 642
% Standard deviation 0.8 6.9 4.3
Mass Loss, % 50.6 44.8 42
% Standard deviation 0.8 3.7 1.4

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