Analysis of kaolinite morphology and dispersion in polyamide-6

composites: impact on fire retardancy and mechanical properties

M. Batistella1, A.S. Caro-Bretelle1*, B. Otazaghine1, P. Ienny1, R. Sonnier1, C. Petter2, J.M.

Lopez-Cuesta1
1C2MA, Ecole des Mines dAls, 6 Avenue de Clavires, 30319 Als-France
2Universidad Federal do Rio Grande do Sul, Av. Bento Gonalves, 8500 Porto Alegre-RS-
Brazil
*Corresponding author: e-mail: Anne-Sophie.Caro@mines-ales.fr, Tel: +33(0)466785631,
Fax: +33(0)466785365

Abstract
The present study focuses on the mechanical properties and fire behaviour of Polyamide-
6/Kaolinite composites. Several kaolinites (exhibiting different shape factor) and different
surface treatments (showing more or less affinity with the matrix) reveal a high level of
disparity in their morphological properties. These morphologies characterised by their
dispersion (interparticular distance) and their distribution (median diameter) are directly
related to mechanical properties. Elastic properties are enhanced, as expected, by kaolinites
addition (with a most effective reinforcement for the kaolinites with the higher shape factor)
but quite unaffected to their surface treatment. The same trend is observed for the resilience.
The yield stress decreases as the median diameter increases: a good interfacial adhesion led to
a better particle desagglomeration and so a higher yield stress. All composites showed a
decrease in the peak heat release rate in comparison with the unfilled polyamide which seems
to be a direct consequence of both particles incorporation and their dispersion/distribution.

Keywords: Fire retardancy, mechanical properties, morphological characterization

*Corresponding author
Tel.: 0033(0)466785631, Fax: 0033(0)466785680
E-mail address: Anne-Sophie.Caro@mines-ales.fr
URL: http://www.ema.fr
1. Introduction

Polymers are widely used since 50 years due to their good mechanical and physical properties
and easy processing. Nevertheless, they present a very low thermal resistance: heat and
oxygen combination leads to ignition and heat release. In this framework, a great challenge
concerns the improvement of polymer fire resistance.
Flame retardancy can be performed through different mechanisms:
Material surface protection: this process raises the question of adhesion/wear
between protection and sample
Material volume protection: flame retardant additives are directly introduced into
the polymer during the mixing stage. Most of the time, these additives lead to the
degradation of mechanical properties of final product and to an increased toxicity.
Mineral particles are among the main flame retardants. The action of these additives is mainly
physical. They can form a non-conductive coating and reduce heat transfer; additives
degradation reaction can also be endothermic and contributes to decrease the heat balance;
additives degradation can also produce inert gases which may dilute combustible gases. In
some cases, metal oxides could also act in a chemical way by absorbing active radicals or
promoting charring. Mineral particles (such as metal hydroxides (ATH, MDH)) offer a great
alternative in the framework of environmental constraint but the needed high level of
incorporation (until 65% by mass fraction) usually leads to poor mechanical properties. On
another hand, nano-mineral particles allow reaching high level of flame retardancy at low
rates (less than 5% by mass fraction). For example organically modified monmorillonite
(oMMT) are used to improve flame retardancy in various polymers: composites PP-g-
MA/oMMT [1], Polyimide(PI)/oMMT [2], PA6/oMMT [3], EVA/oMMT [4] where oMMT
particles are either intercalated or exfoliated, PMMA/Al2O3,TiO2 [5, 6]). Their successful
action in the heat balance can be attributed to
The creation of a diffusion barrier layer [4], [5], [7]
The modification of the polymer degradation: heterogeneous catalysis associated
to a char structure [4], [7]
The modification of the thermal diffusivity [5], [8]
The reduction of the macro molecular mobility (around the charges) [5]
The increase of polymer viscosity [9]
The trapping of radicals formed during the thermal degradation [5]

2
 All these modes of action are highly dependent on the nanoparticle distribution
[5, 6].
Nevertheless nanoparticles are usually used in combination with classical flame retardants
because even if they lead to a more progressive heat release, the global heat balance remains
the same [10, 11, 12]. Moreover their processability limits their level of incorporation (always
under 10% by mass fraction).
Recent researches try to promote another kind of mineral particles: the kaolinites. The
papermaking industry is the main actor regarding its use and the advent of new technologies
promises a great disponibility of this raw material. Regarding its low shape factor, the main
interest is its high potential of incorporation rate in polymer matrix. The broadly potential use
of this material requires investigation on mechanical composite performances. Even if native
particles are submicronic, their level of dispersion in the matrix and their distribution are
usually responsible of poor mechanical properties. A surface treatment is therefore advisable.
The present study focuses on the use of kaolinites (30% by mass fraction) to improve both
mechanical and thermal behavior of PA6 material. At first the composites morphology is
characterized. Then mechanical (static/dynamic) and thermal (cone calorimeter) tests are
performed. Relation between morphology and thermal or mechanical properties is also
discussed. This article is a first step: the kaolinite is introduced alone, and so only a more
progressive heat release is expected. For a composite PA6/kaolinite a good processability is
still reached at 30wt%. A second step will be the addition of flame retardancy agent
(phosphonate additives for example) in the PA6/kaolinite composite.

2. Experimental

2.1 Materials and preparation

The polyamide matrix (PA6) (density 1.14 g/m3) used in this study is supplied by
Rhodia under the trade mark Technyl C206. Polyamide pellets were dried in a vacuum oven
at 80C for a minimum of 8h prior to the compounding. A melt blending of PA6 with
kaolinites was carried out on a co-rotating twin-screw extruder (Clextral, standard profile,
length=1200 mm, speed=250 rpm, screw diameter=20 mm, T=180C to 240C). The samples
were injected in moulds (Krauss Maffei KM 50 t, T=200-240C, mould temperature=80C) to
obtain specific specimens (ISO 527-2 (1A) for uniaxial tests, notched test bars for Charpy
impact and square specimens for cone calorimeter tests see Fig. 1 a,b and c).

3
 Fig. 1 Standard tests specimens (a) tensile (ISO 527-2 1A), thickness 4mm (b)
Charpy impact (c) cone calorimeter tests, thickness 4mm

Two kinds of lamellar kaolinite nanoparticles were selected for this study:
- a commercial one (K1): PARALUX with a specific surface area (BET) of 12.2 1.5
m2/g, a shape factor of 10 and an average primary particle size of 0.9 m,
- a non-commercial one (K2) with a specific surface area (BET) of 19.9 2 m2/g, a
shape factor of 5 and an average primary particle size of 0.2 m.
Both of them are supplied by Imerys and are mainly composed of alumina and silica
(Al2O3 wt % >38, SiO2 wt % >43).
Surface treatment was carried out as follows: kaolinites were dispersed in an
ethanol/water mixture (96/4). The solution was then placed under stirring and the pH was
changed by means of acetic acid to reach pH of 4.5. Coupling agents (treatment A: (3-
aminopropyl)triethoxysilane and treatment E: (3-glycidyloxypropyl)trimethoxysilane) were
added with a mass concentration of 10% of the kaolinite weight. This mixture was stirred
under reflux for 6h. At the end of the reaction, the solvent was evaporated and the kaolinite
was washed three times with ethanol to remove excess reagent.
Fillers are incorporated at 30% by mass fraction (equivalent to a volume incorporation rate
p=15%), which corresponds to a good compromise between processability and expected
flame retardancy. Six different formulations were thus realized and are presented in the Table
1.

Sample PA PAK1 PAK1A PAK1E PAK2 PAK2A PAK2E

Filler -- K1 K1 K1 A K2 K2 K1

4
Grafting -- -- A E -- A E
Table 1 : Materials under study

2.2 Characterization

2.2.1 Morphology by image analysis

Tensile test specimens (Fig. 1a) were cryo-fractured and the central zone of the
samples (perpendicular to the flow direction) was observed using a Quanta SEM instrument
under an accelerating voltage of 5kV. The injection process induces a preferential orientation
of the fillers; we suppose that dispersion of the particles observed in the section qualify the
volume particle size distribution. SEM images of nanocomposites reveal the presence of large
aggregates well distributed of kaolinites stacks (see for example Fig. 2a for PAK2
nanocomposite), at a higher magnitude it appears that these stacks are quite multidispersed
and some platelets are detached from the stacks (Fig. 2b, c). For each sample particle size
distribution is obtained by image analysis (AphelionTM 3.2 (ADCIS)). For each scale of
observation several micrographs (at least 5) are used to cover the whole specimen surface
area.

Fig. 2 SEM micrographs of PA with 30%wt of K2, scale factors (a) 100 (b) 1000 (c) 20000

SEM micrographs (Fig. 3a) are converted in black and white images (Fig. 3b) and kaolinites
stacks sections are identified, filtered by area surface value (A) with respect to the scale of
observation (from 100 to 5000m (scale factor 100); from 15 to 100m (scale factor 1000)
and from 1 to 15 m (scale factor 20000)) and numbered. This procedure is repeated over all
the micrographs and the number of particles identified for each magnification is scaled by the
surface analysis area.

5
 Fig. 3 Image analysis on SEM micrographs (a) initial image (b) selected areas

As selected objects have not a well-defined shape, it is useful for comparison to consider each
object as a disc occupying the same measured surface area. These discs are well described by
their diameters, denoted d. Collecting data of each magnitude analysis, a particle diameter
size distribution can be obtained from d=1m to 80m. For each nanocomposite a distribution
and a cumulated density in d are obtained (see Fig. 4 in the case of PAK1 specimen).

Fig.4 Diameter size distribution for the PAK1 sample: histogram of the normalized
frequencies, cumulative distributions (experiments (full line), identification (dotted line))

The cumulative distribution can be easily fitted by a log-normal law:

1 1 ln( d ) M
f (ln( d )) erf
(1)
2 2 SD 2
where M and SD are the mean and the standard deviation of the log-normal distribution and erf
is the Gauss error function; for each formulation two parameters (M and SD) are then extracted
6
from a well fitted result (see Fig. 4, full and dotted lines). A statistical analysis can therefore
be performed from these variables:
The equivalent diameter dm which is the median value of the distribution
dm eM (2)

The dissymmetry coefficient: a higher dissymmetry coefficient means a more

heterogeneous distribution

2 2
(3)
S (e SD 2) e SD 1

The agglomeration rate

(4)
A d m / d el

The interparticular distance: the equivalent diameter is insufficient alone to explain

the composites mechanical behaviour. Usually particle density is described through
the distance between the edges of two adjacent particles and is related to the confined
matrix thickness [13]. It is possible but complicated from the position of each particle
to evaluate a mean particular distance [14], but the size objects are assumed to be
constant. Regarding to the high level of size distribution of our composites, we
choose a simplified interparticular distance evaluation in which compactness stacking
objects are considered:
1

3
SD2 / 2
(5)
L d m C SD2
e e
6
p

where C is a constant value depending on the compactness stacking. For sake of simplicity
and for all the formulations C was assumed equal to 1 (cubic stacking).

2.2.2 Mechanical properties by quasi-static and dynamic tests

Uniaxial tensile tests were carried out on a Zwick TH010 universal testing machine
according to the ISO 527 standard. The crosshead speed depends on investigated properties: 1
mm/min to describe linear behavior and 50mm/min for the non-linear behavior until breakage.
The software used is TestXpert and allows the recording of time, load (F) and elongation ().
The nominal stress is defined by the following expression: F / S0 where S0 is the initial
sample ISO 527-2 1A section (40mm). Youngs modulus (E) value is given by the slope,

7
calculated between 0 and 1 % elongation of the curve giving F vs. axial . We denote by Ec
the composites modulus, EPA the neat PA6 modulus and if necessary EK1 (equal to EK2) the
fillers modulus in the longitudinal direction. Out of this range of elongation, the whole
stress/deformation profile of these materials is given in Fig. 5. As commonly observed for
these kinds of material, the nominal stress reached a maximum (called the yield stress)
corresponding to the value yield at the deformation yield. We denote by c yield the composites
yield stress and PA yield the neat PA6 yield stress.
100
100

80 80

60 60
(MPa)
(MPa)

PA
40 40 PA-K2
PA PA-K2A
PA-K1 PA-K2E
20 PA-K1A 20
PA-K1E

0 0
0 5 10 15 20 25 0 5 10 15 20 25
(%)
(%)

Fig. 5 Stress vs. strain in uniaxial tensile tests for PA6 composites

Instrumented Charpy impact tests are performed on standard notched Charpy

specimens (Fig. 1b). The specimen is impacted by a pendulum hammer of m=3.14kg at a
velocity of 1.6m/s; the drop height is 130mm which corresponds to a striking hammer energy
up to 4J. The instrumentation enables the evaluation of the load history measurements F(t) as
well as instantaneous displacement of the specimen u(t):
(6)
1 t
v(t ) v0 F (t )dt
m 0
t (7)
u(t ) v(t )dt
0

where v (t ) is the instantaneous velocity of the impactor and v0 its impact velocity. Fig. 6
presents typical trend of the impact force vs. time for the PA6 composites; Sure enough the
impact behaviour is highly dependent on filler and/or surface treatment. All specimens were
totally broken after the impact and fillers provided additional toughening effects.

8
 250

PA
PA-K1
200 PA-K1A
PA-K1E

150
Force (N)

100

50

0
5.0 5.5 6.0 6.5 7.0
Time (ms)

Fig. 6 Impact force as a function of test time for PA6 composites

From these curves a useful global parameter, the energy, can be deduced:
u
(8)
J F (u)du
0

2.2.3 Flame retardancy by cone calorimeter

The flame retardancy of PA6 composites was characterized by cone calorimetry using a
FTT apparatus according to the ISO 5660 standard. This technique has been widely used to
describe polymer flammability. In this framework, reference [15] is devoted to polymer-clay
nanocomposites. In our study irradiance was set at 50 kW/m2. Tests were duplicated for all
composites (with shape referring to Fig 1c) to ensure results repeatability and their results are
reproducible within 10%. Cone calorimeter experiments provide several parameters: Time
To Ignition (TTI), Peak of Heat Release Rate (pHRR), Total Heat Release (THR) which is
formally the integral of the HRR curve with respect to the time, Effective Heat of Combustion
(EHC) and Mass Loss Rate (MLR). Each of these parameters is more or less sensitive to both
filler and their matrix interaction.

3. Results and discussion

The morphological characteristics of all the PA6 composites have been summarized in
Table 2.

Name M SD del dm S A L

9
 m m m m
PA - - - - - - -
PAK1 1.72 1.62 1.1 5.6 10.1 5.1 97.1
PAK1A 1.86 1.61 1.1 6.4 8.1 5.9 106.1
PAK1E 1.68 1.67 1.1 5.4 11.9 4.9 111.4
PAK2 1.90 1.60 0.5 6.7 7.7 13.4 107.7
PAK2A 1.77 1.56 0.5 5.9 7.7 11.8 83.7
PAK2E 1.76 1.64 0.5 5.8 10.3 11.6 109.0
Table 2: Morphological characteristics of the PA6 composites

3.1 Morphological properties

Particles are highly agglomerated in the composite: extrusion process protocol is not
successful from this point of view. Sure enough, the smallest particles lead to the biggest
agglomerates. Except for the K1A particles, the surface treatment induces a reduction of both
the agglomerates size (dm) and the level of agglomeration (A). The coefficient S is not related
to dm: it reveals the heterogeneity of the agglomerates size. The E treatment reduces the
median diameter but increases the number of big aggregates. An opposite trend is observed
for the A treatment. The interparticular distance (L) is defined from all the previous
parameters. Even though a dispersion assumption has been chosen to establish equation (5),
this parameter is a good tool to compare the formulations.

3.2 Relations between morphology and mechanical/thermal properties

The mechanical/thermal properties of all the PA6 composites have been summarized in Table
3.

Name E yield yield J pHRR TTI THR EHC

MPa MPa J kW/m s MJ/m kJ/g-1
PA 3419 86.8 3.6 2.9 1352 40 149 28.2
PAK1 6387 93.0 3.2 1.7 750 72 125 28.2
PAK1A 6200 78.8 3.3 3.2 614 100 115 27.8
PAK1E 6300 93.5 3.9 3.8 470 50 128 29
PAK2 4581 67.2 1.9 1.2 780 80 120 29.9
PAK2A 4641 87.6 4.8 4.6 460 105 110 28.4

10
PAK2E 4500 86.6 4.9 3.5 470 58 125 28.8
Table 3: Mechanical/thermal characteristics of the PA6 composites

3.2.1 Youngs modulus

Kaolinite filler incorporation leads to an enhancement of elastic properties. Prediction
from Mori Tanaka [16] model (for lamellar structures) slightly overestimates this modulus but
is higher for the K1 particles (with a higher shape factor) accordingly to the experimental
values and to the literature [17] (Fig. 7). As widely reported in the literature [18], chosen
elastic parameters for Mori Tanaka model are:

E
MPa
K1 , K2 180 0.20
PA 3.4 0.35
Table 4: Elastic parameters for the Mori Tanaka modeling, p=15%

It appears that surface treatment doesnt impact so much material elasticity. In fact, as
reported in the literature, the Youngs modulus is evaluated at a low level of strain inducing a
little perturbation of the interface area [19]. Nevertheless surface treatment can modify both
matrix and filler dispersion [20]. Considering results of table 2, there is no obvious relation
between the median diameter and the Youngs modulus.

7000
7000
6000
6000
5000
5000
4000
Ec (MPa)

4000
Ec (MPa)

3000 3000

2000 2000

1000 1000

0 0
(a) PA PAK2 PAK2A PAK2E Mori Tanaka (b) PA PAK2 PAK2A PAK2EMori Tanaka

Fig. 7 Youngs modulus of composites, effect of the surface treatment, prevision

via Mori Tanaka modelling p=15%

3.2.2 Stress/strain at the yield point

11
 Usually, yield stress increases and yield strain decreases with the incorporation rate of
well dispersed rigid particles. The reason reported in the literature is the good adhesion
between fillers and matrix (which is responsible for the stress increasing) and the reduction of
the volume matrix which is enable to deform (which is responsible for the strain decreasing).
Some authors involve particle size and shape to explain the stress increasing [21-24]. The key
parameter for the yield stress seems to be the median diameter dm (Fig. 8a) for our study: c
yield depends linearly on the median diameter. Concerning the yield strain the same trend is
observed for each kind of kaolinites: c yield depends linearly on the level of aggregation (A)
(Fig. 8b).
100 40
(A) (B)
95 K1E 35 K2
K1

90 K2A 30 K2A
K2E
yield (MPa)

85 K2E 25
80 20
K1A
A
75 15
70 10 K1A
K2 K1E
65 5 K1

60 0
5.0 5.5 6.0 6.5 7.0 1 2 3 4 5 6
dm (m) yield (%)

Fig. 8 (a) Yield stress as a function of median diameter (b) Yield strain as a
function of agglomeration rate

To better characterize the efficiency of interface modification the model proposed by

Pukansky was used [25]. A parameter B is introduced to describe interface cohesion:

1 yield 1 2.5 p (9)

B ln
p
PA yield 1 p
The higher is B, the better is the interfacial adhesion. A first observation is that a good
interfacial adhesion produced a better desagglomeration (Fig. 9).

12
 4.5

4.0 K1
K1E
3.5 K2A
K2E
3.0

2.5 K1A
B

2.0

1.5

1.0 K2

0.5

0.0
5.0 5.5 6.0 6.5 7.0
dm (m)

Fig. 9 Interfacial adhesion versus median diameter

It seems that the cohesion between matrix and aggregates decreases as the median
diameter increases. In fact the better is the interface adhesion the better is the dispersion.
Cohesion parameter is therefore a consequence of the surface treatment via its impact on
particle dispersion. For both kaolinite, E treatment leads to the lowest median diameter: Commented [AC1]: Belka il faut faire un laus l-dessus :
Marcos dit que les groupes poxy du traitement E peuvent avoir une
interaction plus importante avec les groupes amines du PA6. Pour le
traitement A cest diffrent. Tu confirmes ?
3.2.3 Resilience
Literature results reveal the undeniable relation between breakage and interfacial
quality in composites. In the case of no adhesion, rupture will be conditioned by the matrix
properties; if the interface is fragile, stress concentration around particles will be increased
and will lead to a fragile breakdown; On the contrary, a ductile interface will produce
particles cavitation [26]. Beyond these observations, it seems that rupture is first of all
conditioned by the biggest particles [27]. Some authors define a morphological criterion in
relation with the fragile/ductile composites breakdown [28, 29]. According to these authors, a
morphological analysis is performed from the lowest magnification (100) in order to qualify
only big agglomerates dispersion. These results are summarized in Table 4 with the associated
mode of failure.

Name M SD dm S L J Failure
m m m J mode

PA - - - - - 2.9 -

13
PAK1 3.16 1.99 23.5 12. 1723. 1.7 ductile
PAK1A 3.13 1.94 22.9 7.2 1344. 3.2 fragile
PAK1E 2.88 1.96 17.8 10.1 1149. 3.8 fragile
PAK2 3.48 1.99 32.7 7.1 2588. 1.2 ductile
PAK2A 2.66 1.81 14.3 8. 492. 4.6 fragile
PAK2E 3.00 1.95 20.1 12.5 1303. 3.5 fragile
Table 5: Morphological characteristics of the PA6 composites with the 100
magnification

A great correlation was found between resilience and interparticular distance through a sigmoid
function (Fig. 10). This graph confirms the existence of a critical interparticular value related to the
ductile-brittle material transition.

1.6
Ductile Fragile

1.2
J (J)

0.8

0.4

0.0
0 500 1000 1500 2000 2500 3000
L (m)

Fig. 10 Resilience versus interparticular distance (100 magnification)

3.2.4 Flame retardancy

The burning process is greatly described by the evolution of HRR vs time. As can be
clearly observed in Fig. 11 (example for K1 kaolinites) and Table 3, the HRR curves of the
PA6 composites present different trends, as a consequence of aggregate gradation. PA6
composites show two distinct maxima while pristine PA6 identifies a single. Usually, in the Commented [AC2]: Marcos tu peux mettre une ref ?

case of mineral composites the first maximum corresponds to the formation of a protective
char layer and the second to sample swelling. Nevertheless, in PA6 kaolinites composites
none of this phenomenon has been observed. The unfilled PA6 is fully pyrolized at the same
time as its HRR curve reveals a single sharp peak [30]. The maximum peak reduction
(corresponding to the second one) is of 44% for PAK1, 54% for PAK1A, 65% for PAK1E
Commented [I3]: Je nai pas observ la formation dune couche
la surface ni lexpansion des chantillons PA-Kaolinites. La
prsence dun plateau (ou deux pics selon la formulation) est
difficile expliquer. Rodolphe disait que cela pourrait tre d
larrive de la flamme au fond de lchantillon et la chaleur,
nayant plus une faon de svacuer est retransmisse au polymre
augmentant ainsi le HRR. Mais cela reste encore difficile a montrer.
Commented [AC4]: Rodolphe peux tu dire quelque chose l-
dessus ?
Merci

14
(42% for PAK2, 66% for PAK2A, 65% for PAK2E ). Regardless of their shape factor, the
kaolinites (and even more the treated ones) reduce the pHRR significantly. Moreover it seems
that pHRR evolution is well correlated with the median diameter (from 100 magnification)
(see Fig. 12). The better is the dispersion of the biggest agglomerates (the lower is the median
diameter) the lower is the pHRR. Some authors found qualitatively same trend on PP/MMT
composites even if there does not exist any theoretical background to describe the link
between the pHRR reduction and particle dispersion [32]. In [32] authors suggest that
nacomposites are better than microcomposites regarding pHRR reduction. Nevertheless, they
point out that if nanodispersion is achieved, the nanomorphology (exfoliation, intercalation
and presence of tactoids for clay particles) does not play any significant role. In conclusion, to
decrease the pHRR, a great challenge is the kaolinite global desagglomeration before and Commented [AC5]: Marcos je mets global pour ne pas rentrer
dans les dtails. a te va ?
during the melting process in order to reach a better dispersed system. Commented [I6]: On ne peut pas comparer directement la
dispersion de la kaolinite et la montmorillonite. Dans le cas de la
Regarding the THR values reported in Table 3, lower values are obtained introducing montmorilonite la dispersion est la intercalation/exfoliation que nous
ne regardons pas dans le cas de la kaolinite.
kaolinites. This is a direct consequence of inorganic fillers (so non-combustible)
incorporation. Finally, as indicated in table 3, EHC of all composites does not change
significantly indicating that the main mode-of-action of kaolinite occurs in the condensed
phase.
A notable difference between composites concerns the time to ignition (Table 3). All tested
specimens present a TTI never exceeding 2mn and follow this classification:
< 1 < 2 < 1 < 2 < 1 < 2
Mineral particles delay the ignition. This global augmentation of TTI can be attributed to an
improved thermal stability (TGA measurement could confirm this hypothesis) or to an Commented [AC7]: Marcos as-tu les ATG ?

increase of thermal diffusivity. The A treatment seems to be the best one considering this
parameter but no correlation with the morphology has been found.
Commented [I8]: Cest difficile dexpliquer la diffrence
observ en ce qui concerne le TTI. Certains auteurs parlent de leffet
de la viscosit, dautres parlent de leffet de dgradation du
traitement des argiles ou dun effet catalytique. De toute faon, latg
des diffrentes compositions de montre pas une diffrence
significative (je nai pas lATG pour 30%, seulement pour 20%). Je
pense que le mieux cest de constater cette diffrence et donner des
explications de la littrature. Tu peux regarder larticle de lEVA
que nous avons soumis et utiliser la mme explication.

15
 1500
PA
1250 PA-K1
PA-K1A
1000 PA-K1E
HRR (kW*m-2)

750

500

250

0
150 300 450 600
Time (s)

Fig. 11 : Heat Release Rate (HRR) curves of pristine PA6 and PA6 composites vs time

1000

800
pHRR (kW.m )
-2

600

400

200

0
15 20 25 30 35
dm (m)

16
Fig. 12 : Peak of Heat Release Rate (PHRR) vs median diameter (100 magnification)

4. Conclusion

The PA6-kaolinite composites were prepared by compounding and injection-moulding.

Some of the kaolinites were functionalized and the composites microstructures were
characterized via optical measurements at different magnifications. Statistical analyses reveal
the influence of the functionalization on the composites microstructures. For most composites
the functionalization reduces the median diameter (and much more considering the biggest
particles) and limits the level of agglomeration. The influence of the microstructure on both
flammability and mechanical properties was investigated. The mechanical testing reveals the
strong relationship between Youngs modulus, yield stress/strain, resilience and
microstructure. The Youngs modulus may decrease slightly as the interparticular distance
between particles increases, but in the range of investigated interparticular values the
sensitivity to this parameter is not so important. This result is in accordance with the
literature: the Youngs modulus is not the key parameter to describe the effect of a
functionalization. Indeed the yield stress is clearly decreasing when the median diameter
increases and the yield strain follows the same trend with the level of agglomeration. These
last mechanical parameters seem therefore be dependent of the microstructure in its totality
(from the bigger agglomerates: scale magnification 100, to the smaller ones: scale
magnification 1000, 20000). Dynamical and flammability testing however are sensitive to

17
the biggest agglomerates (scale magnification 100): the resilience decreases when the
interparticular distance increases and below a critical value (around 1500m) the composites
become fragile; the pHRR is reduced when a better dispersion of the biggest agglomerates is
reached (as dm is decreasing).
The next step is to combine kaolinites with a flame retardant additive; the expected
synergy between these two additives should lead to a pHRR and THR decrease.

18
References
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 LIST OF FIGURES

Fig. 1. Standard tests specimens (a) tensile (ISO 527-2 1A), thickness 4mm (b)
Charpy impact tests

Fig. 2. SEM micrographs of PA with 30%wt of K2, scale factors (a) 100 (b) 1000 (c)
20000

Fig. 3. Image analysis on SEM micrographs (a) initial image (b) selected areas

Fig. 4. Diameter size distribution for the PAK1 sample: histogram of the normalized
frequencies, cumulative distributions (experiments (full line), identification
(dotted line))

Fig. 5. Stress vs. strain in uniaxial tensile tests for PA composites

Fig. 6. Impact force as a function of test time for PA6 composites

Fig. 7. Youngs modulus of composites, effect of the surface treatment, prevision via
Mori Tanaka modelling p=15%

Fig. 8. (a) Yield stress as a function of median diameter (b) Yield strain as a function
of agglomeration rate

Fig. 9. Interfacial adhesion versus median diameter

Fig. 10. Resilience versus interparticular distance (100 magnification)

Fig. 11. Heat Release Rate (HRR) curves of pristine PA6 and PA6 composites vs time

Fig. 12. Peak of Heat Release Rate (PHRR) vs median diameter (100 magnification)

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LIST OF TABLES

Table 1. Materials under study

Table 2. Morphological characteristics of the PA6 composites

Table 3. Mechanical/thermal characteristics of the PA6 composites

Table 4. Elastic parameters for the Mori Tanaka modelling, p=15%

Table 5. Morphological characteristics of the PA6 composites with the 100

magnification

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