Analysis of kaolinite morphology dispersion in polyamide composites:

impact on fire retardancy and mechanical properties

M. Batistella, A.S. Caro-Bretelle*, B. Otazaghine, P. Ienny, J.M. Lopez-Cuesta

C2MA, Ecole des Mines dAls, 6 Avenue de Clavires, 30319 Als (France)

Abstract
The present study focuses on the mechanical and the thermal properties of a
Polyamide/Kaolinite composite. Several kaolinites (showing 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. At first result, elastic properties are enhanced, as expected,
by kaolinites addition and the higher is the interparticular distance the lower is the composite
Young modulus. The same trend is observed for the resilience. The yield stress is decreasing
as the median diameter increase: a good interfacial adhesion produced 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 lead to polymers inflammability. In this framework, a great challenge
concerns the improvement of polymer fire resistance.
Fire retardancy can be performed through different mechanisms:
Material surface protection: this process is simple but raises the question of
adhesion/wear between protection and sample
Material volume protection: flame retardant agents 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.
The action of these kinds of additives is either physical or chemical. In the first case, the
additives can form a non-conductive coating and so reduce heat transfer; additives
degradation reaction can also be endothermic and contribute to decrease the heat balance;
additives degradation can also produce inert gases which may dilute combustible gases.
Beyond physical aging flame retardant, 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 lead to poor mechanical
properties. 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 [1, 2, 3]. In this context, nano mineral particles such as organic
monmorillonite (oMMT) are used to improve flame retardancy but their processability limits
their level of incorporation (always under 10t% by mass fraction: composites PP-g-
MA/oMMT [4], Polyimide(PI)/oMMT [5], PA6/oMMT [6], EVA/oMMT [7] where oMMT
particles are either intercalated or exfoliated, PMMA/Al2O3,TiO2 [8, 9]). Their successfully
action in the heat balance can be attributed to
The creation of a diffusion barrier layer [7], [8], [10]
The modification of the polymer degradation: heterogeneous catalysis associated
to a char structure [7],[10]
The modification of the thermal diffusivity [8], [11]
The reduction of the macro molecular mobility (around or inside the charges) [8]
The increase of polymer viscosity
 The trapping of radicals formed during the thermal degradation [8]
The nanoparticle distribution [8, 9].
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 rate incorporation in polymer matrix. 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.
The broadly potential use of this material necessitates investigation on mechanical composite
performances. Even if native particles are submicronic, their level of dispersion in the matrix
and their distribution is 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 morphologies are
characterized. Then mechanical (static/dynamic) and thermal tests (cone calorimeter) are then
performed. Relation between morphology and thermomechanical properties is then discussed.

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, mold 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).
 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).
Some of the fillers are used after surface modification: 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 incorporation. 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 volumic incorporation rate
p=15%), which correspond 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
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 samples 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
and particles granulometry.

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 25000)) 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.
 Fig. 3 Image analysis on SEM micrographs (a) initial image (b) selected areas

As selected objects have not reproducible shape, it is useful for comparison to consider each
object as a disc occupying the same surface measured 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 nanocomposites 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 normalised
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
from a well fitted result (see Fig. 4, full and dotted line). 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: the higher it is, the more heterogeneous is the
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 describe

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 [12]. It is possible but complicated from the position of each particle
to evaluate a mean particular distance [13], but the size objects are assumed to be
constant. Regarding to the high level of size distribution of our composites, we opt for
a simplified interparticular distance evaluation in which compactness stacking objects
are considered:
1

SD2
3 2 (5)
L d m C e e SD / 2
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 conducted on a Zwick TH010 universal testing machine
according to the ISO 527 standard. The crosshead speed is equal to 1 mm/min. The tensile test
is conducted up to the rupture of the specimen. 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, calculated between 0 and 1 %
elongation of the curve giving F vs. axial . Lets denote by Ec the composites modulus, EPA
the neat PA 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 kinds
of 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. Lets denote by c yield the composites modulus and PA yield the neat PA
modulus.
100

80
80

60
60
(MPa)
(MPa)

40 PA
40 PA-K2
PA
PA-K1 PA-K2A
20 PA-K1A PA-K2E
20
PA-K1E
0 0
0 5 10 15 20 25 0 5 10 15
(%) (%)

Commented [ASCB1]: Remplacer PA6 parPA , G par E et ne

pas mettre de couleur : en noir pointills et respecter lordre K1A
Fig. 5 Stress vs. strain in uniaxial tensile tests for PA composites et K1E aprs

Instrumented Charpy impacts testing are performed on standard size 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 filler and/or coating dependent. All specimens were not totally
broken after the impact and fillers provided additional toughening effects.
Fig. 6 Impact force as a function of test time for PA6 composites

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

2.2.3 Fire retardancy by cone calorimeter

The fire retardancy of PA6 composites was characterized by cone calorimetry using a
FFT apparatus according to the ISO 5660 standard. This technique has been widely used to
describe polymer flammability. In this framework, reference [14] is devoted to polymer-clay
nanocomposites. In our study irradiance was selected 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 (TTT), Peak of Heat Release Rate (pHRR), Total Heat Release (THR) Commented [MB2]: TTI

which is formally the integral of the HRR curve with respect to the time, Total Heat Release
Evolved (THE) and Mass Loss Rate (MLR). Each of these parameters are more or less
sensitive to both filler and their matrix interaction.

3. Results and discussion

The morphologies of all the PA6 composites have been resumed in Table 2.

Name M SD del dm S A L
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 agglomerate in the composite: extrusion process protocol is not
successful from this point of view. Sure enough, the smaller particles produce the bigger
agglomerates. Excepted for the K1A particles, the surface treatment induces a reduction of
both the agglomerate size (dm) and the level of agglomeration (A). The coefficient S is not
related to dm: it traduces 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, 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 resumed in Table 3.

Name E yield yield J pHRR TTI THR THE

MPa MPa J kW/m s MJ/m MJ/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 4.6 350 ? ? ?
PAK2E 4500 86.6 4.9 3.5 450 ? ? ?
Table 3: Mechanical/thermal characteristics of the PA6 composites

3.2.1 Young modulus

Kaolinite filler incorporation leads to an enhancement of elastic properties. Prediction
from Mori Tanaka [15] 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 [16] (Fig. 7). As widely reported in the literature [17], chosen
elastic parameters for Mori Tanaka model are:

E
 MPa
K1 , K2 180 0.20
PA 2.9 0.35
Table 4: Elastic parameters for the Mori Tanaka modeling, p=15%

Its seems that surface treatment doesnt impact so much global material elasticity. In
fact, as reported in the literature, the young modulus is evaluated at a low level of strain
inducing a little perturbation of the interface area [18]. Nevertheless surface treatment can
modify both matrix and filler dispersion [19]. Considering results of table 2, there is no
obvious relation between median diameter and Young modulus. Nevertheless PA matrix is
much more confined between aggregates as interparticular distance decreases. For both of
kaolinites, this trend is confirmed in Fig. 8a: the lower is L the higher is Ec (excepted for the
last point K1E plotted in Fig. 8a). This analysis should be completed: in fact the polymer
matrix is impacted by the presence of both filler and grafting agent. Crystallinity degree
evaluation of all the composite reveals a quite constant degree expected for the K1E sample
(Fig. 8b). This explains why the point K1E in Fig.5a is quite marginal. Morphological analysis
is therefore directly related to elastic properties as far as fillers dont modify matrix
properties.

(a) (b)

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

Fig. 8 (a) Young modulus composites as a function of interparticular distance (b)

Crystallinity degree for PA composites

3.2.2 Stress/strain at the yield point

Usually, yield stress increases and yield strain decreases with the incorporation at a
reasonable 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 lower volume matrix restriction which is enable to deform (which is responsible for the
strain decreasing). Some authors involve particle size and shape to explain the stress
increasing [20-23]. The key parameter for the yield stress seems to be for our study the
median diameter dm (Fig. 9a): 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. 9b).

(a)

Fig. 9 (a) Yield stress as a function of median diameter (b) Yield strain as a
function of agglomeration rate
 To better characterize the efficacy of interface modification we use Pukansky
modelisation [24]. 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. 10).

Fig. 10 Interfacial adhesion versus median diameter

It seems that de cohesion between matrix and aggregates decreases as the median
diameter increases. In fact the better is interface adhesion the better dispersion is. Cohesion
parameter is therefore a consequence of the surface treatment via its impact on particle
dispersion. For both kaolinite, E treatment produces the lower median diameter: Commented [AC3]: 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
Bibliography results reveal the incontestable relation between breakage and interfacial
quality between fillers and matrix. 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; contrary, a ductile interface will produce
particles cavitation [25]. Beyond these observations, it seems that rupture is first of all
conditioned by the bigger particles [26]. There are even authors defining a morphological
criterion in relation with the fragile/ductile composites breakdown [27, 28]. According to
these authors, a morphological analysis is performed from the lowest magnification (100) in
order to qualify only bigger 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 -
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

We find a great correlation between resilience and interparticular distance through a sigmoid
function (Fig. 11). This graph confirms the existence of a critical interparticular value related the
ductile-brittle material transition.

Fig. 11 Resilience versus interparticular distance (100 magnification)

3.2.4 Fire retardancy by cone calorimeter Commented [AC4]: Doit on ajouter les analyses ATG ?
 The combustion process is greatly described by the evolution of HRR vs time. As can
be clearly observed in Fig. 12 (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 identify a unique. PA6 composites exhibit a HRR growth until a
maximum which corresponds to the formation of an efficient char layer; after that the HRR
decreases (or slowly increases for the PAK1A composites) before it reaches a second peak
coinciding with the sample swelling. The unfilled PA6 is whole pyrolised at the same time as
its HRR curve reveals a unique sharp peak [29]. Nevertheless the maximum peak reduction
(corresponding to the second one) is of 44% for PAK1, 54% for PAK1A, 65% for PAK1E
(42% for PAK2, x% for PAK2A, 65% for PAK2E ). Regardless of their shape factor, the
kaolinites (and even more the treated one) reduce the pHRR significantly. Moereover it seems
that pHRR evolution behaves as median diameter (from 100 magnification) (see Fig. 13).
The better is the dispersion of the bigger agglomerates (the lower is the median diameter) the
lower is the pHRR. Some authors found qualitatively the same kind of results on PP/MMT
composites even if there exists no theoretical background to describe the link between the
pHRR reduction and particle dispersion [30]. In [31] authors suggest that nacomposites are
better than microcomposite 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, even if the pHRR
is decreased, a great challenge is in the kaolinite desagglomeration before and during the
melting process in order to reach a better dispersed system.
Regarding the THR values reported in Table 3, lower values are obtained introducing
kaolinites. This is a direct consequence of organic fillers (so non-combustible) incorporation.
Finally, as indicated in table 3, THE of all composites does not change significantly indicating
that the main action of kaolinite is in the condensed phase.
A notable difference between composites is the time to ignition (Table 3). All of the tested
specimens present a TTI never exceeding 2mn and follow this classification:
< 1 < 1 < 2 < 1
This parameter is clearly the manifestation of composites thermal inertia and mineral particles
delay the time to ignition. The A treatment seems to be the better one regardless this
parameter but no correlation with the morphology has been found.
 1500
PA
1250 PA-K1
PA-K1E
1000 PA-K1A
HRR (kW*m-2)

750

500

250

0
150 300 450 600
Time (s)

Commented [AC5]: Marcos il me faut juste celle 15% et puis

la police dcriture est moche. Tu peux faire comme dans mes autres
Fig. 12 : Heat Release Rate (HRR) curves of pristine PA6 and PA6 composites vs time figures ?

Cest sur quil va falloir faire des essais pour la K2..

1000
pHRR(kW.m-2)

800

600

400

200

0
14,0 19,0 24,0 29,0 34,0
dm(m)

Fig. 13 : Heat Release Rate peak (PHRR) vs median diameter (100 magnification)
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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 normalised
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. Young modulus composites, effect of the surface treatment, prevision via Mori
Tanaka modelling p=15%

Fig. 8. (a) Young modulus composites as a function of interparticular distance (b)

Cristallinity degree for PA composites

Fig. 9. (a) Yield stress as a function of median diameter (b) Yield strain as a function
of agglomeration rate

Fig. 10. Interfacial adhesion versus median diameter

Fig. 11. Resilience versus interparticular distance (100 magnification)

Fig. 12. Heat Release Rate (HRR) curves of pristine PA6 and PA6 composites vs time
Fig. 13. Heat Release Rate peak (PHRR) vs median diameter (100 magnification)
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 modeling, p=15%

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

magnification