Fire Safety Journal xxx (2017) 1–7

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Fire Safety Journal

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fi r e s a f

Flame-retardant wood polymer composites (WPCs) as potential fire safe

bio-based materials for building products: Preparation, flammability and
mechanical properties
Ehsan N. Kalali a, Lu Zhang a, Marjan E. Shabestari b, Jeremy Croyal c, De-Yi Wang a, *
a
IMDEA Materials Institute, c/Eric Kandel 2, Getafe, Madrid 28906, Spain
b
Department of Materials Science and Engineering & Chemical Engineering, Polytechnic School, Carlos III University of Madrid, Avenida Universidad 30, 28911 Leganes,
Madrid, Spain
c
Ecole Polytechnique de l'universite de Nantes, France

A R T I C L E I N F O A B S T R A C T

Keywords: Improving the efficiency of traditional flame retardant additives is a challenging task in the field of wood polymer
Wood polymer composite (WPC) composites (WPCs). In this work, novel flame retardant system for WPCs was developed based on the combination
Fire performance of ammonium polyphosphate (APP) with phytic acid modified layered double hydroxide (Ph-LDH). Thermog-
Mechanical properties ravimetric analysis illustrated that the incorporation of Ph-LDH resulted in earlier thermal degradation of the
Thermal properties WPCs with more thermally stable products during degradation, giving improved char formation. Limiting oxygen
index (LOI), vertical burning (UL-94) and cone calorimetry tests were used to study the flammability of WPCs and
the results showed that the addition of Ph-LDH had a synergistic effect on their fire performance. The char res-
idues of the WPCs after the cone calorimetry tests were characterised by scanning electron microscopy (SEM).
Mechanical properties of the flame retardant WPCs were analysed using impact and tensile tests. Partial substi-
tution of APP with polypropylene (PP) resulted in a deterioration in the tensile and impact properties, while co-
incorporation of nano-fillers led to an enhancement of the mechanical performances of the flame retardant WPCs.
This WPC with good flame retardant and mechanical properties could potentially be used in the fields of building
or furniture which require high flame retardancy.

1. Introduction incorporation of flame retardants (FRs) during the compounding process

is the most efficient method that can be used to modify the flame retar-
Growing environmental awareness has increased demand for the dant properties of WPCs [5–10].
development of brand new, eco-friendly materials with acceptable Ammonium polyphosphate (APP) is one of the conventional, highly
properties, high biodegradability and relatively low cost. Wood polymer effective and widely used environment-friendly flame retardants used for
composites (WPCs) have emerged as the latest generation of construction the amelioration of the flame retardant properties of WPCs [11–13]. In
engineering materials for different interior and exterior applications, order to improve the flame retardant efficiency of APP on WPCs, other
such as decking for balconies and terraces, fencing, landscaping timbers, flame retardants such as expandable graphite [14], SiO2 or CaCO3 [15]
furniture, automobile products, etc. [1–3]. During recent decades, their were combined with APP to obtain effective fire retardancy for WPCs.
low cost and superior efficiency; including high sustainability, lower Besides APP, several kinds of inorganic additives including aluminum
water uptake, durability against environmental impacts such as fungi and hydroxide [16] and magnesium hydroxide [17] were reported as flame
insects compared with wood, high dimensional stability over their life- retardants for WPCs. Furthermore, some organic flame retardants were
time and high relative stiffness and strength, have attracted manufac- also developed to improve the flame retardancy of WPCs through
turers attention and researchers' interest [4]. However, the main increasing the char yield [18,19]. However, to achieve a satisfactory
drawback of WPCs is their high flammability which limits their appli- flame retardant level, high loading of either inorganic or organic flame
cation in various fields. Therefore, enhancement of their flame retardant retardants mentioned above is usually required. Poor compatibility be-
properties is valuable and much effort has been devoted to this area. The tween these flame retardants and polymer matrix resulted in

* Corresponding author.
E-mail address: [email protected] (D.-Y. Wang).

https://doi.org/10.1016/j.firesaf.2017.11.001
Received 25 January 2017; Received in revised form 1 October 2017; Accepted 4 November 2017
Available online xxxx
0379-7112/© 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: E.N. Kalali, et al., Flame-retardant wood polymer composites (WPCs) as potential fire safe bio-based materials for
building products: Preparation, flammability and mechanical properties, Fire Safety Journal (2017), https://doi.org/10.1016/j.firesaf.2017.11.001
E.N. Kalali et al. Fire Safety Journal xxx (2017) 1–7

deterioration of both tensile and impact strength and the elongation at addition. The pH value was maintained at a constant pH ¼ 10.0 ± 0.5 by
break of the resultant WPCs [5]. Therefore, to develop new technology to the simultaneous addition of a 1 M NaOH solution. The sediment ob-
balance flame retardancy and other properties of WPCs is essential. tained was stirred for 30 min; it was subsequently aged for a minimum
Previous reports have suggested that incorporation of nano-fillers can 18 h at 75  C. The slurry was then filtered and thoroughly washed with
improve the flame retardancy, as well as the mechanical properties and deionised water until a neutral pH was obtained. It was then dried at
thermal stability of polymer composites simultaneously [20–22]. room temperature for 48 h and at 90  C for 12 h, until a constant weight
Nevertheless, few literature have focused on the effect of nano-fillers on was achieved.
the flame retardancy and mechanical properties of WPCs.
Our previous research investigated whether layered double hydrox- 2.3. Preparation of WPCs
ides (LDHs) can also be used as flame retardant additives because of their
endothermic decomposition upon exposure to high temperatures [23]. The wood-flour was dried in an oven at 105  C for about 24 h until a
LDHs [24] are a relatively new category of anionic nano-clays. They constant weight was obtained. Wood polymer composites were com-
possess a brucite (Mg(OH)2)-like layered structure in which some of the pounded in a parallel co-rotating twin-screw extruder (DSE 20/40 D,
divalent cations have been substituted by trivalent cations forming Brabender, Germany) at 190  C for 20 min, cooled under water and
positively charged layers. The general molecular formula of LDHs can be finally pelletized. The formulations are listed in Table 1. The resulting
represented as [M2þ1-xM3þx(OH)2]xþ.[(An)x/n.yH2O]x, where M2þ, pellets were subsequently dried in an oven before the injection. The
M3þ, and An represent divalent metal cations, trivalent metal cations, specimens for cone calorimetry, LOI, UL-94 and mechanical testing were
and interlayer anions, respectively [25]. Incorporation of a low loading prepared by injection moulding (Arburg, model: 320 C, d ¼ 30 mm,
of LDHs into a polymer matrix can provide excellent flame retardant Germany) under 1300 bar and the temperature of the heating zones set as
properties compared with the addition of a high loading of conventional 180  C, 185  C, 190  C, 195  C and 200  C.
flame retardants such as aluminium trihydroxide (ATH) or magnesium
hydroxide (MH). It is thought that the layered structure might be a key
2.4. Characterization methods
factor in this aspect [26]. However, to achieve satisfactory flame retar-
dant synergism it would be necessary to insert some modifiers into the
2.4.1. Flammability test
interlayer gallery space of the LDH in order to dedicate particular func-
The LOI values were examined using an Oxygen Index instrument
tionalisation to the polymer. Different kinds of anionic surfactants, such
(Fire Testing Technology, UK) in accordance with ASTM D2863-97. The
as sulfonates [27,28], phosphates [29–31], fatty acid salts [32], etc. have
dimensions of the prepared sample were 130  6.5  3.2 mm. Vertical
been used as modifiers for LDHs. Among them, phytic acid (Ph) is a
burning testing was carried out using a burning chamber (UL-94, Fire
natural bio-based saturated cyclic acid that can be found in grains and
Testing Technology, UK) with sample dimensions of
cereals, which are well known as a phosphorus resource.
127  12.7  3.2 mm in accordance with the ASTM D3801 standard and
In this work, the goal was to investigate the synergistic effect of phytic
three specimens were tested from each group.
acid modified LDH (Ph-LDH) and APP as a flame retardant on WPCs. The
effects of modified LDHs on the thermal stability of WPCs were analysed
2.4.2. Cone calorimeter test
by thermogravimetric analysis (TGA). The flammability of WPCs was
The combustion tests were conducted using a cone calorimeter (FTT,
characterised by limited oxygen index (LOI) testing, vertical burning
UK), in accordance with the ISO 5660-1 standard procedures. The bottom
testing (UL-94) and cone calorimeter tests (CCT). The morphologies of
and sides of the squared specimens (100  100  4 mm) were wrapped
the chars obtained after the CCT experiments were examined by means of
with aluminium foil and horizontally irradiated at a heat flux of 50 kW/
scanning electron microscopy (SEM). Tensile tests and impact tests were
m2, corresponding to a medium fire scenario. In order to obtain robust
conducted in order to study the influence of the additives on mechanical
results, three specimens from each sample were tested and the average
properties.
results were reported.
2. Materials and methods
2.4.3. Scanning electron microscopy
A scanning electron microscope (Zeiss, EVO MA15, Germany) was
2.1. Materials
used to observe the morphology of the external surface of the char resi-
dues at the end of the cone calorimeter tests and the fracture surface of
Aluminium nitrate nonahydrate, magnesium nitrate hexahydrate,
samples after the impact tests.
sodium hydroxide and phytic acid sodium salt, were supplied by Sigma-
Aldrich and used without further purification. Polypropylene (PP-070)
2.4.4. Thermogravimetric analysis
was supplied by Repsol (Spain), polypropylene grafted with maleic an-
To investigate the effect of Ph-LDH on the thermal decomposition
hydride (PP-g-MA, FUS P353-Canada) was provided by Dupont and
hardwood cubic particles with an average particle size of 0.125 mm were
Table 1
provided by Harimasa S.L (Spain). Ammonium polyphosphate was sup-
Formulations of WPC samples.
plied by Budenheim (Germany).
Sample PP PP-g-MA Wood Flour APP Ph-LDH
(%) (%) (%) (%) (%)
2.2. Synthesis of modified layered double hydroxides via a one-step
method Pure PP 100 – – –
WPC 46.7 3.3 50 – –
APP/WPC 35.7 3.3 50 11.0 –
Modified LDH was synthesised by co-precipitation of Al(NO3)3 and Ph-LDH(0.5%)/ 35.7 3.3 50 10.5 0.5
Mg(NO3)2 in an alkaline solution containing phytic acid sodium salt. In a APP/WPC
1000 ml volume three-neck round flask which was equipped with a pH Ph-LDH(1.0%)/ 35.7 3.3 50 10.0 1.0
APP/WPC 35.7 3.3 50 9.5 1.5
meter, stirrer and reflux-condenser, 300 ml deionised water was intro-
Ph-LDH(1.5%)/APP/
duced and phytic acid sodium salt (0.1 mol) was added and dissolved at WPC
45  C. A solution containing Al(NO3)3.9H2O (0.1 mol) and Ph-LDH(2.0%)/ 35.7 3.3 50 9.0 2.0
Mg(NO3)2.6H2O (0.2 mol) prepared by dissolving the two salts in 300 ml APP/WPC
deionised water, was added drop-wise to the above mixture using an PP: Polypropylene, PP-g-MA: Polypropylene grafted with maleic anhydride, APP: ammo-
isobaric dropping funnel, the solution was stirred vigorously during the nium polyphosphate, Ph-LDH: phytic acid modified LDH.

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Table 3
Limiting Oxygen Index (LOI) and UL-94 test results for the pure PP and WPCs.

Sample LOI UL- T1 T2 Observation

(%) 94 (s)

Pure PP 19.0 No Burn out Intense and sooty flame with

rating dripping
WPC 18.7 No Burn out Intense and sooty flame with no
rating dripping
APP/WPC 22.8 No Burn out Low flame with low white
rating smoke and no dripping
Ph-LDH(0.5%)/ 23.0 V-0 7 8 Immediate extinguish
APP/WPC
Ph-LDH(1.0%)/ 23.2 V-0 5 6 Immediate extinguish
APP/WPC
Ph-LDH(1.5%)/ 24.2 V-0 3 2 Immediate extinguish
APP/WPC
Ph-LDH(2.0%)/ 23.0 V-1 9 23 Low flame with low white
APP/WPC smoke and no dripping

decompose at much lower temperatures compared with the pure PP [33].

In the case of the APP/WPC sample, T5%, T50%, and especially char
residue at 750  C, increased with partial incorporation of ammonium
polyphosphate (APP). Co-incorporation of 0.5, 1 and 1.5 wt% Ph-LDH
Fig. 1. TGA thermograms of pure PP and wood polymer composites. into the flame retardant WPC (APP/WPC) decreased the T5% of the
samples, leading to earlier thermal decomposition of the specimens. In
behaviour of WPCs, TGA analysis was conducted by using a thermo- addition, T50% slightly increased, demonstrating a more stable residue
analyser instrument (TA Instruments, Q50) at a linear heating rate of during decomposition. Moreover, by increasing the loading of Ph-LDH in
10  C/min under nitrogen flow. The samples were dried at 110  C in a the flame retardant WPC, an improvement in composite char residue
vacuum oven for 12 h prior to measurement. Each sample was ground up formation was observed. The residues for Ph-LDH(0.5%)/APP/WPC, Ph-
prior the drying process and 5 ± 0.5 mg was placed in a platinum pan. In LDH(1.0%)/APP/WPC and Ph-LDH(1.5%)/APP/WPC were 17.7%,
order to obtain more accurate results, two specimens from each sample 21.7% and 23.4% respectively, indicating an improvement in the flame
were tested. retardant properties of the flame retardant WPC. Co-incorporation of
2 wt% Ph-LDH into the flame retardant WPC showed an opposite effect in
2.4.5. Mechanical analysis the thermal properties and the remaining residue after the test.
A Universal Testing Machine (Instron, model 3384) was used to
measure the tensile strength and elongation at break of dumbbell-shaped 3.2. Flammability of wood-polymer composites (WPCs)
WPC specimens. The tests were performed with a crosshead speed of
5 mm/min at 25 ± 2  C, in accordance with ASTM D-638. Five dumbbell LOI and UL-94 tests were carried out in order to test the flammability
replicate samples from each group were analysed in order to obtain of WPC specimens and the corresponding results are represented in
reproducible results and the average values were reported. Table 3. Incorporation of wood flour and PP-g-MA into the PP matrix
To examine the impact strength of the WPC samples, a Charpy impact resulted in a slight deterioration in the LOI to 18.7% for the neat WPC
tester (Zorn Standal Instrumented Charpy Impact Tester, Germany) was compared to 19% for pure PP. Partial substitution of APP by PP shows an
used. To achieve reliable results, six notched specimens with the di- increase in the LOI value of APP/WPC. Furthermore, the co-addition of
mensions of 50  6  4 mm, were examined at an impact speed of different loadings of Ph-LDH (0.5, 1, 1.5, 2 wt%) into the flame retardant
2.93 m/s in accordance with the DIN 53753 standard. WPC formulation leads to a notable increase in the LOI with the
maximum LOI value of 24.2% obtained for the Ph-LDH(1.5%)/APP/
3. Results and discussion WPC sample.
It was also observed that co-addition of 0.5, 1, 1.5 and 2 wt% of Ph-
3.1. Thermal properties LDH into the flame retardant WPC provided a positive influence on the
UL-94 testing behaviours. Neat WPC and APP/WPC samples exhibited no
Thermal properties and TGA thermograms of pure PP and WPCs are rating in the UL-94 vertical burning tests. Fire propagated quickly with a
shown in Fig. 1 and Table 2, respectively. Pure PP presented no char sooty flame from ignition in the case of neat WPC and the APP/WPC
residue, a thermal decomposition temperature at 5% weight loss (T5%) of sample ignited with a slight delay, a smaller and continuous flame with
419.5  C and a thermal decomposition temperature at 50% weight loss lower smoke evolution compared with the neat WPC samples. In contrast,
(T50%) of 461.2  C. Neat WPC showed a lower T5% than pure PP. This was by adding 0.5, 1 and 1.5 wt% of Ph-LDH into the APP/WPC formulation,
attributed to the presence of celluloses in the wood fibre which starts to quick self-extinguishing are observed and a V-0 rating was achieved.
Incorporation of excess Ph-LDH had a negative effect on the flammability
Table 2 of the flame retardant wood polymer composite. The improved fire
Thermal properties of pure PP and WPCs.
performance of Ph-LDH/APP/WPCs can be attributed to the formation of
Sample T5% T50% Residue at 750  C a more thermally stable intumescent carbonaceous residue upon ignition
( C) ( C) (%) which protects the surrounded polymer matrix against degradation,
Pure PP 419.5 461.2 0.1 hence effectively improving the fire performance of WPCs.
Neat WPC 272.3 450.1 8.5
APP/WPC 285.6 474.5 16.4
Ph-LDH(0.5%)/APP/WPC 287.8 479.0 17.7 3.3. Combustion behaviors
Ph-LDH(1.0%)/APP/WPC 256.7 476.8 21.7
Ph-LDH(1.5%)/APP/WPC 250.0 483.4 23.4 One of the most effective methods for the laboratory evaluation of the
Ph-LDH(2.0%)/APP/WPC 247.8 481.2 23.0
fire development properties of polymer composites is cone calorimetry,

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Fig. 2. Heat release rate curves as a function of time for pure PP and WPCs.

Fig. 3. Total heat release curves for pure PP and WPCs.

which can simulate the behaviour of materials in a real fire and aid
further interpretation of the results from LOI and UL-94 tests on poly-
mers. Different important parameters including time to ignition (TTI), 83.0 MJ/m2 respectively. These results indicated that incorporation of
peak heat release rate (pHRR), total heat release (THR), etc. can be the Ph-LDH showed a positive effect in reducing the THR, which means a
measured by cone calorimeter tests. The heat release rate (HRR) curves reduction in the volatile products which serve as combustible gases. As a
measured by a cone calorimeter for pure PP and WPCs are given in Fig. 2 result, the addition of Ph-LDH was capable of playing a positive role in
and the corresponding data are listed in Table 4. From Table 4, it can be the flame retardant WPC.
seen that the addition of wood flour did not change the TTI. But, partial Furthermore, Ph-LDH/APP/WPCs specimens left more residual
substitution of APP with PP leads to a reduction in the TTI in flame weight after combustion than WPC/APP, illustrating the formation of an
retardant WPC to 25 s from 34 s for the neat WPC. Incorporation of Ph- effective residual mass yield in a real fire scenario, which could protect
LDH did not provide any positive changes to the TTI of the flame retar- the surrounding materials from further thermal degradation. Ph-
dant WPCs. The TTI reduction in Ph-LDH/APP/WPC samples is attrib- LDH(1%)/APP/WPC and Ph-LDH(1.5%)/APP/WPC displayed the high-
uted to the lower thermal stability of WPCs which is in agreement with est char yield of 26.8% and 23.1% respectively, which are responsible for
the TGA results. As shown in Fig. 2, pure PP burns quickly after ignition the reduction in pHRR and THR values.
and a steep HRR curve appears between 40 and 390 s with a pHRR value Fig. 4 shows the mass loss versus time curves for pure PP and wood-
of 1294 kW/m2. The incorporation of 50 wt% wood flour and 3.3 wt% polymer composites. A steep mass loss curve with no residue left after
PP-g-MA into the PP matrix resulted in a great reduction in pHRR (-54%) burning was recorded for Pure PP. Neat WPC showed a great improve-
from that for neat WPC to 585 kW/m2. Partial incorporation of APP with ment in residual mass yield. However, incorporation of APP into the WPC
PP induced a further reduction in the pHRR (503 kW/m2) of the flame showed a negative effect on the char formation process and residual mass
retardant WPCs (APP/WPC). yield. In contrast, co-addition of Ph-LDH and APP demonstrated a further
Compared to APP/WPC (503 kW/m2), the addition of 0.5, 1 and enhancement in the char yield.
1.5 wt% of Ph-LDH resulted in a further reduction in the pHRR value to The other important parameter that is analysed for flame retardant
301, 285 and 280 kW/m2, respectively. However, further loading with polymer composites is the emission of smoke. Total smoke production
Ph-LDH had a negative effect on the pHRR value for the flame retardant versus time curves are represented in Fig. 5. Following the incorporation
WPC. Additionally, the burning time of flame retardant WPCs is pro- of wood flour into the polymer matrix, smoke emission increased to
longed compared to neat WPC, indicating a synergistic effect of Ph-LDH 31.2 m2 for neat WPC compare with the volume for pure PP of 18.1 m2.
and APP/WPC on the formation of an effective char layer [34]. Furthermore, it was observed that the smoke emission of flame retardant
THR values are shown in Fig. 3. The results indicated that the partial WPCs during the combustion process demonstrated a greater reduction
substitution of APP into the neat WPC showed a notable effect in compared to neat WPC, implying a smoke suppression effect for the flame
lowering the THR of the final composite compared with pure PP. More- retardants.
over, the THR value for Ph-LDH(0.5%)/APP/WPC, Ph-LDH(1.0%)/APP/ It is common knowledge that high temperature smoke is the major
WPC and Ph-LDH(1.5%)/APP/WPC is reduced to 87.5, 91.0 and cause of fire mortalities and it is usually reported as one of the main
critical factors during fire accidents. Therefore, lowering the smoke

Table 4
Cone calorimetry data.

Sample TTI (s) pHRR THR TSP Residue Smoke Temperature ( C)

(kW/m2) (MJ/m2) (m2) (%)

Pure PP 34 ± 1.6 1294 ± 39 154.2 ± 3.4 18.1 ± 0.9 0.2 555.1 ± 7.8
WPC 35 ± 1.2 585 ± 21 139.2 ± 2.7 31.2 ± 1.1 25.2 435.4 ± 6.3
APP/WPC 25 ± 1.3 503 ± 32 132.9 ± 2.4 10.9 ± 0.8 8.5 422.6 ± 5.6
Ph-LDH(0.5%)/APP/WPC 22 ± 2.1 301 ± 19 87.5 ± 3.1 10.2 ± 0.9 20.3 475.5 ± 9.8
Ph-LDH(1.0%)/APP/WPC 25 ± 1.8 285 ± 27 91.1 ± 1.3 13.3 ± 0.5 26.8 376.3 ± 6.0
Ph-LDH(1.5%)/APP/WPC 25 ± 1.7 280 ± 18 103.2 ± 3.2 10.8 ± 0.7 20.32 375.9 ± 8.2
Ph-LDH(2.0%)/APP/WPC 23 ± 1.3 282 ± 17 83.1 ± 2.9 12.1 ± 0.6 23.1 377.6 ± 9.2

TTI: time to ignition, pHRR: peak heat release rate, THR: total heat release, TSP: total smoke production.

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Fig. 4. Mass loss curves for pure PP and WPCs. Fig. 6. Smoke temperature versus time curves for pure PP and WPC composites.

temperature during combustion will be beneficial for the fire rescue constituted a char layer with enhanced physical integrity and a compact
process. Smoke temperature versus time curves for PP and WPC com- and continuous surface, which is desirable as this inhibits heat and mass
posites during combustion are shown in Fig. 6. The smoke temperature of transfer between flames and the polymer matrix.
neat WPC and flame retardant WPCs are lower than that of pure PP. To further investigate the microscopic structure of the residual chars,
However, it was observed that the partial substitution of APP with PP SEM was used to study the exterior surface of the residual chars of the
(APP/WPC) provided almost no change in smoke temperature compared WPC composites, as shown in Fig. 8. In the case of neat WPC and APP/
with neat WPC. Furthermore, co-addition of APP and nano-fillers (Ph- WPC, the char structures are crispy and weak with many channels and
LDH) resulted in a further reduction in smoke temperature. holes in their surface (Fig. 8a and b). These types of residual chars cannot
Some important information regarding flame retardant mechanisms act as an appropriate thermal insulator layer. In the case of flame retar-
can be extracted from the residual chars formed during combustion. The dant WPC with 0.5, 1 and 2 wt% of Ph-LDH, similar residual chars formed
morphology of the char residues of WPCs after cone calorimeter tests after the cone calorimeter tests. A fume-like layer appeared on the surface
were further investigated and digital photographs of the residual chars of the residual chars, but it was still cracked with lots of open holes
are shown in Fig. 7. The residues were affected by the flame retardant (Fig. 8c), which also provides no protection against mass and heat
additives and had an obviously different appearance. Pure PP showed no transfer during combustion. In contrast, the Ph-LDH(1.5%)/APP/WPC
residue after combustion (Fig. 7a). For neat WPC (Fig. 7b), the com- sample formed a more stable, compact and effective barrier layer, which
busted residues from cone calorimeter testing showed discontinuities, prevented the transportation of combustible gases and heat to the surface
were full of superficial cracks and had a fluffy char layer. In the case of of the burning sample, thus decreasing pyrolysis reactions and inhibiting
APP/WPC, residual char became worse compared with the one for neat fire spread (Fig. 8d). All these results implied that Ph-LDH is feasible for
WPC and it obviously did not form an effective char layer (Fig. 7c). In the enhancing the flame retardancy of WPC.
case of Ph-LDH(0.5%)/APP/WPC, the char residue formed was sponge-
like with lots of open holes. The char layer of Ph-LDH(1%)/APP/WPC
3.4. Mechanical properties
and Ph-LDH(2%)/APP/WPC showed slight improvement compared to
that of Ph-LDH(0.5%)/APP/WPC, although there were still lots of open
The mechanical performances, including the tensile and impact
holes on the surface. In contrast, Ph-LDH(1.5%)/APP/WPC (Fig. 7d)
strength of neat WPC, APP/WPC, and Ph-LDH/APP/WPCs are shown in
Table 5. Obviously, the tensile and impact strength properties of neat
WPC reduced after the incorporation of APP by 10.1% and 32.8%
respectively. Furthermore, following partial substitution of the APP with
the PP, the Young's modulus results showed a slight reduction. The
addition of 0.5 wt% Ph-LDH to the flame retardant WPC formulation
(APP/WPC) gave a slight increase in the mechanical properties. With the
co-incorporation of 1 wt% of Ph-LDH, the Young's modulus showed
relatively slight amelioration and the tensile strength, tensile strain and
impact strength of the flame retardant WPC (APP/WPC) increased by
13.8%, 17.2% and 26.8% respectively, illustrating the optimal mechan-
ical properties. Further addition of Ph-LDH demonstrated contradictory
results for mechanical performance. From the results, it can be suggested
that the best loading of Ph-LDH was 1 wt%.
The observed increase in mechanical properties displayed the effect
of a nano-filler as a reinforcing agent that interlocks the polymer chain
inside the wood polymer composite matrix and confines the mobility of
the polymer chains [35]. However, excess Ph-LDH could result in the
initiation of micro-cracks due to the aggregations formed inside the WPC
Fig. 5. Total smoke production curves as a function of time for pure PP and WPCs. matrix, therefore providing a negative effect on mechanical performance.

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Fig. 7. Digital images of the residual char after cone calorimeter test: (a) Pure PP, (b) WPC, (c) APP/WPC and (d) Ph-LDH(1.5%)/APP/WPC.

Fig. 8. SEM images of the charred residue after cone calorimeter test: (a) neat WPC, (b) APP/WPC, (c) Ph-LDH(0.5%)/APP/WPC and (d) Ph-LDH(1.5%)/APP/WPC.

Table 5 matrix have been pulled out together with the wood fibre, indicating an
Tensile and impact properties of WPCs. effective interaction between the wood fibres and the PP/PP-g-MA ma-
Sample Young Tensile Tensile strain Notched trix. Compared with neat WPC (Fig. 9a), the micrograph of the fracture
Modulus strength (mm/mm) charpy surface of WPC/APP (Fig. 9b) displayed lots of cracks and voids and
(MPa) (MPa) impact
randomly distributed APP particles with a naked surface. This indicates
strength (kJ/
m2 ) the incompatibility of APP particles with the WPC matrix, which resulted
in a reduction in the mechanical performance of WPC (Table 5). The
WPC 3787 ± 66 13.8 ± 0.5 0.01605 14.6 ± 0.46
APP/WPC 3561 ± 59 12.4 ± 0.6 0.01479 9.8 ± 0.35
image of Ph-LDH(0.5%)/APP/WPC (Fig. 9d) shows an improvement in
Ph- 3854 ± 63 12.6 ± 0.7 0.01465 10.7 ± 0.33 the interfacial bonding between the wood fibres and the PP matrix and
LDH(0.5%)/ embedded additives, but still with voids and cracks in the fracture sur-
APP/WPC face. Similar images have been recorded for Ph-LDH(0.5%)/APP/WPC.
Ph- 4059 ± 72 14.4 ± 0.5 0.01788 13.4 ± 0.29
In contrast, the micrographs for Ph-LDH(1.0%)/APP/WPC (Fig. 9c)
LDH(1.0%)/
APP/WPC showed no obvious sign of porosity and holes and non-covered
Ph- 3743 ± 49 13.3 ± 0.6 0.01735 11.4 ± 0.38 wood fibres.
LDH(1.5%)/
APP/WPC
4. Conclusion

The effects of the incorporation of APP and nano-fillers on the me- In order to improve the flame retardant efficiency of ammonium
chanical properties of WPC were further investigated and the morphol- polyphosphate (APP), a novel flame retardant system consisting of
ogies of the fracture surfaces of WPCs after the impact tests were studied ammonium polyphosphate (APP) and phytic acid modified layered
by SEM and the images are shown in Fig. 9. Polypropylene grafted with double hydroxide (Ph-LDH) was exploited for wood polymer composites
maleic anhydride (PP-g-MA), which acts as a coupling agent, provides (WPCs). TGA results showed that the earlier degradation of the Ph-LDH/
surface modification and facilitates molecular cohesion, leading to strong APP further improved the char formation. The flame retardant synergism
adhesion with an inconspicuous phase boundary between the wood flour between Ph-LDH and APP was proved by the UL-94 vertical burning
and PP matrix in neat WPC. As seen in Fig. 9a, layers of the polymer measurements: Ph-LDH/APP/WPCs containing 0.5, 1 and 1.5 wt% of Ph-
LDH showed a UL-94 V-0 rating, while neat WPC and APP/WPC

Fig. 9. Micrographs of the fracture surface of the (a) WPC, (b) WPC/APP, (c) Ph-LDH(1.0%)/APP/WPC and (d) Ph-LDH(0.5%)/APP/WPC samples.

6
E.N. Kalali et al. Fire Safety Journal xxx (2017) 1–7

demonstrated no rating. According to the results obtained from the cone [13] H. Seefeldt, U. Braun, M.H. Wagner, Residue stabilization in the fire retardancy of
wood-plastic composites: combination of ammonium polyphosphate, expandable
calorimeter tests, by incorporation of wood flour into the polymer matrix,
graphite, and red phosphorus, Macro. Mol. Chem. Phys. 213 (2012) 2370–2377.
the peak heat release rate (pHRR) value decreased about 54.5% compare [14] C. Guo, L. Zhou, J. Lv, Effects of expandable graphite and modified ammonium
to the pure PP, and the pHRR of Ph-LDH/APP/WPCs samples showed polyphosphate on the flame-retardant and mechanical properties of wood flour-
further reduction by 78.5% compared to pure PP. These results indicate polypropylene composites, Polym. Polym. Compos 21 (2013) 449–456.
[15] L.K. Krehula, Z. Katancic, G. Maric, Z. Hrnjak-Murgic, Study of fire retardancy and
that the incorporation of Ph-LDH was effective in suppressing the smoke thermal and mechanical properties of HDPE-wood composites, J. Wood Chem.
production and lowering the total heat release of the samples. The Technol. 35 (2015) 412–423.
improved fire retardant behaviours of Ph-LDH/APP/WPCs was probably [16] T. Umemura, Y. Arao, S. Nakamura, Y. Tomita, T. Tanaka, Synergy effects of wood
flour and fire retardants in flammability of wood-plastic composites, Energy
attributed to the formation of a compact, continuous and thermally stable Procedia 56 (2014) 48–56.
char layer which effectively inhibited heat and mass transfer and finally [17] M. Sain, S.H. Park, F. Suhara, S. Law, Flame retardant and mechanical properties of
led to the enhancement of the flame retardant properties of the WPCs. natural fibre–PP composites containing magnesium hydroxide, Polym. Degrad.
Stabil. 83 (2004) 363–367.
Furthermore, co-incorporation of APP and Ph-LDH illustrated virtually [18] H. Seefeldt, U. Braun, A new flame retardant for wood materials tested in wood-
no deteriorative effect on the impact and tensile properties of WPC plastic composites, Macromol. Mat. Eng. 297 (2012) 814–820.
composites. [19] Y.H. Guan, W. Liao, Z.Z. Xu, M.J. Chen, J.Q. Huang, Y.Z. Wang, Improvement of the
flame retardancy of wood fibre/polypropylene composites with ideal mechanical
properties by a novel intumescent flame retardant system, RSC Adv. 5 (2015)
Acknowledgement 59865–59873.
[20] F. Bergaya, T. Mandalia, P. Amigouet, A brief survey on CLAYPEN and
nanocomposites based on unmodified PE and organo-pillared clays, Colloid. Polym.
This research is funded by Spanish Ministry of Economy and
Sci. 283 (2005) 773–782.
Competitiveness (MINECO) under Ram
on y Cajal fellowship (RYC-2012- [21] M.Z. Pan, C.T. Mei, J. Du, G.C. Li, Synergistic effect of nano silicon dioxide and
10737) and COST Action FP1404 (Fire Safe Use of Bio-based Build- ammonium polyphosphate on flame retardancy of wood fiber-polyethylene
ing Products). composites, Compos. A 66 (2014) 128–134.
[22] G. Huang, S. Wang, P. Song, C. Wu, S. Chen, X. Wang, Combination effect of carbon
nanotubes with graphene on intumescent flame-retardant polypropylene
References nanocomposites, Compos. A 59 (2014) 18–25.
[23] E.N. Kalali, S. De Juan, X. Wang, S. Nie, R. Wang, D.Y. Wang, Comparative study on
[1] A. Ashori, Wood-plastic composites as promising green-composites for automotive synergistic effect of LDH and zirconium phosphate with aluminium trihydroxide on
industries, Bioresour. Technol. 99 (2008) 4661–4667. flame retardancy of EVA composites, J. Therm. Anal. Calorim. 121 (2015) 619–626.
[2] Y. Arao, S. Nakamura, Y. Tomita, K. Takakuwa, T. Umemura, T. Tanaka, [24] E.N. Kalali, X. Wang, D.Y. Wang, Functionalized layered double hydroxide-based
Improvement on fire retardancy of wood flour/polypropylene composites using epoxy nanocomposites with improved flame retardancy and mechanical properties,
various fire retardants, Polym. Degr. Stab. 100 (2014) 79–85. J. Mat. Chem. A 3 (2015) 6819–6826.
[3] O. Faruk, L.M. Matuana, Nanoclay reinforced HDPE as a matrix for wood-plastic [25] E.N. Kalali, X. Wang, D.Y. Wang, Synthesis of Fe3O4 nano-Sphere@MgAl layered
composites, Compos. Sci. Technol. 68 (2008) 2073–2077. double hydroxide hybrid and application in fabricating multifunctional epoxy
[4] P. Wambua, J. Ivens, I. Verpoest, Natural fibers: can they replace glass in fiber nanocomposites, Ind. Eng. Chem. Res. 55 (2016) 6634–6642.
reinforced plastic, Compos. Sci. Technol. 63 (2003) 1259–1264, 9. [26] F.R. Costa, M. Saphiannikova, U. Wagenknecht, G. Heinrich, Layered double
[5] W. Wang, W. Zhang, S.F. Zhang, J.Z. Li, Preparation and characterization of hydroxide based polymer nanocomposites, Adv. Polym. Sci. 210 (2007) 101–168.
microencapsulated ammonium polyphosphate with UMF and its application in [27] D.Y. Wang, A. Das, A. Leuteritz, R.N. Mahaling, D. Jehnichen, U. Wagenknecht,
WPCs, Constr. Build. Mater 65 (2014) 151–158. G. Heinrich, Structural characteristics and flammability of fire retarding EPDM/
[6] N. Suppakarn, K. Jarukumjorn, Mechanical properties and flammability of sisal/PP layered double hydroxide (LDH) nanocomposites, RSC Adv. 2 (2012) 3927–3933.
composites: effect of flame retardant type and content, Compos. B 40 (2009) [28] D.Y. Wang, A. Das, A. Leuteritz, R. Boldt, L. Haussler, U. Wagenknecht, G. Heinrich,
613–618, 7. Thermal degradation behaviors of a novel nanocomposite based on polypropylene
[7] M.B. Abu Bakar, Z.A. Mohd Ishak, R. Mat Taib, H.D. Rozman, S. Mohamad Jani, and Co-Al layered double hydroxide, Polym. Degrad. Stab. 96 (2011) 285–290.
Flammability and mechanical properties of wood flour filled polypropylene [29] M.A. Woo, T.W. Kim, M.J. Paek, H.W. Ha, J.H. Choy, S.J.J. Hwang, Phosphate-
composites, J. Appl. Polym. Sci. 116 (2010) 2714–2722. intercalated Ca-Fe-layered double hydroxides: crystal structure, bonding character,
[8] M. Garcia, J. Hidalgo, I. Garmendia, J. Garcia-Jaca, Wood-plastics composites with and release kinetics of phosphate, J. Solid. State. Chem. 184 (2011) 171–176.
better fire retardancy and durability performance, Compos. A 40 (2009) [30] G.R. Williams, N.H. Rees, D.T. O'Hare, Incorporation of phosphorus oxyacids into
1772–1776. layered double hydroxides, Solid. State. Sci. 11 (2009) 1229–1238.
[9] M. Sain, S.H. Park, F. Suhara, S. Law, Flame retardant and mechanical properties of [31] X. Wang, Y. Hu, L. Song, W.Y. Xing, H.D. Lu, P. Lv, G. X Jie, Flame retardancy and
natural fibre-PP composites containing magnesium hydroxide, Polym. Degrad. Stab. thermal degradation mechanism of epoxy resin composites based on a DOPO
83 (2004) 363–367, 2. substituted organophosphorus oligomer, Polymer 51 (2010) 2435–2445.
[10] B. Schartel, U. Braun, U. Schwarz, S. Reinemann, Fire retardancy of polypropylene/ [32] N. Nhlapo, T. Motumi, E. Landman, S.M.C. Verryn, W.W.J. Focke, Surfactant-
flax blends, Polymer 44 (2003) 6241–6250. assisted fatty acid intercalation of layered double hydroxides, J. Mat. Sci. 43 (2008)
[11] N. Ayrilmis, T. Akbulut, T. Dundar, R.H. White, F. Mengeloglu, U. Buyuksari, 1033–1043.
Z. Candan, E. Avci, Effect of boron and phosphate compounds on physical, [33] N. Suppakarn, K. Jarukumjorn, Mechanical properties and flammability of sisal/PP
mechanical, and fire properties of wood-polypropylene composites, Constr. Build. composites: effect of flame retardant type and content, Compos. B 40 (2009)
Mater 33 (2012) 63–69. 613–618.
[12] Z.X. Zhang, J. Zhang, B.X. Lu, Z. Xin, C. Kang, J. Kim, Effect of flame retardants on [34] B. Schartel, M. Bartholmai, U. Knoll, Some comments on the main fire retardancy
mechanical properties, flammability and foamability of PP/wood-fiber composites, mechanisms in polymer nanocomposites, Polym. Adv. Technol. 17 (2006) 772–777.
Compos. B 43 (2012) 150–158. [35] J. Wei, T. Vo, F. Inam, Epoxy/graphene nanocomposites- processing and properties:
a review, R. S. C. Adv. 5 (2015) 73510–73524.