Fire Retardancy of Kaolinite/Ethyl Vinyl Acetate composites

Marcos Batistellaa,b, Belkacem Otazaghinea, Rodolphe Sonniera, Carlos Petterb, Jose-Marie Lopez-Cuestaa
a
Centre des Materiaux de Grande Diffusion Ecole des Mines dAles, 6, Avenue des Clavieres Ales
France
b
Universidade Federal do Rio Grande do Sul, Av. Bento Gonalves, 8500 Porto Alegre RS Brazil
(marcos.batistella@mines-ales.fr)

Abstract

The flame retardant effect of an ultrafine kaolinite in ethylene vinyl acetate copolymer
(EVA) was studied and compared with a micronic alumina trihydrate (ATH) up to 60%
wt loading. TGA showed a higher decomposition temperature for EVA/kaolinite and
improved FR performance using cone calorimeter. For 35 wt% loadings, pHRR was
reduced by 55% compared to EVA/ATH. Also, it has been shown that kaolinite leads to
significant intumescent behavior. In addition, viscosity seems to play an important role
on fire retardancy of EVA/kaolinite composites.

Keywords: kaolinite, ATH, EVA, fire behavior.

Introduction

Fire behavior of Ethyl vinyl acetate (EVA) have been extensively studied [19]. Many
systems were proposed (halogenated compounds, phosphorus, inorganic fillers and
nanoparticles). EVA/aluminium hydroxide (ATH) and EVA/magnesium hydroxide
(MDH) composites require a very high proportion of the metal hydrate filler within the
polymer matrix (60% wt.) to achieve a suitable level of flame retardancy (ref). This high
level of incorporation may lead to a lack of flexibility, poor mechanical properties and
problems during compounding.

Kaolinite, with theoretical formula Al2Si2O5(OH)4 and basal interlayer space of 7.1 , is
a 1:1 or TO type clay mineral, since it is formed by combining sheets of SiO4 tetrahedra
(T) and Al(OH)6 octahedra (O), in 1:1 proportion (figure a faire). Each lamella remains
attached to each other because they share common oxygen atoms, giving rise to the
structure of the clay mineral [10], [11]. It is widely used as paper filler and coating
pigment. At the best of our knowledge, kaolinite is not widely used in polymer industry
and few studies have concerned its use in polymers. Therefore, in this study, the flame
retardant effect of an ultrafine kaolinite in ethylene vinyl acetate copolymer (EVA) was
studied and compared with an alumina trihydrate (ATH).

Materials and methods

Kaolinite specific surface area was found to be 14.2 0.3 m2*g-1 (BrunauerEmmett
Teller (B.E.T) method, using N2 as adsorbed gas on a Beckman Coulter SA3100
instrument). The average particle size (d50) of kaolin obtained by laser particle-size
analysis (Coulter LS230) was estimated around 0.8 m. Alumina hydroxide was
supplied by. Apyral OP22, with a mean diameter of 12 m. The EVA was Alcudia
PA440 from Repsol and contained 28% of vinyl acetate.

Compositions were extruded using a Clextral BC21 twin-screw extruder (Clextral

Pacific Pty. Ltd., Sidney, Australia) and injection molded using 50 ton Krauss-Maffei
equipment (Munich, Germany). Square specimens were prepared with dimensions of
100 100 4 mm.

Characterization

Thermogravimetry was carried out on 10-12 mg samples at 10C*min-1 to 800 C under

nitrogen or air using a Perkin-Elmer Pyris-1 TGA. A Scanning Transmission Electron
Microscopy (FEI Quanta 200 SEM) was used to study the morphology of the samples.
All images were obtained under high vacuum at a voltage of 15.0 kV. The cone
calorimeter experiments were carried out using a Fire Testing Technology apparatus
with an irradiance de 50 kW*m-2. PCFC analysis was carried out in a FTT apparatus
with a heating rate of 1 C*s1, the maximum pyrolysis temperature was 750 C and the
combustion temperature 900 C. The flow was a mixture of O2/N2 20/80 at 20 cm3
min1 and the sample weight was 20.5 mg. Viscosity measurements were carried out in
dynamic mode at 160 C using 0.5 % strain and a frequency ranging from 10-1s-1 to
102s-1 (ARES, Rheometric Scientific).

Cone calorimeter results

The HRR plots for the composites at a 50 kW*m-2 are shown in Fig.1 and complete
results are shown in Table 1. It is evident that the pHRR is clearly reduced when the
charges are added to the polymer. The results obtained shows that the weight percentage
of ATH must be at least 50 wt. % in order to reach an improvement in fire retardancy in
terms of pHRR. Also, EVA/ATH composites melt as neat polymer and showed a very
strong bubbling, even in the pre-ignition period. Kaolinite composites showed a
remarkably different behavior: pHRR is largely reduced and combustion time and time
to ignition (TTI) increased in comparison with ATH composites. Also, kaolinite
provides the formation of a rigid protective layer which could be responsible for the
improved fire behavior observed. This behavior was reported for some nanocomposites
(the formation of a protective layer) (ref).

1500 1500

1250 1250
EVA EVA
1000 A20 1000 K20
HRR (kW/m)

A35 K35
750 A50 750 K50
A60 K60
500 500

250 250

0 0
0 200 400 600 800 0 200 400 600 800 1000
Time (s) Time (s)

Fig.1 Cone Calorimeter tests for EVA formulations. Heat flux: 50 kW*m-2.

From Table 1, a decrease in average mass loss and an increase in average specific
extinction area of kaolinite in comparison with ATH composites. Also, it is showed that
TTI decreases for low charge loading and increases as filler load increases.

EHC of ATH composites decreased as a function of filler loading, which confirms that
ATH has an influence in the gas phase. In the case of kaolinite composites, EHC
remained almost constant, confirming the fact that kaolinite has not an effect on gas
phase. This behavior is expected as kaolinite release only 14 % of water at high
temperature (about 600 C).

Time to ignition
Time to ignition showed an interesting behavior. The increase in kaolinite composites
was greater than ATH until 50% loading. While for ATH composites water liberation
could lower the temperature of the polymer and dilute gases at the surface, for kaolinite
it seems that the formation of a protective layer in the surface of the sample could slow
the rate of the transfer of the degradation products to the flame. This leads to the
observed behavior. The formation of this protective layer was confirmed by SEM
images (Fig.4 a and b). As can be seen, kaolinite particles are oriented in the surface of
residue, which confirms the formation of a protective layer.

Table 1.Cone calorimeter results.

ATH Kaolinite PHRR TTI EHC ASEA AMLR
(%) (%) (kW/m) (S) (kJ/g) (m2/kg) (g/s m2)
EVA 0 0 1504 48 35 463 22,4
A20 20 0 1032 29 32 424 17
A35 35 0 602 35 28 340 16
A50 50 0 411 47 26 350 11
A60 60 0 282 64 24 219 7,5
K20 0 20 596 37 33 600 14
K35 0 35 262 42 32 484 6
K50 0 50 199 46 32 407 5
K60 0 60 192 56 29 366 5

Residues are also very different. EVA/ATH leaves a thin grey residue (Fig. 3 b),
whereas the EVA/kaolinite composites The images of the residues in Fig. 3 show a
continuous network structure without cracks for the kaolinite samples with, at least,
35% loading. Also, an intumescent behavior were observed (Fig. 3 a). The formation of
this network was observed in the SEM images in Fig.4. The formation of this network
could reduce the mass loss rate, keeping the degradation products in the interior of the
sample. This effect is supported by the lower mass loss ratio of kaolinite composites
shown in Fig. 2.
 100
100 EVA
EVA
A20 K20
80 A35 K35
80
A50 K50
A60 K60
60
Weight (%)

60

40 40

20 20

0 0
0 200 400 600 800 200 400 600 800
Time (s) Time (s)
Fig. 2. Weight loss in cone calorimeter.

a b

Fig. 3. Cone calorimeter residues: a) K50; b) A50.

This intumescence could slow the velocity of the rising degradation products, allowing
radical recombination reactions. This recombination could lead to more stable products,
stabilizing the polymer. In this case, the degradation will occur over a long time period
reducing pHRR [12] with a reduced weight loss ratio as is observed in Fig. 1 d. This
behavior was confirmed by the observed protective layer that forms on the surface of
the samples before ignition.
 Fig.4. SEM images of K50 cone calorimeter residues.

PCFC

Pyrolysis combustion flow calorimeter (PCFC) has used to study the fire behavior of
mg-sized samples [1316]. Between the parameters obtained in PCFC, the HRC
(maximum heat release rate divided by the constant heating rate in the test) has been
proposed as the single best measure of the fire hazard of a material (ref). The results
obtained in PCFC are shown in Fig.5. As can be seen, HRR is reduced at almost the
same content for both fillers, and the reduction is less than in cone calorimeter. This
effect is expected, because PCFC fails to account for physical effects. For example,
barrier effect could be more important in relatively big samples, but not on 1 - 2 mg-
scale sample [13], [16]. Using this assumption, Sonnier et al. [16] proposed a method to
evaluate the barrier effect of the charges. In the proposed method, two parameters are
calculated: the ratio between HRC of the composite and the neat polymer in PCFC is
named R1 and the ratio between pHRR of the composite and the neat polymer in cone
at the same irradiance is named R2.

1 =

2 =

Fig.6 shows the plot of R2 vs R1. Kaolinite/EVA composites are shifted from the
straight X=Y, even for low wt. loadings. This confirms the hypothesis that, in the case
of kaolinite composites, barrier effect is the most important param eter that improves
fire behavior.

800

EVA PA440 EVA PA440

600 A20 K20
A35 K35
A50 K50
HRR (W/g)

A60 K60
400

200

0
0 150 300 450 600 750 150 300 450 600 750

Temperature (C) Temperature (C)

Fig.5. PCFC curves of the composites.

1,0

0,8

0,6
R1

0,4

0,2 ATH
Kaolinite

0,0
0,0 0,2 0,4 0,6 0,8 1,0
R2

Fig.6. R1 vs R2.
Thermal Degradation

The modification of the thermal and thermooxidative behavior of EVA and EVA
nanocomposites is well reported [1], [2], [17], [18]. Thermal degradation of EVA takes
place in two steeps. The first steep evolves deacylation with the elimination of acetic
acid between 300 and 400 C, with some differences observed if the degradation occurs
in nitrogen or air (ref). The main steep is assigned to the degradation of the unsatured
products (ethylene-co-acetylene [6]).

Thermal gravimetric analysis was conducted in air and results are shown in
Fig.7. The loss of acetic acid of EVA/kaolinite composites is accelerated as a function
of clay loading. It was been shown in the literature that the presence of acid sites could
have a catalytic effect [2, 5]. Camino et al. [9] have speculated that the accelerated loss
of acetic acid could be due to the presence of acid sites in the surface of the clay. To
confirm this hypothesis, Costache et al. [12] conducted a series of experiments changing
the surface of the nanocomposite with a silane coupling agent (chlorosilane). The
authors showed that the degradation of the modified nanocomposite were the same as
the neat polymer and concluded that the acid sites in the surface of the clays had a
catalytic effect in the degradation of EVA. In the case of EVA/kaolinite composites, it
seems that the same effect takes place. It should be noted that the cationic exchange
capacity of the kaolinites is lower than Mt. This fact could lead to the lower change in
the degradation pathway observed in comparison with montmorrilonites. This
modification in the first steep of degradation of kaolinite composites is showed in
100 100

80 80

60 60
Weight (%)

40 EVA PA440 EVA PA440 40

A20 K20
20 A35 K35 20
A50 K50
A60 K60
0 0
0 150 300 450 600 750 0 150 300 450 600 750
-20
Derivative Weight (%*min )

-20
-1

-15 -15

-10 -10

250 300 350 400 450 250 300 350 400 450
-5 -5

0 0
0 150 300 450 600 750 0 150 300 450 600 750
Temperature (C) Temperature (C)

Fig.7. The first steep of degradation starts at temperatures slightly lower than neat
polymer as function of kaolin loading.

In the case of ATH composites, the first degradation steep observed is due to the
degradation of the filler, which takes place around 300C.

In the second degradation steep, kaolin composites are slightly more stable than EVA in
air. The layer formed at the surface of the sample could protect the composite limiting
the emission of the degradation products, changing the degradation [1], [8]. It should be
noted that the last degradation steep observed in Kaolinite composites is due to the
degradation of kaolin which starts at about 500 C.
 100 100

80 80

60 60
Weight (%)

40 EVA PA440 EVA PA440 40

A20 K20
20 A35 K35 20
A50 K50
A60 K60
0 0
0 150 300 450 600 750 0 150 300 450 600 750
-20
Derivative Weight (%*min )

-20
-1

-15 -15

-10 -10

250 300 350 400 450 250 300 350 400 450
-5 -5

0 0
0 150 300 450 600 750 0 150 300 450 600 750
Temperature (C) Temperature (C)

Fig.7. TGA in air.

Viscosity

The linear dynamic mechanical properties of several composites have been wide
exanimated (ref). Kashiwagi et al. [19] showed the influence of the viscoelastic
properties in the mass loss rate of polystyrene nanocomposites.

Viscosity increase is expected to have important effects in fire behavior. Increased

viscosity leads to a reduction in rising bubble velocity and bubble growth. It has been
shown by

The storage modulus G provides a measure of stiffness and its frequency dependence
characterizes whether the material is in the solid-like or liquid like state.
The storage modulus (G) shows the capability of the material to store energy that will
be released after the deformation is recovered.

As can be seen in the Fig. 8, storage modulus increased for all formulations, but the
increase was higher for kaolinite composites (In general, the G values increase with
increasing shear rate (ref). Adding particles to a polymer has the effect of increasing G
values (ref). As the solids loading increases, the slope of G vs. shear rate decreases due
to the increased particle network structure of the mixture (samples develop a more
elastic character)).

105

104
G'(Pa*s)

103

102
6
EVA
A20
4,5
A35
A50
K20
3
tangent

K35
K50

1,5

0,1 1 10 100
w (rad/s)

Fig. 8. Storage modulus (G) and tangent of composites.

Tangent showed a slightly difference. It remained almost constant for ATH
composites but it decreased significantly for kaolinite composites, which indicates a
more solid-like state. It is well known that plate-like charges tends to improve the
viscosity of the composites (ref), in comparison with spherical ones, which explains
why the viscosities of kaolinite composites are higher.

It has been reported that the incorporation of nanocomposites could trap the degrading
polymer, permitting recombination reactions, leading to the formation of new, more
stable products [2].

Fig.9 shows tangent versus pHRR of all composites. As it can be seen, until a certain
point, pHRR is affected by viscosity. Tangent is the ratio between elastic modulus and
loss modulus (E/E). In this case it is expected that a more rigid composite will slow
the rate of degrading products, leading to an improved pHRR. This hypothesis is
confirmed by the lower weight loss ratio of kaolinite composites (Fig. 2).

The above viscoelastic measurements were conducted at 160 C. Moreover, during

burning the sample temperature could rise temperatures up to 400 C.
 1500

ATH
pHRR (kJ*m )
Kaolin
-2

1000

Y Axis Title
500

0
0,4 0,6 0,8 1,0
Tangent c/Tangent EVA
Fig.9. Normalized tan of the composites.

Conclusions

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