FIRE AND MATERIALS, VOL.

18,313-325 (1994)

Fire Performance Studies on Glass-reinforced

Plastic Laminates
M. J. Scudamore*
BP Chemicals Limited

Polyester, epoxy and phenolic glass-reinforced laminates were compared in terms of their fire properties in the cone
calorimeter. The presence of a gel coat on the polyester and epoxy products had some effect, mainly in the FR grades.
The FR polyester with a brominated flame retardant showed a marked decrease in rate of heat release and in rate of
smoke production. Aluminium hydroxide (commonly called alumina trihydrate or ATH) caused a significant delay in
ignition time for the epoxy product and some reduction in rate of heat release but rate of smoke release was still
relatively high. Phenolic laminates showed a long ignition time and relatively low rate of heat release (RHR). The peak
RHR was further reduced by the presence of aluminium hydroxide and by changing the type of glass reinforcement.
The influence of thickness was explored for a series of phenolic laminates in both cone calorimeter and the
International Maritime Organization (IMO) surface flammability test. Ignition delay time was significantly affected
and the cone calorimeter results showed that the shape of the RHR curve was also changed as the thickness increased.
However, the heat release measurements in the IMO test were not sensitive enough to pick up the differences in this
property. The type of substrate under the laminate significantlyaltered the burning rate but this may have been because
they were not glued or mechanically fixed.

INTRODUCTION EXPERIMENTAL

Composite materials such as glass-reinforced plastic lam- Equipment

inates have in the last decade become of great interest in a
number of important application areas such as rail
transport, shipping and offshore,and construction, where
their light weight and mechanical properties are a signific-
ant advantage in comparison with traditional materials
such as steel. An apparent disadvantage, however, is that
under certain circumstances the polymeric component
will burn. It is important to define what these circum-
stances are, using tests that are relevant to the application
for which the product is intended.
Some of the problems and challenges in the above task
have been described by the United States National
Institute for Science and Technology (NIST)' and an-
other NIST report' reviews the early literature on the
subject: Many of the previous studies have relied on
standard small-scale tests which, although currently ac-
cepted by regulators, do not define the early fire proper-
ties in terms of fundamental fire parameters such as
ignition delay time under a defined heat flux, rate of heat
release, flame spread, etc. Where these parameters have
been measured3 details of product construction have not
always been revealed for reasons of confidentiality.
The present study examines the fire properties of well-
defined polyester, epoxy and phenolic glass-reinforced
laminates as measured by the cone calorimeter, a bench-
scale instrument which is capable of yielding data in the
form needed for fire engineering calculations. These types
of composites are used in a wide range of thicknesses and
on a variety of substrates and the paper examines in some
detail the effect of changes of this type.
A commercial cone calorimeter fitted with a laser beam
smoke-measuringdevice was used for the majority of the
small-scale fire tests. This instrument has been described
in detail by Babrauskas4 and the test method is the
subject of ASTM and I S 0 standard^.^.^
Flame spread tests were carried out by Warrington
Fire Research Centre using the apparatus and procedure
described in IMO Res. A. 653(16).'
Test samples
All the glass-reinforced laminates described in this report
were made by a hand lay-up technique and cured at room
temperature followed by 8 hours at 60°C or 75°C. Prior to
fire testing, specimens were conditioned at 23"C/50%
relative humidity to constant mass. The formulations of
samples used for the cone calorimeter comparison be-
tween laminates of various composition are shown in
Table 1 and sample thickness apd glass content are given
in Table 2.
FR polyester laminates were made with a commercial
brominated resin known to be capable of yielding pro-
ducts which achieve Class 1 in the British surface spread
of flame rest.' The F R epoxy laminates, however, con-
tained ATH (Grade FRF 80) at a loading of 67 parts per
100 parts of resin (phr). The same polyester and epoxy gel
coats were used on both non-FR (NFR) and F R products.
ATH (grade Trihyde ON310) was used in the FR phen-
olic laminate at 30 phr.

*Address for correspondence: 64 Spencer Road, Strawberry Hill, Twickenham, Middlesex, TW2 5TQ, UK.

CCC 0308-0501/94/050313-13 Received 13 April 1992

0 1994 by John Wiley & Sons, Ltd. Accepted 26 April 1994
314 M. J. SCUDAMORE

Table 1. Sample formulations

Sample Gel coat Resin Glass Cure

GP polyester
GC Scott Bader 65 PA 500 gm-’ Cray Valley Total QC 3OLSE 3 x 450g CSM (PPG Ind.) 1 Week at room
Catalyst: Butanox M50, 1% Catalyst: Butanox M50, 1% Resin :glass 1.1 : 1.O temperature then 8
hours at 75°C
NGC None As GC sample As GC sample As GC sample
FR polyester
GC As GP polyester Scott Bader 356 PA 3x450g CSM (PPG Ind.) As above
Catalyst: Butanox M50, 1YO Resin :glass 2.5 : 1.O
NGC None As FR GC sample As FR GC sample
GP epoxy
GC Ciba Geigy SW2402B 100 pts Ciba Geigy CY219 100 pts 3x450gCSM As above
Ciba Geigy HY2402 20 pts Ciba Geigy HY219 50 pts Resin : glass 1.8 : 1.O
Coverage 1 kg m-’ Ciba Geigy DY219 4 pts
NGC None As GC sample As GC sample As above
FR epoxy
GC As GP epoxy Ciba Geigy CY219 100 pts As GP epoxy As above
ATH Grade FRF80 100 pts
Ciba Geigy HY219 50 pts
Ciba Geigy DY219 4 pts
NGC None As GC sample As GP epoxy As above
GP phenolic
CSM Cellobond J26/047L Cellobond J2018L 4 x 4 5 0 g CSM 2 hours at 60°C
Catalyst: Phencat 10 then 4 hours at 60°C
WR66 As phenolic CSM 66wtYo WR As phenolic CSM
WR44 As phenolic CSM 44W% WR As phenolic CSM

Cellobond J2018L 100 pts 4 x 450 g CSM As GP phenolic

FR Phenolic As GP phenolic ATH grade Trihyde ON310 30 pts
Catalyst: Phencat 10

GC=with gel coat

NGC=no gel coat
GP =general-purpose
CSM =chopped strand glass mat
WR =woven roving glass mat.

Samples for evaluating the effect of thickness on fire
properties in the cone calorimeter and IMO flame spread
tests were phenolic laminates made with chopped strand
glass mat. The thicknesses were as follows:
Panel no. No. of layers Thickness (mm)
1 1 1.o
2 3 3.0
3 6 5.5
4 10 9.5
The samples used to evaluate effect of substrate were also
phenolic GRP and of thickness 3 mm. The surface was
coated with Trimite AP211/AE245, a flame retarded
paint system developed for phenolic laminates.
Sample preparation
The cone calorimeter specimens were wrapped in alumi-
nium foil as specified in the standard6 and placed in the
specimen holder over a ceramic fibre blanket at least 13
mm thick. All the tests were performed with the retainer
frame in place, as recommended in I S 0 5660-1. The IMO
test specimens were prepared according to the standard
and tested on the specified backing board with no addi-
tional substrate.
RESULTS AND DISCUSSION
Polyester laminate
Results are shown in Table 3 and Figs 1-7. The gel coat
applied to the surface of the general-purpose laminate
tended to slightly lengthen the ignition delay time at
external flux levels of 35 and 50 kW m-’ (Fig. 1)but there
was little or no significant effect on rate of heat release
(Fig. 2). In contrast, the gel coat applied to the FR
laminate tended to have a marginally negative effect on
the ignition delay time at 50 and 75 kW m-’ and increase
rate of heat release. This is not unexpected since the gel
coat itself (Scott Bader 65 PA resin) did not contain a
flame retardant additive. The presence of the gel coat had
no significant effect on smoke production (Fig. 6).
The Class 1 polyester GRP was manufactured from
Scott Bader brominated polyester resin 356PA. Very
pronounced differences from the general-purpose (NFR)
grade were observed in all the measured fire properties
except the smoke specific extinction area. Ignition delay
time was doubled for the non-gel-coated product and
almost double but from a better base line for the product
with the gel coat (Table 3). Peak RHR was more than
halved in both cases. This is clearly seen by comparing the
 GLASS-REINFORCED PLASTIC LAMINATES 315

Table 2. Sample thickness and glass content Table 3. Effect of flame retardant and gel coat - polyester GRP
Description Mean thickness Glass content With gel coat Without gel coat
(mm) (WtYo)
General-purpose (NFR) NFR FR NFR FR
polyester with gel coat 2.38 38.2 Ignition time (s)
General-purpose (NFR) 35 kW m-’ 54 95 41 93
polyester without gel coat 2.0 43.7 50 kW m-2 31 53 25 62
Class 1 Flame retarded (FR) 75 kW m-2 12 24 13 31
polyester with gel coat 3.13 43.4 RHR peak (kWm-2)
Class 1 Flame retarded (FR) 35 kW m-2 347 144 327 112
polyester without gel coat 2.75 43.5 50 kW m-2 37 1 176 374 159
General-purpose (NFR) 75 kW m-2 439 206 47 1 174
epoxy with gel coat 3.25 32.6 RHR t,s to 180 s (kWm-2)
General-purpose (NFR) 35 kW m-’ 190 65 168 24
epoxy without gel coat 2.88 29.6 50 kW rn-’ 202 68 187 52
Flame retarded (FR) 75 kW m-2 199 103 193 100
epoxy with gel coat 3.88 39.5 RHR av. (kWm-2)
Flame retarded (FR) 35 kW m-’ 79 74 78 38
epoxy without gel coat 2.88 42.9 50 kW rn-’ 108 66 115 49
General-purposephenolic 75 kW m-’ 133 78 109 83
woven roving glass mat 3.5 66 EHC ( M J kg-’)
General-purpose phenolic 35 kW m-2 21.6 7.2 21.2 4.9
chopped strand glass mat 3.5 44.3 50 kW m-2 21 6.3 20.8 6.3
General-purpose phenolic 75 kW m-2 20.3 8.1 18 8.3
woven roving glass mat 3.0 40 SEA (m2kg-’)
FR phenolic chopped 35 kW m-’ 935 701 1035 843
strand glass mat 3.7 c 40 50 kW m-2 966 1002 1001 975
75 kW m-2 891 967 971 1004
Note: All the polyester and epoxy samples contained chopped SMK PARAM. (MW kg-’)
strand glass mat as reinforcement. 35 kWm-’ 324 101 338 94
50 kW m-2 358 176 374 155
75 kW m-’ 391 199 457 175

35 w/mZ
50 W/m2

75 w/m2

100 w/ml

g 100

50

. .
1 2 3 4 5 6 ‘ 7 ’ 8 ’ 9 ‘10
Lamblatr
Figure 1. The effect of gel coat and flame retardant. Ignition time in cone
calorimeter.

heat release curves shown in Figs 4 and 5 with Fig. 3. The
FR product burned in two distinct phases under external
heat flux levels of 35 and 50 kW m-2 although a rather
more continuous burn pattern was experienced under an
exposure of 75 kWm-2. Repeatability between speci-
mens was very good-this is shown for the 75 kWm-’
burn in Fig. 5 but similar close correspondence was also
shown at the other two heat flux levels. It is interesting to
note that the NFR laminate showed a single RHR peak
(Fig. 3), suggesting that the lower layers were decom-
posing and producing combustible volatiles at the same
time as the upper layer was burning. The FR species were
presumably able to delay this effect at 35 and 50 kW m-2
but not at the very high flux of 75 kW m-2.
The effective heat of combustion (EHC), calculated
from total heat released and total mass loss, was signific-
antly reduced from an overall average of 20.5 MJkg-’
for the NFR samples to 6.9 MJ kg-’ for the FR ones.
316 M. J. SCUDAMORE

350 1 I
1.R6CwR
ZR6CR I
3001

:
0
200
c
9
+ 150

g 100
50

n
1 . . . . . .
1 2 3 4 5 6 7 8 9 10
Lamlnate

Figure 2. The effect of gel coat and flame retardant. Early RHR in cone
calorimeter.

I \\UkW,d

'0 100 zoo so0

Th&-
Figure 3. NFR polyester laminate, no gel coat. Rate of heat release.

I . .*.........._.
.......
100 200 300 400 500 1 10
Rnq-

Figure 4. FR polyester laminate,'no gel coat. Rate of heat release.

This indicates that the combustion mechanism is being
interfered with, probably in the vapour phase, by the
brominated species from the flame retardant resin. The
above figures represent the EHC for the polyester mater-
ial within the laminate product. A more useful way of
expressing the EHC for the product as a whole would be
to divide the total heat released by the original mass of the
specimen, including the glass layers.
Average specific extinction area (SEA)results were not,
in general, significantly affected by the presence of the
 GLASS-REINFORCED PLASTIC LAMINATES 317

40-
.
20-
.
0 100 200 300 400 so0 800
h q d

Figure 5. FR polyester laminate, no gel coat. Rate of heat release.

1200
1
1000
35 W/mZ

50 W/m2
r” 800
2E 75 W/ml

. 600
>:
100 M/m2

d
d
# 400

200

0 . . . . . . .
1 2 3 4 5 6 7 8 9 10
Laminate

Figure 6. The effect of gel coat and flame retardant. Smoke SEA in cone
calorimeter.

flame retardant (Fig. 6) but is important to note that SEA
takes no account of the rate at which the smoke is
produced. One suggestion for overcoming this problemg
is to express the smoke in terms of smoke parameter
which is defined as the product of the mean SEA and the
peak RHR. When smoke generation is expressed in this
way (Fig. 7) the FR grade polyester is seen to be superior
to the general-purpose grade because the smoke is being
produced at a much reduced rate.
Epoxy laminate
The gel coat used for the epoxy laminates (Ciba Geigy
SW2402B with HY 2402) had little effect on the ignition
delay time when used on the NFR product but this time
was significantly reduced in the case of the gel-coated FR
laminate at 35 and 50 kWm-’ (Fig. 1). There was no
marked effect of the gel coat on RHR or smoke genera-
tion.
The FR epoxy product was made from the same resin
(Ciba Geigy CY 219) as for the general purpose laminate
but with ATH FR agent added. This decomposes at the
relatively low temperature of approximately 200°C and
the large volume of water vapour released is the active
agent in the flame retarding mechanism. It seems clear
from the averaged results in Table 4 that this water
release was having a significant role in increasing ignition
delay time in comparison with the NFR product.
RHR was reduced as a result of ATH incorporation
(Fig. 2) but the reduction was much less than that
produced by the brominated FR polyester resin. Effective
heat of combustion was somewhat reduced for the FR
grade but it appears that the ATH is having a much less
significant effect on the combustion mechanism than is
the halogenated FR agent in the polyester.
The effect of flame retardant on the RHR curve is
illustrated in Figs 8-10. The effect is not as striking as in
the corresponding polyester comparison and the double
peak observed for the FR product was also present in the
NFR grade. Specific extinction area was slightly less in
FR laminates (Fig. 6) and this difference is increased when
smoke production is expressed in terms of smoke para-
meter (Fig. 7) because of the reduction in RHR.
318 M.J. SCUDAMORE

600
U

500 1 I 35 W/m2
P
2 400 50 Wjm2

Fw/m2
300 100 W/m2
s
#& 200
cn

100

n . . . . . . . . .
1 2 3 4 5 6 7 8 9 10
Laminate
Figure 7. The effect of gel coat and flame retardant. Smoke parameter in cone
calorimeter.

and rate of heat release curves are displayed in Table 5

Table 4. Effect of &me retardant and gel coat - epoxy GRP and Figs 11-13 to show the level of repeatability,which is
With gel coat Without gel coat
reasonably good. The main effect of the flame retardant
NFR FR NFR FR was to reduce the peak RHR although a fairly substantial
Ignition time (s) effect on ignition time at 50 kW m-’ was also seen. An
35kWm-2 50 72 41 124 interesting feature of these burns is the long ‘tail’ to the
50 kW rn-2 30 45 26 88 RHR curves during which combustion is still occurring
75 kW rn-2 14 20 10 21 but at a low heat release. This type of burning is manifes-
RHR peak (kWm-2) ted by small, almost transparent blue flames over the
35 kW m-2 415 327 385 338 specimen surface which we have called a ‘corona’ effect.
50kWm-2 478 409 492 363 This was not seen for the NFR polyester or epoxy
75 kW 559 453 528 343
laminates but small flames continued for a significant
RHR fu to 180 s (kWm-2)
35 kW m-2 264 182 244 171
time in the FR polyester burns (Fig. 4). Because of
50 kW m-2 294 211 262 178 the long ‘tail’ the RHR average results may be some-
75 kW m-2 303 260 292 221 what misleading and so in Table 5 the average value
RHR av. (kWm-’) between ignition and 360 second after ignition is also
35 kW m-? 155 117 160 103 shown.
50 kW rn-2 146 98 144 77 Smoke production was significantly reduced as a result
75 kW m-’ 169 122 155 113 of the incorporation of ATH (Table 5). This is evident
EHC (MJkg-’) from the specific extinction area results but even more
35 kW rn-2 21.1 19.3 21.1 19 noticeable when the results are expressed in terms of
50 kW m-’ 22.8 18.2 22.4 17.9 smoke parameter which takes the decrease in peak RHR
75 kW m-2 22.4 18.8 21 17.8
into account. This is in contrast to the negligible effect on
SEA (rn2kg-’)
35 kW 1027 927 1071 886 the epoxy resin system.
50 kW m-’ 1005 858 1044 870 The type of glass mat used in the manufacture of the
75 kW m-2 1055 883 1025 833 laminate can also have an effect on the reaction-to-fire
SMK PARAM. (MW kg-’) properties (Table 6). Laminates made with chopped
35 kW m-’ 426 303 412 300 strand mat (CSM) and woven roving mat (WR) with
50 kW m-’ 480 351 514 316 similar glass contents (40-44%) both showed con-
75 kW m-2 590 400 541 286 siderable resistance to ignition at 35 kW m-’; the CSM
product ignited after approximately 10 minutes while the
WR product did not ignite within the 15 minutes test
duration. At the higher flux levels of 50 and 75 kW m-2,
Phenolic laminate however, the CSM version ignited rather earlier than the
WR type. The type of glass reinforcementalso affected the
A study of the effect of surface finish was not made in the rate of heat release; compare Fig. 14 (woven roving mat)
case of the phenolic laminates, a surface paste consisting with Fig. 11(chopped strand mat). Although in both cases
of phenolic resin filled with glass spheres (Cellobond the RHR was relatively low the CSM gave a rather higher
H26/047L) being used in all cases. The bums were carried and narrower main peak at both heat flux levels and this
out at 50 and 75 kWm-’ with additional bums at peak occurred significantly earlier. Smoke production
100 kW m-2 for the FR product. All the numerical results was also less with the laminate incorporating woven
 GLASS-REINFORCED PLASTIC LAMINATES 319
--- I

J
A75 W/na Table 5. Effect of flame retardant - phenolic GRP
NFR FR

Run 1 Run 2 Run 1 Run 2

Ignition time (s)
35 kW m-’ 638 584
50 kW m-’ 147 142 206 175
75 kWm-’ 66 79 55 53
100 kW rn-’ 49 51
RHR peak (kWm-’)
100 35 kW m-’ 35 37
0 50 kW m-’ 127 129 81 70
Time, seconds 75 kW m-2 154 185 91 98
100kWm-’ 113 120
Figure 8. NFR epoxy laminate, no gel coat. Rate of heat release.
RHR tIPto 180 s (kWm-’)
35 kW m-’ 29 29
50 kWm-’ 60 60 60 51
75 kWm-’ 72 80 54 58
100 kW rn-’ 79 74
RHR tie to 360 s (kWm-’)
35 kWm-2 24 25
50 kWm-’ 42 43 39 45
75 kWm-’ 48 52 48 49
100 kWm-’ 59
RHR av. (kWm-’)
... 35 kW m-’
50 kW m-’
26
30
26
32 29 25
50 75 kW m-’ 64 71 47 43
100 kW m-’ 60 58
100 400 EHC (MJ kg-’)
Time, seconds 35 kW m-’ 23.7 21.7
50 kW m-’ 24.6 25.1 20.8 17
Figure 9. FR epoxy laminate, no gel coat. Rate of heat release.
75 kW m-’ 18.7 20.1 12.2 13.6
100kWm-’ 11.7 12
SEA (m’ kg-’)
400 35 kW m-’ 16 3
50 kW rn-’ 199 166 104 114
380 .c.
75 kW m-’ 299 362 133 186
78 W / M 100kWm-’ 148 144
....... . SMK PARAM. (MW kg-’)
35 kW m-’ 6 11

11 I:, \ 50 kW m-’
75 kW m-’
25
60
21
37
8
12
8
18
100 kW m- ’ 17 17

50

100 200 aoo 400 600 100

rime, seconds
Figure 10. FR epoxy laminate, no gel coat. Rate of heat release.
180
180: 1 78 W/nS

roving glass mat, in terms of both specific extinction area

and, particularly, smoke parameter (Table 6).
The effect of glass loading appears to be much less
significant than the glass mat construction, with lamin-
ates of 44 wt% and 66 wt% woven roving giving largely
similar results. he,seconds
Figure 11. NFR phenolic laminate. Rate of heat release.
Effect of laminate thickness
It is well known that thickness can affect surface flamm- bench-scale reaction-to-fire properties of phenolic glass-
ability characteristics up to a certain limiting value after reinforced laminates as the thickness is increased in stages
which the full depth of the material is not involved in the from 1 mm to 9.5 mm.
early stages of burning and the material is said to be Cone calorimeter results (Table 3) show a significant
‘thermally thick’. O This section describes the changes in effect of thickness on ignitability but this effect decreases
320 M.J. SCUDAMORE

50 W/nQ

40-
20 -
O.6 ’ 100 O* 300 400
Time, seconds
500 600 700 840 oi 100 260 360 460
Time, seconds
560 660 760 6O
:

Figure 12. FR phenolic laminate. Rate of heat release. Figure 13. FR phenolic laminate. Rate of heat release.

as the external heat flux level increases (Fig. 15). Surpris-
ingly, the thinnest laminate (one layer only) did not
exhibit flaming combustion within the 900 seconds limit
put on the test at the lowest flux level of 35 kWm-’
although when the thickness was increased to 3 mm (three
layers) flaming ignition occurred at approximately 200
seconds. The RHR curves also show a significant depend-
ence on thickness (Figs 16-18). At a heat flux level of
35 kW m-’ a single peak was observed at all thicknesses
but this became broader and reduced in height as thick-
ness increased from 3 mm to 9.5 mm. When external flux
was 50 kWm-’ the thinner laminates (1 m m and 3 mm)
showed a sharp, clearly defined peak but the thicker (5.5
and 9.5 mm) products showed a very pronounced double
peak. As the external flux was increased further to 75 and
100 kW m-’ these initial peaks coincided and there was
also some evidence of an initial peak from the 3 mm
product in close proximity to those from the other two.
The second peaks were well separated for the three
different thicknesses and the average times at which the
peaks occurred are summarized in Table 8. A likely
explanation of the above behaviour, largely borne out by

Table 6. Effect of glass type and content - phenolic GRP

Chopped strand Woven roving Woven roving
40 Wt% glass 44 Wt% glass 66 Wt% glass

Run 1 Run 2 Run 1 Run 2 Run 1 Run 2

Ignition time (s)

35 kW m-’ 638 584 NI NI
50 kW m-’ 147 f 42 123 132 132 128
75 kW m-’ 66 79 46 46 40 40
RHR peak (kWm-’)
35 kW m-’ 35 37 - -

50 kW m-’ 127 129 57 61 69 68

75 kW m-’ 154 185 83 84 89 91
RHR t,, to 180 s (kWm-’)
35 kW m-’ 29 29 - -
50 kW rn-’ 60 60 35 42 48 46
75 kW m-’ 72 80 44 46 49 58
RHR t,, to 360 s (kW m-’)
35 kW m-’ 24 25 - -
50 kW m-’ 42 43 33 34 34 34
75 kW m-’ 48 52 38 39 37 43
RHR av. (kW m-’)
35 kW m-’ 26 26 - -
50 kW m-’ 30 32 32 32 36 35
75 kW m-’ 64 71 36 37 33 36
EHC ( M J kg-’)
35 kWm-’ 23.7 21.7 - -
50 kW m-’ 24.6 25.1 13.6 14.9 16.4 16.6
75 kW m-’ 18.7 20.1 12 11.7 14.4 16.9
SEA (m2 kg-’)
35 kW m-’ 16 3 - -
50 kW m-’ 199 166 111 57 129 115
75 kW m-’ 299 362 52 130 150 182
SMK PARAM. ( M W kg-l)
35 kW m-’ 6 <1 - -
50kWm-’ 25 21 6 3 9 8
75 kW m-’ 60 37 4 11 13 1.7
 GLASS-REINFORCED PLASTIC LAMINATES 32 1

expresses smoke production in terms of mass loss during

burning and mass loss tends to be very low towards the
end of a burn of this type of material. The mass effect can

1
“he,,
be eliminated if smoke is expressed directly in terms of
visibility using units of optical density or of obscura”
3-too4 I where 1 obscura (Ob) is equivalent to human visibility of
75 W/ne
approximately 10 m. Thus,

20
0
0 100 200 300 400 5W 000 700 000 Where L-path length and I, and I are the light in-
Time, seconds tensities in the absence and presence of smoke, respect-
Figure 14. NFR phenolic laminate-woven roving. Rate of heat
ively. Swedish workers’ commonly express smoke pro-
release. duction rates as the product of smoke obscura and the
volumetric flow rate through the duct, i.e. Ob.m3s-’.
Results from the present study expressed in these terms
show that the rates of smoke production mirror fairly
the observations, is that the thicker products delaminate closely the rate of heat release curves. This is illustrated in
under heat flux conditions and volatiles released from the Figs 19 and 20 for the 50 kW m-* burns. Smoke ex-
separated lower layers escape through the side of the pressed in terms of smoke parameter (Table 7) show that
specimen, even though these are protected by means of the rate of smoke production tends to increase with
the edge frame, to cause flaming around the edge of the external flux at all thicknesses.
exposed surface. When the same samples were tested in the IMO surface
Smoke results, expressed as specific extinction area, flammability test the effect of thickness on ignitability was
were rather variable and no significant trend with thick- confirmed with the value of Qi, heat required for ignition,
ness could be detected. This is probably because SEA increasing as laminate thickness increased from 1 mm to

Table 7. Hect of thickness - phenolic GRP. Cone calorimeter tests

Thickness (mm) 1 1 3 3 5.5 5.5 9.5 9.5

Ignition time (s)

35 kW m-’ 242 184 473 510 710 912
50 kW m-’ 40 55 160 144 180 175 275 271
75 kWm-’ 20 22 71 80 91 78 83 85
100 kWm-’ 12 16 39 27 49 34 22 23
RHR peak (kWm-’)
35 kW m-’ 88 98 51 73 35 37
50 kW m - 2 123 130 136 122 85 73 70 69
75 kWm-’ 171 188 174 171 104 111 96 97
100 kWm-’ 203 227 201 193 152 137 125 133
RHR r,, to 180 s (kWm-’)
35 kW m-’ 43 37 35 58 20 28
50kWm-’ 33 33 71 60 54 38 38 36
75 kWm-‘ 73 48 86 82 61 36 53 47
100 kWm-’ 83 87 112 87 71 69 58 52
RHR av. (kW m-’)
35 kW m-’ 29 37 29 32 26 26
50 kWm-’ 24 25 41 30 39 35 37 30
75 kW m-’ 55 45 65 58 54 53 53 53
100 kWm-’ 65 71 91 64 75 70 66
EHC (MJ kg-’)
35 kW m-’ 16.9 16.8 18.1 20.9 16.4 17.2
50 kW m-’ 21.5 27.7 26.2 24.9 20.7 17.9 18.8 16.2
75kWm-’ 19.6 23.3 18.9 19.6 15.5 13 14.6 13.5
100 kWm-2 21.6 18.2 16.9 15.7 14.3 12.7 13.7 13.8
SEA (m’ kg-’)
35 kW m-’ 198 283 112 138 39) 9?
50kWm-’ 177 259 104 114 136 227 327 207
75 kW m-’ 451 192 133 186 238 205 224 286
100 kW m-’ 370 265 148 144 269 239 287 326
SMK PARAM. ( M W kg-’)
35 kW m - 2 - - 8 ? ?
50 kW m-’ 22 34 8 8 12 17 23 6
75 kW m-’ 77 36 12 18 25 23 22 28
100 kW m - 2 75 60 17 17 41 33 36 43
322 M.J. SCUDAMORE

1000 -I i
900 -
800 -
{
53 700-
600-
500-
/-
-

:::w
400
2 300-

OO 2 12
Thldaress, mm
Figure 15. Phenolic laminate. The effect of thickness on ignitability.

1000 1600 2000 2! 80

T b - 0
Figure 16. The effect of thickness on RHR-external flux 35 kW m-'. Phenolic GRP.

im.

20.
n
-0
L& 200 400 600 800 1000 1200 1400 1600 11

Figure 17. The effect of thickness on RHR-external flux 50 kW m-'. Phenolic GRP.

5.5 mm but not thereafter (Table 9). There was no obvious
effect on flame spread, however, with critical flux for
extinguishment (CFE) staying approximately constant.
At all thickness the product satisfied the requirements for
bulkhead, wall and ceiling lining in ships. No clear trend
was observed in the heat release measurements from
the IMO apparatus, probably because of the rather
cruder measurement system in comparison with the cone
calorimeter and because of the single heat flux profile
employed.
Substrates
For the short series of cone calorimeter tests run with
phenolic laminates over various substrates the laminate
 GLASS-REINFORCED PLASTIC LAMINATES 323

200 'I 1

lmjn 'gp.
110

Tlirywc
Figure 18. The effect of thickness on RHR-external flux 75 kW m-2. Phenolic GRP.

was placed but not mechanically fixed or glued onto the

substrate. The resulting composite was then wrapped in
c
aluminium foil and placed on the ceramic fibre blanket in
the specimen holder as normal. The 'air' substrate was
constructed by using an 11 mm x 11 mm frame of calcium
silicate board within the dimensions of the sample holder.
Tests were carried out at an external flux of 50 kW m-2
5: 0.06
4 0.06
0.04
0.02
Table 8. Phenolic laminates - effect of thickness nod external %EO O

flux on mean time of RHR peaks v) The# sac

Time of RHR peaks (s)
Figure 19. The effect of thickness on smoke production. Phenolic
External flux Thickness
laminate-external flux 50 kW m-2.
(kW m-*) (mm) 1st peak 2nd peak

35 1 - -
3 350 -
5.5 650 -
9.5 1300 -
50 1 80 -
3 190 -
5.5 200 420
9.5 300 900
75 1 50 -
3 90 100
5.5 100 320
9.5 1 00 750
100 1 25 - 2!
3 40 80
5.5 50 280
9.5 30 500 Figure 20. The effect of thickness on smoke production. Phenolic
laminatesexternal flux 50 kW m-2.

Table 9. Phenolic laminates - effect of thickness. IMO surface flammability test

Thickness (mm) 1 3 5 9 Criteria a

Heat for ignition Qi(MJ 3.2 13.5 24.7 23.3

Heat for sustained flaming, Q ( M J m-2) 3.6 16.2 25.2 22.7 >1.5
Critical flux at extinguishment (kW m-2) 37.7 37.1 37 42.5 >20
Peak RHR (kW 0.73 0.9 0.65 0.6 <4
Total heat released (MJ) 0.05 0.22 0.35 0.25 <0.7

a For bulkhead, wall and ceiling linings.

324 M. J. SCUDAMORE

Table 10. Effect ef substrate - phenolic Ialgimate

Calcium silicate Plasterboard Wood
Air Monolux 40 Dsflerfaced
. . Parbck board
~ ~ - ~ ~ ~ ~ ~

1 2 1 2 1 2 1 2
Ignition time (s)
50 kW -’ 1’39 97 157 206 265 60 95 176 240
75 kW m-’ 60 30 110 97 103
RHR peak (kWm-’)
50 kW m - z 95 89 85 39 60 72 48 130 152
75 kW m-’ 77 64 65 71 187
RHR t,, to 180 s (kWm-’)
50kWm-’ 26 53 59 31 41 48 103
75 kWm-’ 43 55 50 102
RHR t, to 360 s (kWm-’)
50 kW m-’ 39 39 43 26 32 65 93
75 kW m-’ 34 43 40 106
RHR av. (kW m-’)
50 kW m-’ 29 20 29 22 28 24 21 46 57
75 kW m - z 29 36 37 27 89
EHC ( M J kg-l)
50 kW m-’ 20.4 11.9 11.7 6.6 7.8 4..1 3.2 5.6 12.6
75 kWm-2 20.4 26.4 13.2 8.1 13.6
SEA (m’kg-’)
50 kW m-’ 167 96 89 17 24 35 7 33 67
75 kW m-’ 138 101 137 12 40
SMK PARAM. ( M W kg-’)
50 kW 21 11 10
75 kW m-’ 14 7
Smoke vol(m30D1)
50 kW m-’ 0.73 1.01 0.91 0.23 0.43 0.13 0.13 2 2.1
75 kW m-‘ 0.65 0.62 1.?2 0.16 1.44

200 - -
180-
(in duplicate) and at 75 kW m-’ (singly). The results in
Table 10 show that repeatability was not very good
aIthough some significant differences can be discerned.
Ignition time was shortest for the runs with plasterboard
substrate followed by Rockwool and air whiie specimens
with calcium silicate board and wood particleboard
substrates took longest to ignite.
The substrate had a significant effect on the rate of heat
release curves (Fig. 21). This graph shows the most severe
burn from each replicate pair tested at 50 kW m-2. The
large double peak obtained when the wood particleboard
was used can be explained by the involvement of the
substrate itself in the fire after approximately 600 seconds
but the difference in the shapes of curves from the other,
largely inorganic, substrates is less easy to explain.
Specific extinction area and effective heat of com-
bustion results would be expected to be misleadingly low
for those substrates which evolve water or other volatiles
on heating. In these cases a non-mass-related smoke
value is preferable and in Table 10 total smoke volume in
m3 of smoke of unit optical density is also shown. The
greatest volume of smoke resulted from the specimens
tested on the particleboard but calcium silicate board and
paper-faced plasterboard showed low smoke volumes.
Overall, it appears that more consideration needs to be
given to ways in which thin materials should be tested on
their end use substrate in the cone calorimeter. It is
probably not sufficient to place the material on the
substrate as in these examples; some form of giueing or
mechanical fixing may be necessary to prevent the under-
side of the specimen or the top of the substrate becoming
involved in the fire even though the edge frame is in
position. The selection of glue is, of course, very import-
ant since this may also become involved in the fire and
have a bearing on the results.
CONCLUSIONS
The reaction-to4re properties of glass-reinforeed thermo-
set plastic laminates depend on the type of resin and flame
 GLASS-REINFORCED PLASTIC LAMINATES
retardant, the type of glass reinforcement and, for thin
laminates, the thickness. The type of substrates can also
have a significant effect for thin laminates.
Brominated or inorganic flame retardants were re-
quired for polyester and epoxy laminates in order to
reduce the rate of heat release and rate of smoke produc-
tion. In the case of the phenolic laminates, however, no
FR additive or treatment was required to obtain results
for these properties which were already lower than for the
FR polyester. Incorporation of ATH in the phenolic resin
resulted in an even lower RHR and smoke production.
REFERENCES
1. T. Ohlemiller, Assessing the flarnmabjlity of composite mater-
ials. NET Report NlST JR 89-4039 (1989).
2. J. E. Brown, J. J. Loftus and R. A. Dipert, Fire characteristicsof
composite materials-a review of the literature. NlST Report
NBSlR 85-3226 (1986)
3. J. E. Brown, E. Braun and W. H. Twilley, Cone Calorimeter
evaluation of the flammability of composite materials. NlST
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4. V. Babrauskas, Developmentof the Cone calorimeter-A bench
scale heat release rate apparatus based on oxygen consump-
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6. IS0 5660-1:1993 Fire tests-reaction to fire. Rate of heat
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325
The cone calorimeter edge frame as normally used is
probably not capable of preventing delamination and
escape of combustible volatiles to the sides of the specimen
and hence to the exposed surface. This phenomenon was
most clearly observed for the phenolic laminates. For this
type of product a redesigned frame which prevents lateral
escape of volatiles is needed to obtain meaningful cone
calorimeter results.
7. IMO Resolution A653 (16). Recommendation on improved fire
test procedurefor surface flammability of bulkhead, ceiling and
deck finish materials. Adopted on 19 October 1989. Inter-
national Maritime Organization, London.
8. BS 476: Part 7: 1987. Fire tests on building materials and
structures, Part 7. Method for classification of surface spread of
flame of products. British Standards Institution, London.
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