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Composites Part B
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Article history: The effect of the so called environment friendly hybrid flammability reducing fillers, i.e. the halogen/
Received 21 September 2015 antimony-free ones containing phosphorous, nitrogen and silicon on the utility properties of carbon
Received in revised form reinforced epoxy laminates was studied. The total content of the fillers did not exceed 23 wt.%. The flame
16 February 2016
resistance of the laminates aimed as parts of aircraft construction was determined. The fire retardancy
Accepted 25 March 2016
mechanism of the hybrid fillers was investigated by SEM/EDS examination of partially burned laminates.
Available online 5 April 2016
The best combination of flammability reducing fillers for the epoxy composite matrices consisted of
15 wt.% ammonium polyphosphate, 5 wt.% dipentaerythritol, and 3 wt.% organofilized bentonite. The
Keywords:
A. Flame resistance
synergy of silicon and phosphorus in this composition provided material of UL-94 flammability class V-0.
A. Carbon fibre © 2016 Elsevier Ltd. All rights reserved.
A. Resins
A. Laminates
D. Thermal analysis
http://dx.doi.org/10.1016/j.compositesb.2016.03.074
1359-8368/© 2016 Elsevier Ltd. All rights reserved.
2 R. Oliwa et al. / Composites Part B 95 (2016) 1e8
There are numerous papers dealing with hybrid flame re- bentonite to obtain organophilized layered aluminosilicate (BSQPS)
tardants, the components of which would interact and better of grain sizes below 60 mm.
protect materials by joint action. The most of these reports
concentrated on a synergetic effect obtained by modifying DOPO 2.3. Preparation of epoxy compositions
with silanes or siloxanes [30e33] or by introducing both DOPO and
silicon-rich modifiers [34,35]. The latter solution, however, cause In our previous research on the applications of organophilized
some problems in the modified material processing. aluminosilicates we have found these products to substantially
In our studies on the effect of organophilized layered alumino- reduce flammability of polymers when used as fillers and act as
silicates on the mechanical properties and flame resistance of environment friendly flame retardants [39]. Epoxy resin composi-
epoxy based glass or carbon fiber reinforced composites [36], we tions were prepared containing 3 wt.% of bentonite modified with
attempted to reach a synergetic effect in reducing flammability of quaternary phosphonium salt and commercial flame retardants so
these composites by modifying of the epoxy resin with a bentonite that total amount of filler did not exceed 23 wt.%. Preparation of the
treated with quaternary phosphonium salts and with commercial compositions started with introducing modified bentonite to the
flame retardants containing phosphorous and nitrogen. resin and homogenizing the mixture. Then, the remaining flame
retardants were introduced and the composition homogenized.
2. Experimental section After introducing each component, the four-stage homogenization
procedure was applied [37]. In the choice of type and amount of
2.1. Materials fillers, suggestions of producers were taken into account. The
mechanisms of flame retardancy of each component were also
The epoxy resin and the curing agent used in this work were considered in order to find possibly a synergetic effect. The com-
Epidian® 6 (EP6) containing mostly diglycidyl ether of bisphenol A positions selected are listed in Table 1.
and triethylenetetramine (Z1) respectively, both commercial grade
products of Ciech-Sarzyna Plant, Poland. Halogen-free commercial 2.4. Preparation of carbon fiber/epoxy compositions laminates
flame retardants used are listed in Table 1. Unidirectional carbon
fabric 200 g/m2 (TC) was purchased from Havel Composites. All The epoxy composition based on EP6, containing mixtures of
these materials were commercial grade and used without further flame retardants as shown in Table 1, were used to prepare four-
purification or modification. The organoclay, bentonite “Specjal” layer laminates with unidirectional carbon fabric (200 g/m2)
(Zebiec SA Plants, Poland) was modified with a butyl- acting as reinforcement. The contact method was used. Successive
triphenylphosphonium chloride (BSQPS, Xiamen Pioneer Technol- sheets of fabric were laid on a Teflon film and impregnated with
ogy Inc., China). epoxy composition containing amine curing agent using a grooved
roller. The top layer, after removing the excess of resin, was covered
2.2. Modification of bentonite with quaternary phosphonium salt with another Teflon film before the sample was placed between
two steel plates of dimensions 200 ! 300 mm which acted as a
The modification procedure of smectic clays with quaternary mold. The plates were pressed to exert a pressure of about 10 MPa.
ammonium or phosphonium salts has been previously patented The laminates were left to cure at room temperature overnight and
[37,38] and described in detail in our previous papers [36,39]. It then post-cured in an oven with hot air circulation at 100 " C for 6 h.
consists of introducing aqueous solution of quaternary salts to a The resulting laminates contained ca. 40% of carbon fabric by
suspension of a montmorillonite-rich bentonite in water, removal weight. The samples were cut from the laminates in the direction
of supernatant liquid, drying, grinding and sieving modified parallel to the direction of fibers with an oscillating cutting disk.
The samples were used in flammability tests as well as to measure
their thermal properties.
Table 1
Epoxy compositions with flame retardants.
2.5. Characterization of carbon fibre/epoxy compositions laminates
Composition Percentages of component of epoxy compositions [%]
BSQPSa APPb DPERc MPYPd TEPe EGf ATHg The thermal decomposition of laminates was followed in a
termogravimeter TG 209 (Netzsch, Germany) in temperature range
K0 3 e e e e e e
K1 3 10 10 e e e e
0e800 " C with heating rate 10 deg/min.
K2 3 15 5 e e e e The limiting oxygen index (LOI) for the samples was determined
K3 3 e 10 10 e e e according the standard EN ISO 4589-3 at room temperature using
K4 3 e 5 15 e e e an instrument of Fire Testing Technology Ltd. (United Kingdom).
K5 3 10 5 5 e e e
The flammability tests by using UL-94 method were carried out
K6 3 5 5 10 e e e
K7 3 7.5 5 7.5 e e e in a chamber produced by FTT Ltd. (United Kingdom). The mea-
K8 3 e 10 e 10 e e surements were made according to standard PN-EN 60695-11-10
K9 3 e 5 e 15 e e with vertical sample beam position and methane fed burner of
K10 3 e e e 15 5 e 25 mm height.
K11 3 15 e e 5 e e
K12 3 15 e e e 3 e
The heat release rate (HRR in kW/m2) during sample combus-
K13 3 e e e e e 20 tion as well as other parameter characterizing flammability were
K14 e 17 6 e e e e evaluated for composite plates 100 ! 100 ! 2 mm in size using a
K15 e e 6 17 e e e cone microcalorimeter, a product of FTT Ltd. (United Kingdom),
a
Bentonite modified with buthythriphenylphosphonium chloride [36]. according to standard ISO 13927, by applying the heat flow 25 kW/
b
Aluminum trihydroxide, APYRAL 200 SM, (Nabaltec, Germany). m2 and the distance from ignition source 25 mm.
c
Melamine polyphosphate, Ecoret MPP (Alwernia Poland). To verify the assessments of flame resistance of laboratory
d
Amonium polyphosphate, (Tecnosintesi S.p.A., Italy).
e
Dipentaerythritol, (SigmaeAldrich).
samples made by specialized instruments, direct flammability tests
f
Triethyl orthophosphate, (SigmaeAldrich). were made for reinforcing plates of unmanned plane (DRON) sta-
g
Expanded graphite EG096, (Sinograf, Poland). bilizer. The plates were formed in a vacuum mold from carbon
R. Oliwa et al. / Composites Part B 95 (2016) 1e8 3
In order to verify the effectiveness of bentonite modification the 3.3. Flame resistance by UL-94 method
modified samples were compared with unmodified ones by using
differential scanning calorimetry (DSC) Mettler Toledo DSC 822e In the UL-94 flammability test two quantities were determined:
and wide angle X-ray scattering (WAXS) Bruker Nanostar. The re- total burning time tc, i.e. the sum of times t1 and t2 of burning the
sults are described in detail in our previous paper [36]. sample after first and second ignition, respectively, and the mass
loss of the sample. In case the sample all burned out, the material
3.2. Limiting oxygen index (LOI) was classified as the flammable one (Table 2).
The results presented in Table 2 indicate that V-0 flammability
As can be seen in Fig. 1, the presence of hybrid flame retardants class had only the laminates prepared from compositions con-
significantly improves the oxygen indices of laminates. The highest, taining ammonium polyphosphate. The lowest burned mass was
almost doubled increase of LOI was found for the sample prepared recorded for the laminate containing composition K2, in agreement
using composition K2, containing, by weight, 15% of ammonium with its LOI. It is worth noticing that laminates prepared from K4
polyphosphate (APP), 5% of dipentaerythritol (DPER) and 3% of matrix containing 15% of MPYP, 5% of DPER and 3% of BSQPS and
bentonite Specjal modified with quaternary phosphonium salt having high LOI value (over 30%) in the vertical UL-94 test did not
(BSQPS). A clear synergetic effect was observed between the com- perform well and could not be classifies as fire resistant. The reason
mercial flame retardants and the modified aluminosilicate, as the might be the poorer thermal stability of ammonium polyphosphate
laminate with K0 matrix, with only a small amount of BSQPS (3 wt.%) (APP) compared to that of melamine polyphosphate (MPYP). The
and that with K14 matrix, containing no bentonite had their LOI former starts to decompose at 275 " C, whereas the latter, at above
higher only by 4 and 11% of O2 compared to the reference sample, 330 " C.
respectively (Fig. 1, EP6). On the other hand, although melamine The earlier decomposition of APP flame retardant seems to be
polyphosphate (MPYP) belongs to the category of intumescent flame advantageous in this case. The char that forms is reach in phos-
retardants, similarly as APP, the laminates with K3 and K4 matrices phorous acid. The acid reacts with dipentaerythritol thus
where APP was replaced by MPYP, had significantly lower LOI values, improving thermal stability of the char. Furthermore, released
namely 27 and 31% O2, respectively. Among the laminates with ammonia acts as the foaming agent and additionally dilutes flam-
matrices containing other hybrid flame retardant systems, the mable gases.
lowest increase of LOI was noted for those with K8 and K9 matrices Good flame resistance had also the laminates prepared using
containing triethyl phosphate (TEP), DPER, and BSQPS. matrix K11, containing 15% APP, 5% TEP, and 3% BSQPS. Although LOI
Table 2
The results of UL-94 test for carbon reinforced laminates.
Matrix Burning time, t1 (s) Burning time, t2 (s) Weight loss (%) Flamability class
K0 e e e Flammable
K1 0 10.0 2.86 V-0
K2 0 2.3 0.76 V-0
K3 32 e e Flammable
K4 5.5 e e Flammable
K5 0 5.3 0.72 V-0
K6 1.4 6.8 1.18 V-0
K7 0 7.4 0.97 V-0
K8 e e e Flammable
K9 e e e Flammable
K10 e e e Flammable
K11 0 5.1 1.05 V-0
K12 0 19.7 0.98 V-1
K13 e e e Flammable
K14 0 18.8 2.88 V-1
K15 e e e Flammable
4 R. Oliwa et al. / Composites Part B 95 (2016) 1e8
Table 3 measured for these laminates reached only 28%, in UL-94 test they
The results of flammability test in the cone microcalorimeter. had flammability class V-0 and low burning times t1 and t2.
Parametersa Matrix On the other hand, the laminates with matrices (K3, K4,
EP6 K0 K2 K14
K8eK10) containing TEP or MPYP (10e15%) turned out to be
2
flammable. Matrices containing slightly less of these flame retar-
HRR [kW/m ] 130 82.3 57.9 66.8
dant, but also APP reached the flammability class V-1 or V-0. These
pHRR [kW/m2] 322 187 122 163
THR [MJ/m2] 18.2 16.7 16.2 15.7 flame retardants have to be considered as the additives acting
TTI [s] 130 130 155 136 synergistically. Particularly useful is TEP which is a liquid reducing
PML [%] 67.2 66.3 51.6 53.2 viscosity of epoxy compositions.
MLR [g/m2s] 0.093 0.066 0.137 0.200
The results also show that replacement of a part of commercial
tpHRR [s] 135 156 220 150
EHC [MJ/kg] 12.3 8.94 9.87 10.6 flame retardants with 3 wt.% of bentonite modified with quaternary
a
phosphonium salt significantly reduces flammability of laminates.
HRR e average heat release rate; pHRR e peak (highest) heat release rate; THR e
total heat released; TTI e time to ignition; PML e percent of mass loss; MLR e mass
Although both the carbon fabric reinforced laminates prepared
loss rate; tpHRR e time to peak heat release rate; EHC e effective heat of using K15 or K2 matrices ceased to burn immediately after
combustion. removing burner, after second ignition, time t2 for the sample with
K14 matrix was by 16 s longer than that for the laminate with K2
matrix containing modified bentonite. Hence the former was
classified as V-1, only. The longer burning times caused also four
times larger mass loss of the sample with K14 matrix, compared to
that with K2 matrix (Table 2).
Fig. 3. The photographs of samples after flammability test in cone microcalorimeter of carbon reinforced laminates with matrix: a) EP6, b) K2 and c) K14.
R. Oliwa et al. / Composites Part B 95 (2016) 1e8 5
Fig. 4. A composite plate reinforced with carbon fiber with matrix: a) K2, b) K14, 10 s after removing the flame source.
retardants burn less violently, their HRR peaks are lower and effect consists of formation of a glassy sintered char in the burning
broader. The time of burning is also prolonged. The laminates with carbon laminate. Consequently, upon the second ignition, the
K0 matrix, containing just 3 wt.% of BSQPS burn almost as quickly as partially burned laminate carbon fabric/K2 matrix kept the flame
the laminates with pristine epoxy resin EP6, but the HRR peak is for only 16 s due to the presence of the sintered char of high
considerably lower than in previous cases with HRR and pHRR thermal stability (Fig. 4a), whereas the composites prepared
reduced by 37% and 42%, respectively. The highest reduction of HRR without the presence of bentonite burned completely (Fig. 4b,
and pHRR, by 55 and 65%, respectively, was observed for the lam- Table 4).
inates prepared using the epoxy matrix containing bentonite
Specjal modified with quaternary phosphonium salt (BSQPS, 3%),
beside the commercial flame retardants (Table 3). Moreover, the 3.6. Thermogravimetric analysis (TGA)
samples prepared using epoxy resin EP6 containing 15% APP, 5%
DPER, and 3% BSQPS had ignition time delayed by 25 s., i.e. 10 s. The thermogravimetric analysis carried out in nitrogen atmo-
longer compared to that for laminates with K14 matrix. The lami- sphere indicates a slight thermal stability decrease of laminates
nates with K0 matrix had ignition time similar to that for those prepared using the modified resin, compared to that prepared from
prepared with plain epoxy. The laminates with K2 and K14 matrices
had considerably reduced mass loss, by 23.5 and 20.8% compared to Table 4
mass loss recorded for laminates with plain EP6. These results The results of Mecker's burner flammability test.
confirm the synergetic effect of the flame retardants used and
Matrix Burning time, t1 [s] Burning time t2 [s] Mass loss [%]
support the conclusions following from LOI and UL-94 experi-
ments. The samples became porous upon burning (Fig. 3). This EP6 e e e
K0 e e e
confirms the intumescent effect caused by releasing gases and the
K2 10 16 0.94
fact that the effect is not hindered by the presence of modified K14 80 e e
bentonite. On the contrary, it helps to form highly porous char. The
effect might be related to different viscosity characteristics of
matrices having the dominant role in build up of porous structure
morphology described also in Zhang et al. papers [31e34] and
carbonization agents action presented in the Bugajny's paper [40].
Table 5 by 10 " C higher than that for the sample prepared using matrix K14.
The results of thermogravimetric analysis under nitrogen. This extra presence of silicon moved up also T5% of K2 laminate,
Parameters measureda Matrix compared to that of K14 one, by 5 " C. The TGA results confirm again
EP K0 K2 K14
the conclusion about the synergetic effect of phosphorous and
silicon in formation of a sintered char improving its thermal sta-
T5% [ C]
"
356.0 344.0 300.6 310.7
bility at elevated temperature. Still, T50% temperatures for the
T50% [" C] 412.2 388.6 405.7 395.8
Tmax [" C] 384.6 370.5 351.8 347.2 composites with K2 or K14 matrices were lower than the value for
Mass loss at Tmax [%] 47.4 32.4 50.3 52.9 laminates with unmodified matrix. This confirms formation of
Residue [%] at 750 " C 30.0 32.0 39.0 38.0 gaseous phosphorus products that on the early decomposition
a
T5%, T50%, and Tmax are the temperatures at 5%, 50%, and at the highest mass loss stages may hinder the flame [41].
rate, respectively. TGA results are consistent with those obtained from the cone
microcalorimeter measurements. Despite of slightly more rapid
decomposition, the laminates prepared using matrices modified
plain epoxy resin. The temperature at which the mass loss of the with both commercial and aluminosilicate flame retardants left
sample reached 5 wt.% (T5%) was in each case lower for the of behind more of solid residue.
modified resins, as compared to the laminate obtained from plain
epoxy (Fig. 5). The lowest decrease of T5% (12 " C) was recorded for 3.7. SEM/EDS analysis of partially burned laminates
the matrix containing only the modified aluminosilicate (K0). The
laminate of flammability class V-0 prepared with matrix K2 started The SEM/EDS analysis of partially burned carbon fabric rein-
to decompose at temperature T5% by 55 " C lower than the un- forced laminates with modified epoxy matrices reveals differences
modified one, but left the highest amount of residue at 750 " C equal in distribution of phosphorous and silicon elements in various parts
39% (Table 5). Clearly, the early start of degradation of this laminate of the char. An enhancement of silicon content was particularly
was due to the presence of thermally unstable ammonium poly- well seen for the sample containing 3 wt.% of BSQPS, where in area
phosphate. The latter decomposes yielding phosphorous-rich res- 2 (Fig. 6b), partially melted in high temperature flame, concentra-
idue which improves stability of the material at higher tion of silicon was 10 times higher than in area 1, more distant from
temperatures as compared to that of the unmodified laminate. This the flame. Also noticed was the doubled concentration of phos-
effect manifested itself particularly for the sample: carbon fabric/ phorous in area 2, compared to the average amount of this element,
K2 matrix, which on top of phosphorous and carbon contained also suggesting formation of silicon and phosphorous rich glassy sin-
silicon. Consequently, the temperature at 50% mass loss, T50%, was tered char (Table 6).
Fig. 6. SEM microphotographs of partly burned laminates with matrix: a) EP6, b) K0, c) K2, d) K14. EDS elemental analyses were made for areas marked 1 through 5.
R. Oliwa et al. / Composites Part B 95 (2016) 1e8 7
Table 6 One of the major factors improving the flame resistance of the
The results of EDS element analysis of partly burned carbon fiber reinforced lami- laminates was formation of porous and tight char having improved
nates with matrices EP6, K0, K2, or K14.
thermal resistance caused by silicon accumulation as confirmed by
Matrix Number of Element contents [%] SEM/EDS analysis.
area in Fig. 6.
C N O Si P
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