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Defence Research and Recherche et développement
Development Canada pour la défense Canada

&
DEFENCE DÉFENSE

Formulation and Characterization of Nanoclay


Composites
Towards Multifunctional Materials for the Dismounted
Soldier

Royale S. Underhill
Allison Nolting
Gary Fisher
Irv Keough
Defence R&D Canada – Atlantic

Nathalie Chapleau
Industrial Materials Institute
National Research Council Canada

Defence R&D Canada – Atlantic


Technical Memorandum
DRDC Atlantic TM 2009-017
September 2009
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Formulation and Characterization of Nanoclay
Composites
Towards Multifunctional Materials for the Dismounted Soldier

Royale S. Underhill
Allison Nolting
Gary Fisher
Irv Keough
Defence R&D Canada — Atlantic
Nathalie Chapleau
Industrial Materials Institute
National Research Council Canada

Defence R&D Canada – Atlantic


Technical Memorandum
DRDC Atlantic TM 2009-017
September 2009
Principal Author

Original signed by Royale S. Underhill


Royale S. Underhill

Approved by

Original signed by Leon M. Cheng


Leon M. Cheng
Head/Dockyard Laboratory (Atlantic)

Approved for release by

Original signed by Ron Kuwahara for


Calvin V. Hyatt
Chair/Document Review Panel


c Her Majesty the Queen in Right of Canada as represented by the Minister of National
Defence, 2009

c Sa Majesté la Reine (en droit du Canada), telle que représentée par le ministre de la
Défense nationale, 2009
Abstract
Nanocomposites are a promising new area in material science. Many researchers have
described the benefits of nanoscale fillers. The incorporation of nanosized particles with
high aspect ratios into polymers has led to new composites with improved physical prop-
erties such as improved strength, UV absorbance and fire resistance. The work reported
here compared the physical properties of various nanoclay formulations. Degree of clay
loading, the use of compatibilizing agent and natural vs. synthetic clay were all examined.
Polyamide and polypropylene were chosen as the matrix materials, with Cloisite 15A as
the natural clay and Perkalite F100, Somasif ME or Lucentite SWN as the synthetic clays.
Samples of neat, 2 wt.% and 4 wt.% clay were prepared and analyzed using scanning elec-
tron micrography and x-ray diffraction to determine dispersion. The physical properties
of the nanocomposites were then examined using thermogravimetric analysis, dynamic
mechanical analysis, quasistatic tensile testing, impact testing, abrasion testing and cone
calorimetry. The particles in the polyamide nanocomposites appeared to be better dispersed
than in the polypropylene nanocomposites. The physical properties of the nanocomposites
showed minor improvements over the parent polymer, while the addition of nanoclays
to the polyamide system imparted better physical properties than the polypropylene. It
is believed that poor dispersion played a role in the lack of significant improvements in
material properties.

Résumé
L’étude des nanocomposites constitue un nouveau domaine prometteur de la science des
matériaux. De nombreux chercheurs ont déjà décrit les avantages que comporte l’utilisation
de matières de charge nanométriques. L’incorporation de nanoparticules possédant un rap-
port de forme élevé à des polymères a permis de produire de nouveaux composites dont
les propriétés physiques améliorées comprennent une résistance accrue, une meilleure ab-
sorption du rayonnement UV et une résistance au feu supérieure. Les travaux décrits dans
le présent rapport visaient à comparer les propriétés physiques de diverses formulations à
base de nanoargile. On a examiné les effets de l’importance de la charge de nanoargiles, de
l’utilisation d’agents de compatibilité et de l’emploi d’argile naturelle ou synthétique. Les
matériaux de matrice étudiés étaient un polyamide et un polypropylène, l’argile naturelle
choisie était la Cloisite 15A, et les argiles synthétiques comprenaient la Perkalite F100, la
Somasif ME et la Lucentite SWN. On a préparé des échantillons purs et des échantillons
contenant 2% en poids et 4% en poids d’argile ; leur analyse a été effectuée par microscopie
électronique à balayage et par diffraction des rayons X afin de déterminer le degré de dis-
persion des particules. On a ensuite étudié les propriétés physiques des nanocomposites au
moyen des techniques d’analyse thermogravimétrique et d’analyse mécanique dynamique,
d’essais de traction en mode quasi statique, d’essais au choc, d’essais d’abrasion et d’essais
au calorimètre à cône. Les résultats semblent indiquer que la dispersion des particules est

DRDC Atlantic TM 2009-017 i


meilleure dans les nanocomposites de polyamide que dans ceux de polypropylène. Les
propriétés physiques des nanocomposites sont légèrement supérieures à celles du polymère
initial ; d’autre part, l’ajout de nanoargiles au polyamide a produit des nanocomposites
présentant de meilleures propriétés physiques que dans le cas de leur ajout au polypropylène.
On considère que la mauvaise dispersion des particules a joué un rôle dans la piètre amé-
lioration des propriétés physiques des produits finaux.

ii DRDC Atlantic TM 2009-017


Executive summary

Formulation and Characterization of Nanoclay


Composites: Towards Multifunctional Materials for the
Dismounted Soldier
Royale S. Underhill, Allison Nolting, Gary Fisher, Irv Keough, Nathalie
Chapleau; DRDC Atlantic TM 2009-017; Defence R&D Canada – Atlantic;
September 2009.

Background: Nanocomposites are a promising new area in material science. Many re-
searchers have described the benefits of nanoscale fillers. The incorporation of nanosized
particles with high aspect ratios into polymers has led to new materials with unique proper-
ties. Nanoclay/polymer composites are polymers reinforced with nanosized clay particles.
The nanosized clay particles are achieved by either intercalating the polymer into the
clay galleries or completely exfoliating the clay platelets to yield particles with average
dimensions of 1 nm in thickness and 70–150 nm in width.

It has been shown that incorporating nanoclays into polymers can increase the mechanical
and thermal properties of the polymers. These include improved strength, modulus, UV
absorbance and fire resistance. This project compares the physical properties of various
nanocomposite formulations to determine the degree of improvement. The core of this
research is the examination of the effects of different levels of exfoliation and different
degrees of loading on polypropylene and polyamide.

Polyamide and polypropylene were chosen as the matrix material for these nanocomposites
because they can be used in clothing. Polyamide is also known as nylon, while polypropy-
lene has been used as a synthetic material for thermal clothing (i.e., long johns). By adding
nanoclays to these materials, it is hoped that the resulting nanocomposites will be imparted
with multifunctionality; regular clothing will have improved fire resistance, UV protection,
etc.

Results: The progress to date in preparing and characterizing polypropylene and polyamide
nanoclay composites is reported here. Samples of neat, 2 wt.% and 4 wt.% Cloisite
15A have been prepared. Micrographs and X-ray Diffractometry data suggest that the
particles in the polyamide nanocomposites are better dispersed than in the polypropylene
nanocomposites. The physical properties of the nanocomposites show minor improvements
over the parent polymer, while the addition of nanoclays to the polyamide system imparts
better physical properties than the polypropylene. It is believed that poor dispersion played
a role in the lack of significant improvements in material properties.

DRDC Atlantic TM 2009-017 iii


Significance of Results: This work represents an initial examination of nanoclay compos-
ites as multifunctional materials for the dismounted soldier. The predicted improvements
in physical properties were not realized, likely due to poor dispersion of the clay. This
technology has a low technology readiness level (TRL 2-3). More basic research focused
on dispersion issues is needed to determine if the physical property improvements and
multifunctionality can be achieved, before these composites can be evaluated as viable
technologies for military applications.

Future Plans: The primary concern is the dispersion of the clays. Improved dispersion
was explored through the examination of synthetic clays that were chosen to optimize
interactions with the polymer matrices. The polyamide/synthetic clay systems showed the
most significant improvements in physical properties, thus they will be further character-
ized using cone calorimetry.

In situ synthesis of the polymer, such that it is “grown” within the clay galleries is another
option to improve clay/polymer dispersion. This method for making polyamide nanoclay
composites will be explored.

The goal was to create materials with multifunctionality. One possible function is the
ability to prevent transmittance of UV light, yielding a nanocomposite with a sun protection
factor (SPF). Thus the transmittance of UV wavelengths will also be investigated.

iv DRDC Atlantic TM 2009-017


Sommaire

Formulation and Characterization of Nanoclay


Composites: Towards Multifunctional Materials for the
Dismounted Soldier
Royale S. Underhill, Allison Nolting, Gary Fisher, Irv Keough, Nathalie
Chapleau ; DRDC Atlantic TM 2009-017 ; R & D pour la défense Canada –
Atlantique ; septembre 2009.

Contexte : L’étude des nanocomposites constitue un nouveau domaine prometteur de la


science des matériaux. De nombreux chercheurs ont déjà décrit les avantages que com-
porte l’utilisation de matières de charge nanométriques. L’incorporation de nanopartic-
ules possédant un rapport de forme élevé à des polymères a permis de produire de nou-
veaux matériaux aux propriétés exceptionnelles. Les composites à base de polymère et
de nanoargile sont composés d’un polymère renforcé de particules d’argile nanométriques.
Celles-ci sont obtenues en effectuant l’intercalation du polymère dans les strates d’argile ou
en exécutant une exfoliation complète des plaquettes d’argile afin de produire des particules
ayant, en moyenne, 1 nanomètre d’épaisseur et de 70 à 150 nanomètres de largeur.

Les résultats de certaines études démontrent que l’incorporation de nanoargiles aux poly-
mères peut entraı̂ner une amélioration des propriétés mécaniques et thermiques des poly-
mères, et se traduire, entre autres, par une résistance et un module accrus, une meilleure
absorption du rayonnement UV et une résistance au feu supérieure. Le projet faisant l’objet
du présent rapport avait pour but de comparer les propriétés physiques de diverses formu-
lations de nanocomposites afin d’établir l’importance de leur amélioration par rapport à
celles des composés initiaux. L’objectif principal des travaux de recherche était d’étudier
les effets de différents degrés d’exfoliation des argiles et de différentes quantités de matière
de charge ajoutées au polypropylène et au polyamide.

Un polyamide et un polypropylène ont été choisis comme matériaux de matrice des nano-
composites, car ces types de polymères peuvent être utilisés pour fabriquer des vêtements.
Le polyamide le plus courant est appelé nylon, alors que le polypropylène est utilisé comme
matériau synthétique dans les vêtements thermiques (c. à-d. les caleçons longs). On s’at-
tend à ce que l’ajout de nanoargiles à ces matériaux donne des nanocomposites de nature
multifonctionnelle et que les vêtements courants fabriqués avec ceux-ci possèdent, entre
autres propriétés, une résistance au feu supérieure et une meilleure protection contre le
rayonnement UV.

Résultats : Le présent rapport contient la description des progrès réalisés jusqu’ici en


matière de préparation et de caractérisation de composites à base de nanoargiles et d’un

DRDC Atlantic TM 2009-017 v


polymère (un polypropylène ou un polyamide). On a préparé des échantillons purs et des
échantillons contenant 2% en poids et 4% en poids de Cloisite 15A. Leurs micrographies
et les données de leur analyse par diffraction des rayons X semblent indiquer que la disper-
sion des particules est meilleure dans les nanocomposites de polyamide que dans ceux de
polypropylène. Les propriétés physiques des nanocomposites sont légèrement supérieures
à celles du polymère initial ; d’autre part, l’ajout de nanoargiles au polyamide a produit des
nanocomposites présentant de meilleures propriétés physiques que dans le cas de leur ajout
au polypropylène. On considère que la mauvaise dispersion des particules a joué un rôle
dans la piètre amélioration des propriétés physiques des produits finaux.

Portée : Les travaux décrits dans le présent rapport constituent une étude initiale de l’u-
tilisation possible de composites à base de nanoargile comme matériaux multifonctionnels
pour le soldat de l’infanterie débarquée. L’amélioration prévue des propriétés physiques ne
s’est toutefois pas concrétisée, probablement à cause de la piètre dispersion des nanopar-
ticules d’argile. La technologie associée à ces travaux présente un faible niveau d’état de
préparation de la technologie (TRL de 2 à 3). Avant d’entreprendre l’évaluation de com-
posites ce type comme matériaux techniques ayant des applications militaires pratiques,
il faudra exécuter d’autres travaux de recherche fondamentale portant sur les questions
de dispersion des particules dans ceux-ci et déterminer s’il est possible d’améliorer leurs
propriétés physiques et de les intégrer à des matériaux multifonctionnels.

Travaux futurs : Le problème de dispersion des particules d’argile constitue le principal


sujet d’intérêt. On a étudié des moyens d’améliorer la dispersion, notamment en examinant
des argiles synthétiques choisies en fonction de leur capacité d’optimiser les interactions
avec les matrices polymères. Les composites de polyamide et d’argile synthétique étant
ceux dont les propriétés physiques présentent les plus importantes améliorations, leur car-
actérisation plus poussée sera réalisée en effectuant des essais au calorimètre à cône.

La synthèse in situ du polymère utilisé dans les composites, c’est-à-dire sa  croissance 


dans les strates mêmes de l’argile, constitue une autre solution possible au problème de
dispersion des particules d’argile. On envisage donc d’étudier en détail l’emploi de cette
méthode pour produire des composites de nanoargile et de polyamide.

L’objectif global du projet était de fabriquer des matériaux multifonctionnels. Parmi les
nombreuses fonctions que pourraient présenter ces matériaux, on trouve la capacité de
réduire le facteur de transmission du rayonnement UV, ce qui correspondrait à un nanocom-
posite possédant un facteur de protection solaire (FPS) intrinsèque. Par conséquent, les
futurs travaux de recherche comprendront aussi l’étude du facteur de transmission des
longueurs d’onde du rayonnement UV.

vi DRDC Atlantic TM 2009-017


Table of contents
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i

Résumé . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i

Executive summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

Sommaire . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Table of contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

List of figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

List of tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3 Nanoclay dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1 Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.2 Polyamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

4 Nanocomposite physical properties . . . . . . . . . . . . . . . . . . . . . . . . . 12

4.1 Thermogravimetric analysis . . . . . . . . . . . . . . . . . . . . . . . . . 12

4.2 Differential scanning calorimetry . . . . . . . . . . . . . . . . . . . . . . 13

4.3 Dynamic mechanical analysis . . . . . . . . . . . . . . . . . . . . . . . . 14

4.4 Quasi-static tensile testing . . . . . . . . . . . . . . . . . . . . . . . . . . 15

4.5 Impact testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

4.6 Abrasion testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

4.7 Flammability testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

6 Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

DRDC Atlantic TM 2009-017 vii


References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

Annex A: Abrasion Test Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

Annex B: Cone Calorimetry Test Data . . . . . . . . . . . . . . . . . . . . . . . . . 35

viii DRDC Atlantic TM 2009-017


List of figures
Figure 1: Preparation of clay nanocomposites. a) conventional microcomposite,
b) intercalated, c) exfoliated (i.e., nanocomposite). . . . . . . . . . . . . 1

Figure 2: SEM images of natural and synthetic clay PP nanocomposites. . . . . . . 6

Figure 3: XRD of uncompatibilized natural clay (Cloisite 15A) in PP. . . . . . . . 7

Figure 4: XRD of synthetic clay (Perkalite F100) in PP. . . . . . . . . . . . . . . . 7

Figure 5: SEM images of natural clay (Cloisite 15A) PA nanocomposites. . . . . . 9

Figure 6: SEM images of synthetic clay PA nanocomposites. . . . . . . . . . . . . 10

Figure 7: XRD of uncompatibilized natural clay (Cloisite 15A) in PA. . . . . . . . 11

Figure 8: XRD of synthetic clay (Somasif ME) in PA. . . . . . . . . . . . . . . . . 11

Figure 9: Example of dogbone specimens . . . . . . . . . . . . . . . . . . . . . . 16

Figure 10: Schematic drawing of a typical stress-strain curve. . . . . . . . . . . . . 17

Figure 11: Stress-displacement curve for PA nanocomposites incorporating


different nanoclays, measured at a crosshead displacement rate of
25 mm/min. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Figure 12: Stress-displacement curve for PP nanocompsites incorporating different


concentrations of uncompatibilized and compatibilized Cloisite 15A,
measured at a crosshead displacement rate of 25 mm/min. . . . . . . . . 18

Figure 13: Maximum and necking strength of PA nanocomposites. . . . . . . . . . 19

Figure 14: Maximum and necking strength of PP nanocomposites. . . . . . . . . . . 19

Figure 15: Stress-displacement curve for PA/ 5% wt. Lucentite SWN


nanocomposites at 10, 25 and 50 mm/min crosshead displacement rates. . 21

Figure 16: Stress-displacement curve for PP/ 4% wt. Cloisite 15A nanocomposites
at 10, 25 and 50 mm/min crosshead displacement rates. . . . . . . . . . 21

Figure 17: Maximum stress vs. loading rate for the PA nanocomposites. . . . . . . . 22

Figure 18: Maximum stress vs. loading rate for the PP nanocomposites. . . . . . . . 22

DRDC Atlantic TM 2009-017 ix


Figure 19: Necking stress vs. loading rate for the PA nanocomposites. . . . . . . . . 23

Figure 20: Necking stress vs. loading rate for the PP nanocomposites. . . . . . . . . 23

Figure 21: Relative total energy to break PP samples with natural Cloisite 15A
filler and compatibilized Cloisite 15A filler during impact. . . . . . . . . 24

Figure 22: Abrasion data for all samples studied: weight loss after 1000 cycles. . . . 25

Figure 23: Abrasion data: weight loss as a function of number of cycles for
PA-based nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . 26

Figure 24: Comparison of heat release rate for all samples . . . . . . . . . . . . . . 27

Figure 25: Comparison of ignition time for all samples . . . . . . . . . . . . . . . . 27

Figure 26: Comparison of smoke production rate for all samples . . . . . . . . . . . 28

List of tables
Table 1: Matrix of nanoclay composite samples prepared. . . . . . . . . . . . . . 3

Table 2: Decomposition temperatures of the nanoclay composites of PP and PA. . 13

Table 3: Crystallization temperatures of the nanoclay composites of PP and PA. . 14

Table 4: Young’s modulus (at 1 Hz) of the nanoclay composites of PP and PA. . . 15

Table A.1: Abrasion (weight loss) after 1000 cycles for all nanocomposites studied. 33

Table A.2: Abrasion (weight loss) as a function of number of cycles for PA series. . 33

Table B.1: Cone calorimetry data for all samples studied, exposed at 25 kW/m2 . . . 35

Table B.2: Cone calorimetry data for all samples studied, exposed at 35 kW/m2 . . . 35

x DRDC Atlantic TM 2009-017


Acknowledgements
The authors would like to thank Dr. Shannon Farrell (XRD), Ms. Manon Plourde (abrasion
tests), Mr. Yves Simard (compounding), Mr. Michel Carmel (sheet casting and injection
moulding) and the group of Dr. Joseph Su (cone calorimetry) for their technical contribu-
tions.

DRDC Atlantic TM 2009-017 xi


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xii DRDC Atlantic TM 2009-017


1 Background
In the Canadian Forces (CF) the dismounted soldier is being referred to as a system of
systems. In the future s/he will have the requirement to be a system that integrates all that
s/he wears and/or carries. The future soldier will carry more, utilize more technology and
withstand more extreme environments. To accomplish this, the integrated soldier system
project (ISSP) is considering multifunctional materials; materials that are lightweight while
enhancing stealth, ballistic protection, chemical/biological protection, supply power, or
exhibit increased durability/comfort. One possible class of materials to meet these demands
are nanocomposites.

Nanocomposites are a promising new area in material science. Many review articles have
been written describing the benefits that can be achieved from the nanoscale manipulation
of fillers [1–3]. The incorporation of nanosized particles with high aspect ratios into
polymers has led to new materials with unique properties. The platelet structures of clays
make them interesting high aspect ratio fillers. Clays have aluminosilicate layers (i.e.,
platelets) interspersed with interlayer cations (i.e., the space between the parallel layers of
clay platelets is the gallery. The gallery spacing changes depending on what cation occupies
the space). Although the bulk clay particle is not nanosized, each platelet has an in-plane
dimension of >100 nm and a thickness of 1–10 nm. To achieve nanoclay composites, the
clay layers must be delaminated and dispersed in a polymer matrix. The smectic class of
clays can be swollen, such that the gallery spacing is increased. Montmorillonite is the
most common type of smectite clay. To fully disperse the clay, the particles are sheared
apart, giving tactoids or polymer intercalated particles (Figure 1(b)). The intercalated
particles contain stacks of clay layers approximately 100–150 nm high. These can be
further exfoliated and dispersed when polymer enters the galleries of the clay, pushing the
platelets apart (Figure 1(c)). Nanoclay/polymer composites were first utilized industrially
by Toyota in 1990, where clays were incorporated into Nylon-6.

It has been shown that incorporating nanoclays into polymers can increase the mechanical
and thermal properties of the polymers [4–8]. These include improved strength, modu-

Clay Filler
Polymer Chain

(a) (b) (c)

Figure 1: Preparation of clay nanocomposites. a) conventional microcomposite, b) inter-


calated, c) exfoliated (i.e., nanocomposite).

DRDC Atlantic TM 2009-017 1


lus, UV absorbance and fire resistance. In this study, the physical properties of various
nanocomposite formulations are examined to determine the degree of improvement. The
goal of this project is the examination of the effects of different levels of nanoclay exfolia-
tion and different degrees of nanoclay loading on polypropylene (PP) and polyamide (PA).
PA and PP were chosen as the matrix materials for these nanocomposites because they can
be used in clothing. By adding nanoclays to these materials, it is hoped that they will be
imparted with multifunctionality, yielding regular clothing with improved fire resistance,
UV protection, etc.

2 DRDC Atlantic TM 2009-017


2 Materials
The matrices consisted of a PP homopolymer (Profax 1274 from Basell) or a PA-6 ho-
mopolymer (PA 1015B from UBE). The natural clay used was Cloisite 15A (Southern
Clay Products). In the case of the PP series, a compatibilization strategy was developed in
order to increase the adhesion between the matrix and the clay. Two low molecular weight
grafted polypropylenes (Epolen 3015; Eastman and Polybond 3150; Chemtura) were used.
Compatibilization was achieved by grafting these two low molecular weight PP to the clay
prior to compounding with the PP matrix polymer. The two compatibilizers were blended
in equal parts and then mixed 1:1 with the Cloisite 15A. In the case of the PA series, no
compatibilization was needed.

In addition to the formulations produced at the National Research Council of Canada


— Industrial Materials Institute (NRC—IMI), a commercially available PA-based nano-
composite was tested for comparison purposes. A 2 % wt. Cloisite 15A in PA was
purchased from UBE (PA 1015C2).

Synthetic clays were also investigated. For PP, the synthetic clay chosen was Perkalite F100.
In the case of PA, two clays were investigated; Lucentite SWN (low aspect ratio: 50) and
Somasif ME100 (high aspect ratio: 6000). The sample matrix is shown in Table 1.

Preparation of nanocomposites at NRC-IMI utilized a 34 mm Leistritz co-rotating twin-

Table 1: Matrix of nanoclay composite samples prepared.


Polymer Clay Conc. (% wt.)
Polypropylene (PP) None 0
(Profax 1274) Natural 2
(Cloisite 15A) 4
Compatibilized Natural 2
(Cloisite + Low MW PP) 4
Synthetic 2
(Perkalite F100) 4
Polyamide-6 (PA) None 0
(a.k.a. Nylon 6) Natural 2
(PA1051B) (Cloisite 15A) 4
Synthetic 2.5∗
(Lucentite SWN) 5∗
Synthetic 2.5∗
(Somasif ME100) 5∗
∗ 2 % wt. and 4 % wt. loadings were used for dynamic mechanical analysis (DMA)

and abrasion tests

DRDC Atlantic TM 2009-017 3


screw extruder having a length to diameter ratio of 42. All materials were dried before
any processing. Master batches containing 20 % wt. clay were prepared and subsequently
diluted, also by twin-screw extrusion, to the final clay content (see Table 1). The screw
speed was 100 rpm and the throughput was 5 kg/h. The melt temperature was maintained
at 200◦ C and 240◦ C for the polypropylene and polyamide systems, respectively. The neat
PP and PA matrices were also processed under the same conditions so that all materials
experienced the same thermomechanical history. The nanocomposites were pelletized and
kept for further processing.

Three types of specimens were prepared for characterization. To evaluate mechanical


properties, Type I dogbones were prepared by injection moulding using a 30 ton Boy
injection press [9]. The mould was kept at 20◦ C. For abrasion and flammability tests,
cast sheets (PP system) or square plaques (PA system) were produced. The cast sheets
were extruded using a RandCastle cast film line equipped with a flat die. The sheets were
1 mm thick and 8 inches wide. The Boy injection press was also used to produce 10 cm ×
10 cm × 1 mm square plaques.

4 DRDC Atlantic TM 2009-017


3 Nanoclay dispersion
3.1 Polypropylene
Samples of PP were taken as prepared and freeze fractured by dipping in liquid nitrogen
and hitting with a hammer. The resulting fracture surface was examined using scanning
electron microscopy (SEM). The SEM was a Leo 1455VP model. Samples were imaged
using an accelerating voltage of 20 kV and a working distance of 8 mm. Variable pressure
was used to eliminate the need to gold coat the samples. The two detection techniques
used were secondary electron (SE) imaging and back-scattered electron (BSE) imaging. In
SE imaging, the primary contrast mechanism is the variation in topography. Since it is a
fracture surface being examined, the changes in contrast show areas where failure initiated
or where crack growth faces joined. The BSE images primarily show variations in atomic
number. High atomic numbers appear bright. For the current nanocomposites, the clay
will appear bright, while the polymer will appear darker. The SEM images for PP loaded
with 4 % wt. clay, both natural and synthetic, are shown in Figure 2. Comparing the SE
images (i.e., left hand side of figure) with the BSE images (i.e., right hand side of figure),
both show similar features. In many instances, the areas that are “bright” in the secondary
electron image are also “bright” in the back-scattered electron image. This indicates that
the fracture occurred where the clay particle concentration was highest, possibly due to
poor dispersion. The exception to this is for the Perkalite F100 sample (Figures 2(e) and
2(f)). In this case, the secondary electron image shows the variations in topography but the
back-scattered electron image shows a near uniform distribution of atomic number. This
indicates that the clay is dispersed, which is to be expected since the Perkalite F100 was
chosen because of its compatibility with PP.

Intercalation rather than exfoliation for the PP samples was evidenced through X-ray Dif-
fractography (XRD). XRD analysis measures the order in a sample and can provide the
gallery spacing between the platelets of the clay. As polymer intercalates into the clay, the
gallery spacing is increased (i.e., swells). This swelling can be followed using XRD.

X-ray diffractograms were collected on a Philips X’Pert system using CuKα radiation.
Samples were analyzed from 1.5 to 10 or 15◦ 2θ, as appropriate. Divergence slits of 1◦ and
1◦
4 were used for the incident and diffracted beams respectively to minimize signal received
by the detector as a result of the low analysis angles. Figure 3 shows the X-ray diffrac-
togram for uncompatibilized Cloisite 15A in PP, where d is the gallery spacing. Comparing
the gallery spacing of pure Cloisite 15A to the PP/Cloisite nanoclay composites, the d-
spacing decreased from 3.1 nm to 2.9 nm. This is contrary to prediction. Introduction
of the polymer should result in an increase of the gallery spacings. The decrease was
possibly due to heating during processing. The twin screw extruder used to compound
these materials is operated at >100◦ C, as a result it is possible that it drove water out of the
clay, resulting in a contraction of the galleries. If the clay was not mixing well with the PP,
then intercalation/exfoliation would not offset this contraction.

DRDC Atlantic TM 2009-017 5


(a) SE (b) BSE

(c) SE (d) BSE

(e) SE (f) BSE

Figure 2: SEM images of natural and synthetic clay PP nanocomposites. a-b) uncompati-
bilized Cloisite 15A, c-d) compatibilized Cloisite 15A, e-f) Perkalite F100.

6 DRDC Atlantic TM 2009-017


300
cloisite
d=3.1 nm PP + 2% cloisite
d=2.9 nm PP + 4% cloisite
250

200
counts/s

150

100

50

0
2 3 4 5 6 7 8 9 10
2 Theta

Figure 3: XRD of uncompatibilized natural clay (Cloisite 15A) in PP.

180
perkalite F100
160 PP + 2.5% F100
d=2.93 nm PP + 5% F100
140

120
counts/s

100
d=4.0 nm
80

60

40

20

0
2 3 4 5 6 7 8 9 10
2 Theta

Figure 4: XRD of synthetic clay (Perkalite F100) in PP.

DRDC Atlantic TM 2009-017 7


Figure 4 shows the X-ray diffractogram for Perkalite F100 in PP. Here, the synthetic clay
was chosen to be compatible with PP, and the d-spacing reflects the intercalation with
a shift from 2.9 nm to 4.0 nm. The presence of a peak indicates that intercalation has
occured, but full exfoliation was not reached. In the case of fully exfoliated clay platelets,
the XRD would show no peaks due to a lack of ordering in the sample.

3.2 Polyamide
Samples of PA were taken as prepared and freeze fractured using the same method de-
scribed for PP. The SE and BSE SEM images for PA loaded with 4 % wt natural clay are
shown in Figure 5. Figures 5(a) and 5(b) show the images of the PA samples prepared in
this study, while Figures 5(c) and 5(d) are the commercially available PA/Cloisite nanoclay
composite. Again, the secondary electron image shows the variations in topography. The
images for the commercial nanocomposite appear identical to the in-house composites. The
synthetic clays Lucentite SWN and Somasif ME 100 were also examined (Figure 6). These
show similar results to the natural clay nanocomposites. Comparing the images from both
the PP and PA nanocomposites (Figures 2, 5 and 6), it can be seen that as the clay becomes
more compatible with the matrix, the SE images show smoother fracture surfaces and the
BSE images become more uniform, losing detail.

XRD analysis of PA with Cloisite 15A (Figure 7) shows that the d-spacing increases from
3.4 nm to 3.7 nm. With the PA and Somasif ME 100, the d-spacing increased only 0.01 nm.
The initial d-spacing for the Somasif ME 100 was only 0.96 nm (Figure 8). It is believed
that this spacing is too low and the CuKα radiation used in this XRD method is not precise
enough to measure changes in its value. Since peaks were observed, there were still clay
galleries, and full exfoliation did not occur. The additional peaks at 2θ=3 and 6◦ are a
result of the crystalline portions of the PA. Polyamide-6 is typically approximately 50%
crystalline [10]. In the case of the commercially available nanocomposite, no clay peaks
were detected, indicating full exfoliation.

Lucentite SWN was also analysed using XRD. Unfortunately, no usable peaks were iden-
tified in the neat clay sample, so further analysis of the nanocomposite was impossible.

Micrographs and XRD data suggest that PA has better dispersion than PP nanoclay com-
posites.

8 DRDC Atlantic TM 2009-017


(a) SE (b) BSE

(c) SE (d) BSE

Figure 5: SEM images of natural clay (Cloisite 15A) PA nanocomposites. a-b) in-house
samples, c-d) commercial sample.

DRDC Atlantic TM 2009-017 9


(a) SE (b) BSE

(c) SE (d) BSE

Figure 6: SEM images of synthetic clays in PA nanocomposites. a-b) Lucentite SWN


samples, d-e) Somasif ME 100 sample.

10 DRDC Atlantic TM 2009-017


450
d=3.7 nm cloisite
400 d=3.4 nm PA + 2% cloisite
PA + 4% cloisite
350

300
counts/s

250

200

150

100

50

0
2 3 4 5 6 7 8 9 10
2 Theta

Figure 7: XRD of uncompatibilized natural clay (Cloisite 15A) in PA.

100
somasif ME
PA + 2.5% ME d=0.96 nm
PA + 5% ME
80

60
counts/s

40

20

0
2 3 4 5 6 7 8 9 10
2 Theta

Figure 8: XRD of synthetic clay (Somasif ME) in PA.

DRDC Atlantic TM 2009-017 11


4 Nanocomposite physical properties
4.1 Thermogravimetric analysis
Decomposition of the nanocomposites was examined using thermogravimetric analysis
(TGA) on a TGA Q500 Thermogravimetric Analyzer (TA Instruments, New Castle, Dela-
ware). Between 5 and 20 mg of the sample was placed in the TGA weigh pan and analyzed
using a high resolution dynamic TGA technique. Nitrogen was used as the purge gas
(flow rate 100 mL/min). The sample was equilibrated at 35◦ C and then heated at a rate of
50◦ C/min to 800◦ C. The high resolution mode allows the TGA to auto adjust the heating
rate as the sample undergoes decomposition. As the sample decomposes and loses weight,
the heating rate is lowered to near isothermal conditions. The lowering of the heating rate
prevents thermal lag in the sample and allows for separation of components in the sample
that may decompose at similar temperatures. Once the decomposition of the sample had
slowed, the heating rate returns to the original conditions of 50◦ C/min. The purge gas was
switched from nitrogen to air at 650◦ C to burn off any remaining organics and allow for
the determination of the amount of inorganic residue present in the samples.

Depending on the polymer, the decomposition occurred between 400 and 500◦ C (Table 2).
The temperature of maximum weight loss was determined by the location of the first
derivative peak of weight loss versus temperature. The mass of the remaining inorganic
ash was used to confirm the sample weight percent compositions.

The PP/Cloisite 15A showed an increase in decomposition temperature of 9◦ C over neat


PP. The PP/Perkalite F100 showed a decrease of 3◦ C from neat PP. For the PA samples,
the change in decomposition temperature was more significant; PA/Cloisite 15A showed a
31◦ C drop (Table 2). There appears to be no trend relative to concentration of filler.

Schartel claims that [11]:

The results reported on the thermal and thermooxidative decomposition of


layered silicate nanocomposites are rather contradictory and do not lead to
unambiguous or consistant conclusions. The results vary from enhanced de-
composition to no significant influence, to a strong improvement depending
on the source and system discussed.
The influence on thermal decomposition is determined by specific interactions
with the nanoscaled additive during polymer decomposition. The influence on
the thermal and thermooxidative decomposition is a specific characteristic for
each system.

The results reported here are consistent with Schartel [11]. Better nanoparticle dispersion
would yield increased nanoclay/polymer interactions, causing their influence on the ther-
mal decomposition to be more pronounced.

12 DRDC Atlantic TM 2009-017


Table 2: Decomposition temperatures of the nanoclay composites of PP and PA. Temper-
atures reported are averaged of three trials.
Polymer Clay % wt. Decomp.
clay Temp. (◦ C)
Polypropylene (PP) None 0 456
(Profax 1274) Natural 2 465
(Cloisite 15A) 4 465
Compatibilized Natural 2 465
(Cloisite + Low MW PP) 4 465
Polypropylene (PP) None 0 463
(Profax 1274) Synthetic 2 460
(2nd round) (Perkalite F100) 4 460
Polyamide-6 (PA) None 0 441
(a.k.a. Nylon 6) Natural 2 410
(PA1051B) (Cloisite 15A) 4 410
Commercial 2 450
Synthetic 2.5 438
(Lucentite SWN) 5 430
Synthetic 2.5 444
(Somasif ME100) 5 444

4.2 Differential scanning calorimetry


Differential scanning calorimetry (DSC) was used to determine the crystallization tem-
peratures of the nanocomposites (Table 3). Samples were analyzed using a DSC Q1000
Differential Scanning Calorimeter equipped with a DSC Refrigerated Cooling System (TA
Instruments, New Castle, Delaware). Between 3 and 10 mg of sample was encapsulated in
an aluminum sample pan. Nitrogen was used as the purge gas (flow rate 50 mL/min). The
samples were cooled to –80◦ C and then exposed to a heat/cool/heat cycle up to 250◦ C at a
heating and cooling rate of 10◦ C/min. As the samples were heated and then cooled, they
underwent melting and crystallization phase changes. The melting temperature was deter-
mined to be the maximum of the endothermic peak while the crystallization temperature
was determined to be the maximum of the exothermic peak. The degree of crystallinity
was taken as the area under the exothermic peak.

For the PP nanocomposite, a 3–5◦ C drop in crystallization temperature was observed when
uncompatibilized Cloisite 15A was used. When 4% wt. compatibilized Cloisite 15A was
added, the amount of crystallinity decreased and the crystallization temperature decreased
by 7◦ C. When the Perkalite F100 synthetic clay was added, the crystallinity didn’t change,
but the crystallization temperature increased by 8◦ C. This last result is counter-intuitive
because addition of an impurity is usually accompanied by a freezing point depression. The

DRDC Atlantic TM 2009-017 13


Table 3: Crystallization temperatures of the nanoclay composites of PP and PA. Tempera-
tures reported are averages of three trials.
Polymer Clay % wt. Area Cryst. Cryst.
clay (J/g) Temp. (◦ C)
Polypropylene (PP) None 0 92.87 122
(Profax 1274) Natural 2 92.09 117
(Cloisite 15A) 4 85.18 119
Compatibilized Natural 2 88.56 118
(Cloisite + Low MW PP) 4 81.02 115
Polypropylene (PP) None 0 96.75 123
(Profax 1274) Synthetic 2 98.22 129
(2nd round) (Perkalite F100) 4 97.30 131
Polyamide-6 (PA) None 0 67.68 190
(a.k.a. Nylon 6) Natural 2 66.55 189
(PA1051B) (Cloisite 15A) 4 66.51 189
Commercial 2 58.93 183
Synthetic 2.5 64.78 188
(Lucentite SWN) 5 60.41 188
Synthetic 2.5 66.66 188
(Somasif ME100) 5 65.69 189

DSC data for the PA nanocomposites showed a 1–2◦ C drop in crystallization temperatures
as a result of the addition of clay. The exception being the commercial PA/Cloisite 15A
nanocompsite which exhibited a 7◦ C decrease in crystallization temperature. The lower
crystalline temperatures indicate that the nanoclay particles do not act as a nucleating agent
for crystallization, in fact they have the opposite effect. The partially intercalated nanoclay
particles inhibit large scale crystal growth [12].

4.3 Dynamic mechanical analysis


Nanoclay composite samples were analyzed using dynamic mechanical analysis on a DMA
Q800 Dynamic Mechanical Analyzer equipped with a Liquid Nitrogen Gas Cooling Acces-
sory (TA Instruments, New Castle, Delaware). Samples approximately 30 mm × 6.3 mm
× 1.5 mm were cut from the polymers sheets and mounted in a tension clamp. A pre-load
force of 0.2 N was applied to the sample, keeping it in tension. An oscillation amplitude of
40 µm was used during the analyses. The Force Track (keeps the static load at a proportion
greater than the dynamic load required to drive the selected amplitude) was set at 125%.
Samples were cooled to –60◦ C, then heated in 5◦ increments up to 60◦ C. At each increment,
the storage modulus was determined using the preset frequencies of 0.1 Hz, 0.2 Hz, 0.5 Hz,
1.0 Hz, 2.0 Hz, 5.0 Hz, 10.0 Hz, 50.0 Hz and 100 Hz. For simplicity, data was reported
only for 1 Hz and only at the temperatures of –20, 20 and 40◦ C (Table 4).

14 DRDC Atlantic TM 2009-017


Table 4: Young’s modulus (at 1 Hz) of the nanoclay composites of PP and PA. Moduli
reported are averages of three trials.
Polymer Clay % wt clay Young’s Modulus (GPa)
-20◦ C +20◦ C +40◦ C
Polypropylene (PP) None 0 3.774 1.797 1.114
(Profax 1274) Natural 2 3.870 1.965 1.255
(Cloisite 15A) 4 4.258 2.158 1.367
Compatibilized Natural 2 4.073 2.153 1.384
(Cloisite + Low MW PP) 4 4.283 2.301 1.470
Polypropylene (PP) None 0 4.220 1.926 1.138
(Profax 1274) Synthetic 2 4.098 2.043 1.229
(2nd round) (Perkalite F100) 4 4.134 2.109 1.318
Polyamide-6 (PA) None 0 2.587 1.983 0.756
(a.k.a. Nylon 6) Natural 2 3.141 2.112 0.881
(PA1051B) (Cloisite 15A) 4 3.566 2.577 1.214
Commercial 2 3.363 2.253 1.089
Synthetic 2 2.965 2.344 0.957
(Lucentite SWN) 4 3.144 2.453 0.982
Synthetic 2 3.096 2.521 1.018
(Somasif ME100) 4 3.273 2.745 1.140

In general, when a hard filler is added to a soft matrix, the modulus increases. The general
trend when adding clays to polymers is that the modulus increases with an increase in clay
loading. The PP nanocomposites using the compatibilized Cloisite 15A tended to be stiffer
than the uncompatibilized counterparts.

The goal for many textiles is to increase the modulus of the thread by a factor of 2, which
may correspond to a decrease in volume of material by a factor of 2 and thus a decrease
in weight while maintaining strength (i.e., improved durability) [4]. For the PP and PA
examined here, a doubling was not achieved. The PP showed an increase in Young’s
modulus of approximately 15%, independant of compatibilization. The PA showed an
approximate 40% increase in Young’s modulus. The increase was more pronounced at
higher temperatures (e.g., 40◦ C) than at lower temperatures (e.g., –20◦ C).

4.4 Quasi-static tensile testing


Quasi-static tensile tests were conducted in order to determine the effects of the nanoclays
on the initial yield strength and the deformation behaviour of the polymers. The tensile
properties of the nanocomposites give an indication of how the presence of nanoclays
affect the load required to permanently deform the materials and an indication of the
stiffness of the nanocomposites. Dogbone specimens (length = 16.5 cm; width = 1.3 cm)

DRDC Atlantic TM 2009-017 15


Figure 9: Example of dogbone specimens; 4% wt. compatibilized Cloisite 15A in PP.

of the nanocomposites (Figure 9), were injection moulded. The thickness of the specimens
varied for the different nanocomposite compositions due to differences in the shrinkage
that occurred during curing. The target thickness for the specimens was 0.12500 , however,
shrinkage that occurred during curing resulted in slight variations. The flash was carefully
removed using a sharp utility knife. Care was taken to remove the flash in a single cut,
thus avoiding the introduction of “nicks” or stress concentrators along the gage length.
The width and the thickness of the specimens were measured using Vernier calipers and a
micrometer, respectively.

The tensile specimens were tested on a 100 kN servo-hydraulic load frame with closed-
loop feedback control. The use of an extensometer to measure strain resulted in premature
failures that initiated at the extensometer knife edges. To avoid these failures, the crosshead
displacement was used to calculate the strain during the tensile test. The maximum actuator
displacement was approximately 130 mm, which was inadequate to cause failure in most of
the specimens. When the specimens did not fail before the maximum actuator displacement
was achieved, the test was stopped at the maximum actuator displacement.

Three tensile tests were conducted at a constant crosshead displacement rate of 25 mm/min
for each nanocomposite composition. As extra specimens were manufactured for some of
the nanoclay formulation, some additional tests were conducted at crosshead displacement
rates of 5, 10, 50 and 100 mm/min to assess the effects of strain rate on the mechanical prop-
erties. It was found that the mechanical behaviour and the failure mode of the nanocom-
posites were sensitive to strain rate. Consequently, the behaviour of these nanocomposites
in high strain rate spinning processes may not be well represented by the quasi-static stress-

16 DRDC Atlantic TM 2009-017


Figure 10: Schematic drawing of a typical stress-strain curve.

strain curves. However, these quasi-static tests should give a good indication of the relative
behaviour of the nanocomposite materials.

A schematic drawing of a typical stress-strain curve is shown in Figure 10. The maximum
stress was calculated as the peak stress sustained by the specimen before necking occurred.
The necking stress was calculated as the average stress sustained by the specimen as the
necked area propagated along the gage length of the specimen. As indicated above, the
test was arrested when the limit of the actuator displacement was reached. The stress-
strain curves of specimens that failed during testing typically did not experience significant
necking prior to failure.

Representative stress-displacement curves for the various PA-based and PP-based nanocom-
posites are shown in Figures 11 and 12, respectively. For the PA nanocomposites, the con-
centration of nanoclay particles had significantly less effect on the mechanical behaviour
than the type of particle, so for clarity only the lower concentrations are presented in
Figure 11.

The maximum and necking stresses for the various nanocomposites are shown in Figures
13 and 14. The values reported are the average of three tests. The presence of nanoclays
increased both the maximum stress and the necking stress for both the PP and PA.

For the PA nanocomposites, the 5% synthetic Lucentite SWN caused the largest increase
in maximum stress (approx. 21%). The 4% Cloisite 15A had the least influence on
the maximum strength, with an increase of approximately 8%. The increase in necking
strength was approximately 5% for all of the additives. The percentage of nanoclay added
to the specimens did not seem to have a large effect on the mechanical properties.

The addition of nanoclays to PP resulted in maximum stress increases of approximately


30%. The necking stress of the uncompatabalized Cloisite 15A nanocomposites increased

DRDC Atlantic TM 2009-017 17


Figure 11: Stress-displacement curve for PA nanocomposites incorporating different
nanoclays, measured at a crosshead displacement rate of 25 mm/min.

Figure 12: Stress-displacement curve for PP nanocompsites incorporating different con-


centrations of uncompatibilized and compatibilized Cloisite 15A, measured at a crosshead
displacement rate of 25 mm/min.

18 DRDC Atlantic TM 2009-017


70
Max stress (MPa)
60 Necking stress (MPa)
50
40
30
20
10
0
Neat PA

2%
Cloisite 15A

4%
Cloisite 15A

2.5%
Somasif ME 100

5%
Somasif ME 100

2.5%
Lucentite SWN

5%
Lucentite SWN
Figure 13: Maximum and necking strength of PA nanocomposites, measured at a
crosshead displacement rate of 25 mm/min.

70
Max stress (MPa)
60 Necking stress (MPa)
50
40
30
20
10
0
Neat PP

2%
Cloisite 15A

4%
Cloisite 15A

2%
Cloisite 15A
(compatibilized)

4%

(compatibilized)
Cloisite 15A

Figure 14: Maximum and necking strength of PP nanocomposites, measured at a


crosshead displacement rate of 25 mm/min.

DRDC Atlantic TM 2009-017 19


by approximately 19%. One of the 4% wt. uncompatabalized Cloisite 15A specimens
failed before distinguishable necking occurred. All of the compatabalized Cloisite 15A
samples failed before significant necking occurred. Compatabalizing the Cloisite 15A only
caused a marginal effect on the maximum strength (compared to the uncompatabalized
Cloisite 15A), yet had a significant and detrimental effect on the nanocomposite ductility.

Figures 15 and 16 show the stress-displacement curves measured at different strain rates for
the PA/ 5% wt. Lucentite SWN and PP/ 4% wt. Cloisite 15A nanocomposites, respectively.

For the PA nanocomposites (Figure 15), the strain rate of the tests affected the maximum
stresses of the nanocomposites, but had a very small effect on the necking stress. For the PP
nanocomposites, the strain rate affected the maximum strength and the fracture elongation
(i.e., ductility).

The maximum stress vs. strain rate for the PA and PP nanocomposites are shown in Figures
17 and 18, respectively. The values plotted at 25 mm/min are the average of 3 tensile tests,
while each of the other points represents a single tensile test.

The maximum strength of the nanocomposites tended to increase with increasing strain
rate. The trend and the relative ranking of compositions was fairly consistent for the
different PA nanocomposite composititions. Although fewer data points were obtained
for the PP nanocomposites, the trend and relative ranking of compositions seem to be
similar for these nanocomposites as well. The neat specimens (both PA and PP) did not
consistently follow the trends of increasing strength with increasing strain rate that was
displayed by the nanocomposite. Only one sample was available per strain rate, with
more extensive statistical sampling, scatter in the data could be minimized and a trend
determined.

The necking stress of the polyamide nanocomposites was less affected by the strain rate,
as shown in Figure 19. It should be noted that at the higher strain rates, many of the
polypropylene nanocomposites failed without propagation of the necked region, and there-
fore it was not possible to calculate a “necking stress” for those specimens. The few data
points in Figure 20, which shows the necking stress vs. strain rate for the polypropylene
nanocomposites, appear to show a trend of decreasing necking stress with increasing strain
rate.

20 DRDC Atlantic TM 2009-017


Figure 15: Stress-displacement curve for PA/ 5% wt. Lucentite SWN nanocomposites at
10, 25 and 50 mm/min crosshead displacement rates.

Figure 16: Stress-displacement curve for PP/ 4% wt. Cloisite 15A nanocomposites at 10,
25 and 50 mm/min crosshead displacement rates.

DRDC Atlantic TM 2009-017 21


65

60

55
Maximum Stress (MPa)
50

45

40

35 Neat PA
2.5% Somasif ME 100
30 5% Somasif ME 100
2.5% Lucentite SWN
5% Lucentite SWN
25
0 20 40 60 80 100 120
Loading Rate (mm/min)

Figure 17: Maximum stress vs. loading rate for the PA nanocomposites.

65
Neat PP
2% Cloisite 15A
60 4% Cloisite 15A
2% Cloisite 15A (compatibilized)
55 4% Cloisite 15A (compatibilized)
Maximum Stress (MPa)

50

45

40

35

30

25
0 20 40 60 80 100 120
Loading Rate (mm/min)

Figure 18: Maximum stress vs. loading rate for the PP nanocomposites.

22 DRDC Atlantic TM 2009-017


44

42

Necking Stress (MPa)


40

38

Neat PA
36 2.5% Somasif ME 100
5% Somasif ME 100
2.5% Lucentite SWN
5% Lucentite SWN
34
0 20 40 60 80 100 120
Loading Rate (mm/min)

Figure 19: Necking stress vs. loading rate for the PA nanocomposites.

28
Neat PP
2% Cloisite 15A
4% Cloisite 15A
26 2% Cloisite 15A (compatibilized)
Necking Stress (MPa)

24

22

20

18
0 5 10 15 20 25 30
Loading Rate (mm/min)

Figure 20: Necking stress vs. loading rate for the PP nanocomposites.

DRDC Atlantic TM 2009-017 23


4.5 Impact testing
High velocity impact testing was performed to determine the energy required to break the
sample. A Dynatup R
MiniTowerTM instumented impact tester was used following ASTM
D3763-02 [13]. The test specimens were 3.2 mm thick, 60 mm diameter disks. A 12.7 mm
diameter steel rod with a hemispherical end was used with testing speed of 200 m/min.
Integration of the area under the force vs. time curve yields the toughness of the material.
Figure 21 shows the relative total energy needed to break 2 mm thick cast sheet samples of
PP nanocomposites with Cloisite 15A; each value is the average of 5 measurements. The
4% compatibilized Cloisite 15A showed the best result for these nanocomposites.

3.5
Relative Total Energy

2.5

1.5

0.5

0
Neat PP

2% nat.

4% nat.

2% comp.

4% comp.

Figure 21: Relative total energy to break PP samples with natural Cloisite 15A filler and
compatibilized Cloisite 15A filler during impact. Absolute total energy of a 1mm thick
sheet of neat PP was 2 J.

4.6 Abrasion testing


Abrasion tests were performed on 1 mm thick square plaques (10 cm × 10 cm). The PP-
based and PA-based nanocomposites were tested. The neat matrices were also evaluated.
The plaques were cut from cast sheets (PP series) or injection moulded (PA series). The
specimens were tested according to ASTM D1044-08 and D1242-87 on a Taber Platform
Abraser (model 5155) [14, 15]. Preliminary trials were performed using CS-10 abrading
wheels, designed to simulate abrading actions such as normal handling, cleaning and
polishing (medium grade). It was observed that the abrasion was very low (abraded weights
often below 10 mg) and the reproducibility of the results was poor. A second, slightly
coarser grade of abrasive wheel was utilized (model H-18). Results were more reproducible
and the abraded weights larger: therefore, the H-18 wheel was used for the rest of the trials.

24 DRDC Atlantic TM 2009-017


70
PP
65 PA
60

Weight Loss (mg)


55
50
45
40
35
30
25
20
0%

2% nat.

4% nat.

2% comp.

4% comp.

2% syn.

4% syn.

0%

2% nat.

4% nat.

2 % comm.
Figure 22: Abrasion data for all samples studied: weight loss after 1000 cycles.

Figure 22 shows the weight loss for both PP and PA systems after 1000 cycles. The
specimens (3 for each test) were cleaned and weighed prior to testing, and at the end of
the abrasion test. The frequency was 1 Hz and the weight of the abrading device (weight
applied on sample) was 500 g. Since the values of abraded material for the PA series were
relatively low and the effect of the clay addition appeared to be more significant than in the
case of PP, additional tests were carried out on the PA nanocomposites, exploring higher
numbers of cycles (Figure 23). In this case, the PA sample was cleaned and weighed at
several intervals. The degree of weight loss of PA as a function of the number of cycles
was recorded. As the clay loading increased, the mass loss due to abrasion increased,
indicating that the abrasion resistance is lower at larger concentrations.

It has been reported that the mechanism by which nanoparticles improve abrasion resis-
tance involves them supporting part of the applied load, thus reducing the penetration
into the polymer surface [16]. This hypothesis may hold for solid nanoparticles such as
the calcium carbonate used by Lu and Liu, but the nanoclays reported here had layered
structures. It is possible that the clay platelets cleaved, in an analogous way to mica. The
platelet cleaving is a possible explanation as to why the nanoclay loaded polymers behaved
worse than the neat polymers. This phenomena would be more pronounced if the clay was
not fully exfoliated. To prevent cleaving of the platelets, a strong polymer/clay surface
interaction was needed. It can be seen in Figure 22 where the synthetic clay, which was
chosen for its compatibility with the PP, performed better than the natural one.

DRDC Atlantic TM 2009-017 25


120
neat PA
commercial PA (2% clay)
100 PA + 2% nat. clay
PA + 4% nat. clay

Weight Loss (mg)


80

60

40

20

0
200 400 600 800 1000 1200 1400 1600 1800 2000
Number of cycles

Figure 23: Abrasion data: weight loss as a function of number of cycles for PA-based
nanocomposites.

4.7 Flammability testing


Flammability tests were performed on 1 mm thick square plaques (10 cm × 10 cm).
The PP-based and PA-based nanocomposites were tested. The neat matrices were also
evaluated. The plaques were cut from cast sheets (PP series) or injection moulded (PA
series). The specimens were tested according to ASTM E1354 using a cone calorimeter
[17]. This test measures the response of materials exposed to controlled levels of radiant
heating. This method is used to determine the time to ignition, heat release rate, mass loss
rate, effective heat of combustion and visible smoke development of materials. The rate of
heat release is determined by measurement of the oxygen consumption as determined by
the oxygen concentration and the flow rate in the exhaust. In this work, the samples were
exposed to heating fluxes of 25 and 35 kW/m2 . Tests were performed in duplicate on each
nanocomposite.

From each set of cone calorimetry results and for all samples studied, the following prop-
erties were determined:

• Ignition time (s) — time to sustained flaming

• Heat release rate (HRR, kW/m2 ) — heat evolved from the specimen per unit of time

• Smoke production rate (SPR, m2 /s)

The data for all conditions (both heat fluxes and all samples) are reported in the tables
of Annex B. The results are summarized in the form of histograms in Figures 24–26.

26 DRDC Atlantic TM 2009-017


650
PP-25
600 PP-35
PA-25
550 PA-35

HRR (kW/m2)
500

450

400

350

300

250
0%

2% nat.

4% nat.

2% comp.

4% comp.

2% syn.

4% syn.

0%

2% nat.

4% nat.

2 % comm.
Figure 24: Comparison of heat release rate for all samples at both a 25 kW/m2 and a
35 kW/m2 flux.

300
PP-25
PP-35
250 PA-25
PA-35
Ignition time (s)

200

150

100

50

0
0%

2% nat.

4% nat.

2% comp.

4% comp.

2% syn.

4% syn.

0%

2% nat.

4% nat.

2 % comm.

Figure 25: Comparison of ignition time for all samples at both a 25 kW/m2 and a
35 kW/m2 flux.

DRDC Atlantic TM 2009-017 27


0.07
PP-25
PP-35

Smoke Production Rate (m2/s)


0.06 PA-25
PA-35
0.05

0.04

0.03

0.02

0.01 0%

2% nat.

4% nat.

2% comp.

4% comp.

2% syn.

4% syn.

0%

2% nat.

4% nat.

2 % comm.
Figure 26: Comparison of smoke production rate for all samples at both a 25 kW/m2 and
a 35 kW/m2 flux.

PA-based nanocomposites had the lowest HRR values at low radiant heats. At high ra-
diant heats, the PA-based nanocomposites were as good as, or better than the PP-based
ones. More importantly, the HRR values for PA/Cloisite 15A were lower than those of
neat PA. No significant improvement on ignition time was observed, although addition of
Cloisite 15A resulted in a slight decrease with increasing loading levels. All nanoclay
composites resulted in increased smoke levels.

As reported in Section 4.1, the polymer nanocomposites show only minor changes in
polymer decomposition compared to the neat sample. Schartel claims that with few excep-
tions, neither decomposition temperatures nor effective heat of combustion of the volatile
polymer degredation products change significantly [11]. As a result the time to ignition
is not improved either. Nanoclays may need to be combined with more traditional flame
retardants to acheive better fire retardancy. As an example, Perkalite is marketed as a
flame retardant synergist and should be used in conjunction with other flame retardant
additives. Where nanoclays alone may prove advantageous is in the nanocomposite drip-
ping behaviour. During processing, it was observed that the addition of high aspect ratio
nanoparticles increased the melt viscosity of the polymer nanocomposite. A higher viscos-
ity results in less likelihood of dripping, thus the nanoclay could be used as an antidripping
agent to reinforce char.

28 DRDC Atlantic TM 2009-017


5 Conclusions
In this study, nanocomposites using natural and synthetic clays were made with PP and PA
matrices. Micrographs and XRD data suggest that Cloisite 15A was better dispersed in PA
than in PP, although not as well as in the commercially available sample. To optimize
dispersion, ideally PA nanoclay composites are made by intercalating the caprolactam
monomer into the clay galleries and polymerizing in situ. The physical properties of the
nanocomposites showed minor improvements over the parent polymers. It is believed that
poor dispersion played a role in the lack of significant improvements.

This study suggests that processing plays an important role in realizing the improved
properties of nanoclay composites. In the work reported here, adequate dispersion of the
clays was not accomplished. PA (i.e., nylon) appears to be the better matrix for nanoclay
composites. More basic research is needed before these composites can be transitioned to
viable technology for military applications.

DRDC Atlantic TM 2009-017 29


6 Future work
The primary concern for realizing true nanocompositions is the dispersion of the clays.
Future work will include an investigation of the in situ polymerization of PA. Physical
properties testing will focus on durability testing (i.e., the effect of UV, humidity, and
temperature) as well as chemical/biological resistance. If an appropriate nanocomposite is
developed, further testing of microfibre and nanofibre properties will be of interest.

30 DRDC Atlantic TM 2009-017


References
[1] Mai, Y. and Yu, Z., (Eds.) (2006), Polymer Nanocomposites, Cambridge England:
Woodhead Publishing Limited.

[2] Jang, B., Costache, M., and Wilkie, C. (2005), The relationship between thermal
degradation behavior of polymer and the fire retardancy of polymer/clay
nanocomposites, Polymer, 46(24), 10678–10687.

[3] Zheng, Q., Yu, A., Lu, G., and Paul, D. (2005), Clay-Based Polymer
Nanocomposites: Research and Commercial Development, Journal of Nanoscience
and Nanotechnology, 5, 1574–1592.

[4] Fornes, T. and Paul, D. (2003), Formation and Properties of Nylon 6


Nanocomposites, Polimeros: Ciência e Tecnologia, 13(4), 212–217.

[5] Kanny, K. and Moodley, V. (2007), Characterization of Polypropylene


Nanocomposite Structures, Journal of Engineering Materials and Technology, 129,
105–112.

[6] Sarkar, M., Dana, K., Ghatak, S., and Banerjee, A. (2008), Polypropylene-clay
composite prepared from Indian bentonite, Bull. Mater. Sci., 31(1), 23–28.

[7] Dong, W., Zhang, X., Liu, Y., Wang, Q., Gui, H., Gao, J., Song, Z., Lai, J., Huang, F.,
and Qiao, J. (2006), Flame retardant nanocomposites of polyamide 6/clay/silicone
rubber with high toughness and good flowability, Polymer, 47, 6874–6879.

[8] Zhang, J., Jiang, D., and Wilkie, C. (2006), Thermal and flame properties of
polyethylene and polypropylene nanocomposites based on an
oligomerically-modified clay, Polymer Degradation and Stability, 91, 298–304.

[9] ASTM Standard D638–99 (2000), Standard Test Method for Tensile Properties of
Plastics. ASTM International, West Conshohocken, PA.

[10] Odian, G. (1991), Principles of Polymerization, 3 ed, Ch. 2, pp. 102–106, New York:
Wiley-Interscience.

[11] Schartel, B. (2007), Flame Retardant Polymer Nanocomposites, Ch. 5, pp. 115–116,
New Jersey: Wiley-Interscience.

[12] Bhat, G., Hegde, R., Kamath, M., and Deshpande, B. (2008), Nanoclay Reinforced
Fibers and Nonwovens, Journal of Engineered Fibers and Fabrics, 3(3), 22–34.

[13] ASTM Standard D3763–02 (2002), Standard Test Method for High Speed Puncture
Properties of Plastics Using Load and Displacement Sensors. ASTM International,
West Conshohocken, PA.

DRDC Atlantic TM 2009-017 31


[14] ASTM Standard D1044 - 08 (2008), Standard Test Method for Resistance of
Transparent Plastics to Surface Abrasion. ASTM International, West Conshohocken,
PA.

[15] ASTM Standard D1242-87 (1987), Standard Test Methods for Resistance of Plastic
Materials to Abrasion. ASTM International, West Conshohocken, PA.

[16] Lu, X. and Liu, T. (2006), Polymer Nanocomposites, Ch. 16, p. 433, Cambridge,
England: Woodhead Publishing Limited.

[17] ASTM Standard E1354-08 (2008), Standard Test Method for Heat and Visible
Smoke Release Rates for Materials and Products Using an Oxygen Consumption
Calorimeter. ASTM International, West Conshohocken, PA.

32 DRDC Atlantic TM 2009-017


Annex A: Abrasion Test Data
Table A.1: Abrasion (weight loss) after 1000 cycles for all nanocomposites studied.
Matrix Comment Wt.% clay Weight loss (mg)
0 47.2±0.7
2 55.7±3.9
PP 4 61.2±3.6
compatibilized 2 60.5±7.5
4 63.8±1.3
0 21.6±1.4
2 36.2±1.6
PA 4 43.4±2.6
commercial grade 2 49.3±2.2

Table A.2: Abrasion (weight loss) as a function of number of cycles for PA series.
Number Weight loss (mg)
of cycles Neat PA Comm. PA PA + 2 Wt% PA + 4 Wt%
250 0.72 0.97 5.74 10.2
500 3.59 13.9 11.8 20.2
750 9.95 22.3 17.9 31.6
1000 15.2 36.5 29.0 48.0
1500 35.0 65.4 60.1 83.0
2000 55.4 97.2 83.6 119

DRDC Atlantic TM 2009-017 33


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34 DRDC Atlantic TM 2009-017


Annex B: Cone Calorimetry Test Data
Table B.1: Cone calorimetry data for all samples studied, exposed at 25 kW/m2 : ignition
time, heat release rate, time at peak, smoke production rate, carbon monoxide and carbon
dioxide yields at peak.
Matrix Comment wt.% Ignition HRR Time at SPR CO Yield CO2 Yield
clay time (s) (kW/m2 ) peak (s) (m2 /s) (×103 g/s) (g/s)
0 75 277 140 0.0295 3.30 0.171
75 304 140 0.0353 3.62 0.189
2 100 487 180 0.0569 5.67 0.289
85 460 160 0.0582 5.41 0.278
PP 4 80 474 155 0.0553 5.20 0.283
70 454 150 0.0550 4.87 0.257
Compatibilized 2 80 485 150 0.0592 5.63 0.289
85 450 155 0.0607 5.38 0.267
4 80 452 150 0.0524 5.28 0.267
85 423 155 0.0522 4.93 0.252
0 250 394 290 0.0154 2.82 0.231
245 480 305 0.0173 3.89 0.310
2 160 270 290 0.0238 3.04 0.178
180 262 340 0.0173 2.96 0.176
PA 4 155 311 265 0.0226 2.76 0.189
150 300 255 0.0223 3.14 0.199
Commercial 2 245 400 295 0.0197 3.58 0.259
Grade 210 397 275 0.0190 3.46 0.255

Table B.2: Cone calorimetry data for all samples studied, exposed at 35 kW/m2 : ignition
time, heat release rate, time at peak, smoke production rate, carbon monoxide and carbon
dioxide yields at peak.
Matrix Comment wt.% Ignition HRR Time at SPR CO Yield CO2 Yield
clay time (s) (kW/m2 ) peak (s) (m2 /s) (×103 g/s) (g/s)
0 45 352 95 0.0337 3.79 0.208
35 359 100 0.0424 3.68 0.215
2 30 609 115 0.0676 7.17 0.357
40 597 115 0.0694 6.60 0.349
PP 4 45 527 105 0.0682 5.95 0.314
– – – – – –
Compatibilized 2 45 493 105 0.0598 5.52 0.293
45 525 100 0.0675 6.14 0.316
4 40 491 100 0.0599 5.14 0.294
45 520 110 0.0660 5.97 0.307
0 100 533 150 0.0230 4.07 0.348
135 615 180 0.0230 4.57 0.401
2 70 483 150 0.0342 4.40 0.315
70 436 155 0.0342 4.18 0.282
PA 4 65 396 150 0.0308 3.74 0.259
60 394 155 0.0273 3.68 0.256
Commercial 2 100 500 145 0.0361 3.96 0.325
Grade 95 498 145 0.0238 3.93 0.324

DRDC Atlantic TM 2009-017 35


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36 DRDC Atlantic TM 2009-017


Distribution list
DRDC Atlantic TM 2009-017

Internal distribution
2 Royale Underhill (1 hard copy, 1 CD)

1 Allison Nolting

1 Gary Fisher

1 Irv Keough

1 Leon Cheng (H/DLA)

5 DRDC ATLANTIC LIBRARY FILE COPIES

Total internal copies: 11

External distribution
2 Nathalie Chapleau (1 hard copy, 1 CD)
Industrial Materials Institute
National Research Council Canada
75 de Mortagne Blvd.
Boucherville QC J4B 6Y4

1 NDHQ/DRDC/DRDKIM 3

1 Library & Archives Canada


Attention: Military Archivist, Government Records Branch

1 Suzanne Paradis
RDDC Valcartier
2459 Pie-XI Blvd North
Val-Bélair QC G3J 1X5

Total external copies: 5

Total copies: 16

DRDC Atlantic TM 2009-017 37


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38 DRDC Atlantic TM 2009-017


DOCUMENT CONTROL DATA
(Security classification of title, body of abstract and indexing annotation must be entered when document is classified)

1. ORIGINATOR (The name and address of the organization preparing the 2. SECURITY CLASSIFICATION (Overall
document. Organizations for whom the document was prepared, e.g. Centre security classification of the document
sponsoring a contractor’s report, or tasking agency, are entered in section 8.) including special warning terms if applicable.)

Defence R&D Canada – Atlantic UNCLASSIFIED


PO Box 1012, Dartmouth NS B2Y 3Z7, Canada

3. TITLE (The complete document title as indicated on the title page. Its classification should be indicated by the appropriate
abbreviation (S, C or U) in parentheses after the title.)

Formulation and Characterization of Nanoclay Composites: Towards Multifunctional Materials


for the Dismounted Soldier
4. AUTHORS (Last name, followed by initials – ranks, titles, etc. not to be used.)

Underhill, R. S.; Nolting, A.; Fisher, G.; Keough, I.; Chapleau, N.

5. DATE OF PUBLICATION (Month and year of publication of 6a. NO. OF PAGES (Total 6b. NO. OF REFS (Total
document.) containing information. cited in document.)
Include Annexes,
Appendices, etc.)

September 2009 54 17

7. DESCRIPTIVE NOTES (The category of the document, e.g. technical report, technical note or memorandum. If appropriate, enter
the type of report, e.g. interim, progress, summary, annual or final. Give the inclusive dates when a specific reporting period is
covered.)

Technical Memorandum
8. SPONSORING ACTIVITY (The name of the department project office or laboratory sponsoring the research and development –
include address.)

Defence R&D Canada – Atlantic


PO Box 1012, Dartmouth NS B2Y 3Z7, Canada

9a. PROJECT OR GRANT NO. (If appropriate, the applicable 9b. CONTRACT NO. (If appropriate, the applicable number under
research and development project or grant number under which the document was written.)
which the document was written. Please specify whether
project or grant.)

12si11
10a. ORIGINATOR’S DOCUMENT NUMBER (The official 10b. OTHER DOCUMENT NO(s). (Any other numbers which may
document number by which the document is identified by the be assigned this document either by the originator or by the
originating activity. This number must be unique to this sponsor.)
document.)

DRDC Atlantic TM 2009-017


11. DOCUMENT AVAILABILITY (Any limitations on further dissemination of the document, other than those imposed by security
classification.)
( X ) Unlimited distribution
( ) Defence departments and defence contractors; further distribution only as approved
( ) Defence departments and Canadian defence contractors; further distribution only as approved
( ) Government departments and agencies; further distribution only as approved
( ) Defence departments; further distribution only as approved
( ) Other (please specify):

12. DOCUMENT ANNOUNCEMENT (Any limitation to the bibliographic announcement of this document. This will normally correspond
to the Document Availability (11). However, where further distribution (beyond the audience specified in (11)) is possible, a wider
announcement audience may be selected.)
13. ABSTRACT (A brief and factual summary of the document. It may also appear elsewhere in the body of the document itself. It is highly
desirable that the abstract of classified documents be unclassified. Each paragraph of the abstract shall begin with an indication of the
security classification of the information in the paragraph (unless the document itself is unclassified) represented as (S), (C), or (U). It is
not necessary to include here abstracts in both official languages unless the text is bilingual.)

Nanocomposites are a promising new area in material science. Many researchers have
described the benefits of nanoscale fillers. The incorporation of nanosized particles with high
aspect ratios into polymers has led to new composites with improved physical properties such
as improved strength, UV absorbance and fire resistance. The work reported here compared
the physical properties of various nanoclay formulations. Degree of clay loading, the use
of compatibilizing agent and natural vs. synthetic clay were all examined. Polyamide and
polypropylene were chosen as the matrix materials, with Cloisite 15A as the natural clay and
Perkalite F100, Somasif ME or Lucentite SWN as the synthetic clays. Samples of neat, 2 wt.%
and 4 wt.% clay were prepared and analyzed using scanning electron micrography and x-ray
diffraction to determine dispersion. The physical properties of the nanocomposites were then
examined using thermogravimetric analysis, dynamic mechanical analysis, quasistatic tensile
testing, impact testing, abrasion testing and cone calorimetry. The particles in the polyamide
nanocomposites appeared to be better dispersed than in the polypropylene nanocomposites.
The physical properties of the nanocomposites showed minor improvements over the parent
polymer, while the addition of nanoclays to the polyamide system imparted better physical
properties than the polypropylene. It is believed that poor dispersion played a role in the lack
of significant improvements in material properties.

14. KEYWORDS, DESCRIPTORS or IDENTIFIERS (Technically meaningful terms or short phrases that characterize a document and could
be helpful in cataloguing the document. They should be selected so that no security classification is required. Identifiers, such as
equipment model designation, trade name, military project code name, geographic location may also be included. If possible keywords
should be selected from a published thesaurus. e.g. Thesaurus of Engineering and Scientific Terms (TEST) and that thesaurus identified.
If it is not possible to select indexing terms which are Unclassified, the classification of each should be indicated as with the title.)

Cloisite, Perkalite, Lucentite, Somasif, polyamide, polypropylene, nanocomposite, nanoclay


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