Polyamide-6/Clay Nanocomposites: A Critical Review

Polyamide-6/Clay Nanocomposites: A Critical Review

Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak*

Ecole des Mines de Douai, Polymers and Composites Technology Department, 941 rue Charles Bourseul,
BP 10838, F-59508 Douai Cedex, France

Received: 2 December 2004 Accepted: 24 May 2005

SUMMARY
The plastics business is gathering around nanocomposites because of the unusual
performance of these materials in some technologically important applications, such as
automotive parts, packaging, textiles and flame resistant materials. The use of clay as
the reinforcing component of polymers has transformed the properties of the resultant
materials. These nanocomposites are regarded as futuristic. However the science of clay-
polymer interaction is still a subject of intense investigation. The industrialization of
nanocomposites is accelerating and efforts are being made to achieve still better performance
by optimising of their compounding and processing conditions. Nanocomposites based
on many different polymers have been, or are being developed. The current scenario in
relation to polyamide-6/clay nanocomposites is presented in this article. Preparation,
processing and application issues are addressed in particular.

1. INTRODUCTION Nanocomposites have been attracting attention

since the 1990’s when Toyota, for the first time,
Nanocomposites are gaining acceptance in the produced polyamide-6/clay nanocomposites,
mainstream of the global plastics processing used them to manufacture timing belt housings for
industry and there has been a great recognition of the automotive industry, and demonstrated their
their enormous potential in relation to a wide range unprecedented thermo-mechanical properties5,6.
of product development. The term nanocomposite This event proved to be the signal for a great deal
relates to the dispersion of nano-sized particles of international academic and industrial research.
within the polymer matrix1. In the last few years, Several other nanofillers, such as mica, graphite
a large number of nanomaterials consisting of and carbon tubes are now also being exploited. Wu
particles measuring a billionth of a metre (one et al7 have carried out a comparative evaluation of
nanometre) or less have been commercialised. some of these nanoadditives. However, huge interest
The new polymeric materials made by using these has arisen in layered silicate (clay) nanocomposites
particles in an appropriate matrix may be classified based on thermoplastics, elastomers or thermosets.
as advanced materials because of their superior In spite of initially slow progress, there has since
tensile strength, modulus and dimensional stability been tremendous growth and success in product
compared with conventional composite materials. development, with significant achievements in the
The nanoparticles are so small and their aspect ratio plastics processing industry. These new materials
is so high that the material properties improve even have already brought so many innovations in
when the filler component is very low compared technologically important domains that they are
to conventional reinforcements like talc and glass. expected to shake up the industrial world, for
The nanocomposite materials also offer lower example in packaging industry (e.g. barrier films),
permeability to moisture, gases and hydrocarbons automotive and aerospace industries (e.g. high
along with significant improvements in thermal strength polymers), textiles, and fire resistant or
behaviour, flame resistance, ionic conductivity, abrasion resistant materials. Figure 1 illustrates the
chemical resistance and bulk clarity2-4. worldwide market potential for nanocomposites. An
annual growth rate of about 20% is forecast over
the next five years, with a dominating position for
thermoplastics8. It is expected that the industry will
be using 500000 tonnes of nanocomposites in 2010
*Author to whom correspondence should be sent
compared to 1500 tonnes today9.
©
Rapra Technology Limited, 2006

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 13

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

Figure 1. Worldwide futuristic scenario of nanocomposites (sales by value)8

180 Thermoplastic
160 Thermoset
140
120
$ millions

100
80
60
40
20
0
2003 2008
Year

Nanocomposites have been or are being developed achieved when the clay platelets are completely
based on several different thermoplastics. Among dispersed, without aggregates in the matrix.
them, considering its relatively low cost and high
performance, polyamide-6 (PA-6) is an interesting
The challenging issues of PA-6/clay nanocomposite
polymer with several potential or actual applications,
preparation are therefore intercalation (introduction
such as in films, textiles and engineering parts. The
nanocomposites based on PA-6 are also attracting of polymer between the clay platelets), exfoliation
significant interest since they exhibit unexpected (separation of individual platelets leading to an
hybrid properties, synergistically derived from their homogeneous dispersion within the matrix), and
two components10,11. The PA-layered aluminosilicate control of the polymer-filler interaction, which may
nanocomposites have been quite promising because be favoured by clay surface treatment with organic
they offer exceptional reinforcement at a very low ions, so as to make it hydrophobic, and by adding
filler concentration (usually lower than 10 wt%). compatibilisers. The resulting nanocomposite has
Typically, the type of silicate used in polymer- a polymorphic structure, which may be modified
silicate nanocomposites is montmorillonite by annealing and by changing the filler nature or
(MMT), a 2:1 layered smectite clay, and extensive amount. Processing conditions at high temperatures
studies have been reported on the development of and high shearing rates are also likely to induce
nanocomposites based on such PA/clay hybrids12- thermal degradation and preferential orientation of
16
. This type of clay is an inorganic mineral and the platy structured fillers. These key issues, together
has a natural platy structure with the individual with the possible applications and performance of
platelets having a thickness of 1 nm and a width polyamide-6/clay nanocomposites, are addressed
and length of several tens of nm, which explains in the following sections.
their very high surface area (100-1000 m2/g) and
aspect ratio (length/thickness > 100). Associating
2. PREPARATION AND PROCESSING OF
this type of nanofiller with a polymer matrix is a key
challenge. Montmorillonite has a layered structure, POLYAMIDE-6/CLAY NANOCOMPOSITES
where the silicate layers have sodium or calcium 2.1 Intercalation and Exfoliation
ions in the interlayer space. During nanocomposite
fabrication, these spaces have to be filled with Various efforts have been made to prepare
polymer, causing the clay to swell and increase nanocomposites by different routes4. One promising
the distance between the layers to an intercalated strategy is the intercalation of monomers or polymers
state once the electric charges and Van der Waals into the silicate hosts followed by exfoliation
forces have been sufficiently lowered (Figure 2). (Figure 3)7. The term intercalation describes the case
Other types of clay such as saponite, laponite or where a small amount of polymer moves into gallery
boechmite may be used as well. However, the spacing (interlayer) between the clay platelets to a
expected performance improvement can only be level of 2 - 3 nm. The exfoliation or delamination

14 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

Figure 2. Polymer/clay nanocomposites: intercalated and delaminated or exfoliated structures

Figure 3. Schematic route to the PA-6/clay nanocomposites preparation7

Intercalation
Na+Na+Na+
CL/water
Clay Clay
Exfoliation Polymerisation

Nylon-6
Intercalation/
exfoliation
Nanocomposite
CL stands for caprolactum

occurs when the polymer further separates the The incorporation of clay into thermoplastics by
clay platelets (e.g. 8-10 nm or more). The initial melt compounding using a conventional extrusion
preparations were confined to the polymerisation process has become the favoured practice and will
of caprolactam in the presence of organophilic greatly influence commercial opportunities for this
montmorillonite ions, exchanged with ammonium technology in the near future20. Here, organophilic
ions10,17. This in-situ process was further improved clay (organo-clay) is necessarily used to yield
by Liang et al18, who dispersed clay into molten exfoliated compounds because the silicate layers
caprolactam at 90 °C for 2-4 h and then carried out do not exfoliate during compounding without
polymerisation at 260 °C for 10 h under a nitrogen organo-modification. The advantages of forming
blanket in a reactor. However, although it was taken nanocomposites by melt processing are very
up by the Toyota Research group, the in-situ process interesting. The process does not require a solvent,
has not been used in practice any more because of so it is an eco-friendly approach. Moreover, it shifts
the difficulty of finding a suitable monomer and a nanocomposite production downstream, thereby
compatible solvent system. So others elaboration giving end-use manufacturers freedom with respect
strategies (such as melt compounding) have been to the final product specification.
designed and commonly used for commercial
products, even if nanocomposites made by the in-
situ process have been found to out-perform other Efforts are currently directed to the optimisation
ones by a significant margin19. of melt compounding conditions so as to achieve

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 15

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

an homogeneous dispersion of the clay exfoliated reported using a sodium montmorillonite slurry
platelets within the polymer matrix. For example, in PA-6 where the silicate clay layers exfoliate and
the influence of the extruder type and the screw disperse homogeneously at the nanoscale level24.
design (single- or twin-screw, co-rotating or counter- The sodium montmorillonite is first blended with
rotating, intermeshing or non-intermeshing, low/ molten PA-6 in an extruder. Water is removed from
medium/high shear intensity obtained according to the vent by applying a vacuum. The removal of water
screw geometry) has recently been investigated19,21. also helps to prevent the PA-6 degradation.
It has been demonstrated that the degree of
exfoliation (delamination) and dispersion of organo-
modified layered silicate nanocomposites (PA-6/ 2.2 Polymorphism
montmorillonite) is affected by the compounding The evolution of polymorphism in polyamide
conditions. For example, increasing the mean nanocomposites has been observed by various
residence time in the twin-screw extruder generally authors25-28. PA-6 has two major crystalline phases (a
increases the delamination and dispersion. monoclinic α-phase and a pseudoclinic hexagonal
However, there appears also to be an optimum shear γ-phase)29. The polymorphic structure of polyamides
intensity and an optimum extent of back mixing (a results from the different spatial arrangement in
measure reflecting the broadness of the residence the hydrogen bonding between the oxygen in the
time distribution). Representative X-ray diffraction carbonyl group of polyamide molecular chain
scans and transmission electron microscopy (TEM) and the hydrogen attached to the nitrogen in the
micrographs are shown on Figures 4 and 5, while neighbouring polyamide molecular chain30. The
Table I summarises some results obtained over a wide principal difference between the two phases is the
range of process conditions. Further investigation molecular packing. The α-phase consists of fully
are still required to differentiate the effects of shear extended planar zigzag chains in which adjacent
intensity, mean residence time and mean residence antiparallel chains are joined by the hydrogen bonds.
time distribution, as well as feed rate, temperature Therefore, it is thermodynamically the most stable
profile and screw rpm, which are all critical to crystalline phase and can be obtained during slow
achieve the desired exfoliation21. cooling from the melt. The γ-phase consists of pleated
sheets of parallel chains joined by hydrogen bonds.
However, the compounding process is quite This is a less stable phase and is obtained during
expensive. So natural (virgin) clay minerals without fibre spinning at high speed, or fast cooling31. The
organo-modification have been studied with the aim γ-phase can be converted into the α-phase by melting
of further developing the industrial process. Under and subsequent crystallization. If the polymer is
such circumstances, a compatibiliser is needed to crystallized isothermally, it shows an amorphous
achieve the desired characteristics, and the clay halo in the X-ray diffraction pattern, with a maximum
minerals and polymers are compounded with at 20.8°. Evolution of its crystalline nature takes
alkylammonium salts and maleic anhydride22,23. place with increasing annealing temperature, finally
Recently, a novel compounding process has been leading to the two-peak diffraction pattern25.

Figure 4. Wide angle X-ray diffraction scans for PA-6/3,1 wt% montmorillonite organoclay (non-optimised chemical
treatment) prepared by melt compounding using different extruder/screw configurations21

16 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

Figure 5. Transmission electron microscopy view for PA-6/3,1 wt% montmorillonite organoclay (non-optimised
chemical treatment) prepared by melt compounding using different extruder/screw configurations21

Single screw Co-rotating, low shear

Co-rotating, medium shear Counter-intermeshing, medium shear

Table 1. Influence of different extruder/screws configuration on PA-6/montmorillonite organoclay nanocomposites

prepared by melt compounding21
Extruder and screw type X-ray X-ray TEM platelets Extruder Normalized
diffraction diffraction or intercalates mean variance
basal spacing area under per 6.25 cm3 (at residence (measure of
(10-1 nm) curve 130500 X) time (s) back mixing)
Single screw extruder
Clay treatment A * 30.9 120 13 141 0.0049
Clay treatment B * 32.2 825 4 141 0.0049
Twin screw extruder
Co-rotating intermeshing
Low shear/clay treatment B 36.2 382 7 67 0.090
Medium shear/clay treatment B 37.7 146 16 153 0.113
Counter-rotating intermeshing
Low shear/clay treatment B 34.4 263 8 47 0.0557
Medium shear/clay treatment B 38.0 106 14 102 0.0557
Medium shear/clay treatment A No Peak No Peak 35 102 0.049
High shear/clay treatment B 37.9 164 10 117
Counter-rotating non-intermeshing
Low shear/clay treatment B 34.7 581 11 108 0.0895
Medium shear/clay treatment B No Peak No Peak 27 162 0.0653
High shear/clay treatment B 37.9 277 20 136 0.0579
* Montmorillonite clay chemical treatments A and B correspond to optimised and non-optimised organo-
modifications respectively. The organoclay A is designed to easily delaminate and disperse in PA-6 (better
compatibility). The mineral content of the nanocomposites is 3,7 and 3,1 wt% for A and B respectively

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 17

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

The scenario changes when PA is blended with of PA-6/montmorillonite nanocomposites depends

nanoclay15. The cooling pattern of PA and its on the isothermal crystallization temperature26.
nanocomposites is distinctly reflected in its X-ray With increasing crystallization temperature, the
diffraction behaviour. The X-ray diffraction pattern α-phase in PA-6 converts steadily into the γ-phase
of virgin PA-6 and its nanocomposites shows that and increases the perfection of the crystallites.
the α1 and α2 peaks are very prominent (Figure 6, Fourier Transform Infrared Spectroscopy (FT-
plot a). The γ-phase shows a single peak at 21.5° IR) studies on monofilaments have confirmed
(plot b). The slow cooling of the nanocomposite the above observations that the cooling pattern
shows both α and γ-phases in the polymer (plot c). has a strong influence on phase development in
However, quench cooling of the composite shows nanocomposites15. Linkolm et al32 suggested that
a peak in the γ-phase, with virtually no evidence the addition of clay layers forces the amide groups
of the α-phase (plot d). These observations are well of PA-6 out of the plane formed by the chains. This
supported by subsequent studies by Wu et al28 on results in conformational changes to the chains,
PA-saponite nanoclay composites, where the clay which limits the formation of H-bonded sheets, so
addition changes the crystalline pattern of the the γ-phase is favoured.
nanocomposites. The addition of a small amount
(2.5 wt%) of clay to the PA matrix leads to two
The annealing process is thus an important factor
crystalline peaks at 20.5 and 24°, with no indication
controlling the phase transition in nanocomposites26.
of a γ-phase. However, during fast cooling of the
Fast cooling such as quenching leads to a different
same film, a γ-phase peak also arises.
X-ray diffraction behaviour for PA and PA
nanocomposites. The PA-6 sample quenched in
It is important to mention that the high saponite liquid nitrogen is amorphous (Figure 7a). Annealing
content (5 wt%) in PA-6 favoured a sharp γ- at 100°C induces crystallinity in the polymer and
crystalline peak and only traces of α-peaks during a diffraction peak appears at 2θ=21.8° which is
the fast and slow cooling of films. The authors contributed by the γ-crystalline peak of PA-6.
proposed that the higher saponite contents promote Subsequent annealing at 120°C introduces two
heterophase nucleation of the γ-phase. An important additional peaks at 2θ=20.3° and 23.7°, which are
finding of the study is that even the quenching of characteristic of α1 and α2, respectively. As the
the nanocomposites leads to a matrix with the same annealing temperature increases to 160 °C, the α-
crystallinity as pure PA. The polymorphic behaviour peaks become more visible and the γ-peak begins to

Figure 6. X-ray diffraction patterns of (a) α-phase PA-6; (b) γ-phase PA-6; (c) PA-6 nanocomposite is cooled down in
oil bath from 250 to 20 °C by natural convection; (d) PA-6 nanocomposite is removed from the 250°C oil bath and
quenched in a water bath at 20 °C; curves were vertically offset for clarity15

18 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

Figure 7. X-ray diffraction patterns of (a) PA-6 and Annealing produces isothermal crystallization,
(b) PA-6/clay nanocomposites annealed at different which has recently been investigated by Zhao et al25.
temperatures26 These authors showed that the overall crystallinity
increases as the crystallization temperature
(annealing temperature) increases (Figure 8). This is
essentially related to the segmental mobility, which
increases at higher temperatures. The variation in
crystallinity takes into consideration both the α and
γ-phases. Above all it was observed that there is a
gradual transition of the γ-phase to the α-phase in
pure PA-6. However, the addition of montmorillonite
to the PA-6 at various temperatures results in a
strong tendency of the PA-6 to crystallize, and the
α-peaks become dominant at higher annealing
temperatures.

2.3 Polymer/Clay Interactions

2.3.1 Clay Nature and Content
The nature of the clay plays a crucial role in structural
developments relating to PA-6 based materials.
Wu et al33 have carried out an interesting study
on nanocomposites based on montmorillonite and
saponite clays. In contrast to dioctahedral smectites
with predominantly octahedral substitution in
the montmorillonite, the saponite is composed of
trioctahedral smectites with mainly isomorphous
substitution of Si4+ by Al3+ in the tetrahedral sheets.
For this reason, the montmorillonite structure is in
the form of hexagonal lamellae, while the saponite
structure is in the form of ribbons and laths34. A
comparison of these two types of clay in PA-6 is
depicted in Figure 9.

decrease. With a subsequent increase in temperature PA-6 samples were prepared by hot pressing at
to 180 °C, the α-peaks become more prominent. 240 °C and then cooled down to room temperature
However, at 200 °C, α-peaks still dominate and the at 10 °C/min. As already mentioned in the previous
γ-peak becomes smaller. section, PA-6 contains multi-crystalline forms and
usually exhibits a more stable α-crystalline state in
In nanocomposites, the situation is a sharp contrast to the form of two α-crystalline peaks at 2θ=20.5 and 24°
that of PA-6. The quenched sample is still crystalline along with an additional distinct diffraction peak at
and characterized by a sharp γ-peak (Figure 7b). The 2θ=21.5° characteristic of the γ-phase (Figure 9, curve
annealing up to 140 °C still maintains the γ character. a). The amount of saponite clay plays a key role in
The two diffraction peaks arise when the annealing the structural development of the nanocomposites.
temperature is further enhanced to 160 °C and α- The addition of 2.5 wt% synthetic saponite to the
peaks become more prominent at the temperature of PA-6 matrix leads to a diffraction pattern with two
180 °C. However, the γ diffraction peak dominates α-crystalline peaks, without any indication of the
and at 200 °C an almost complete transformation γ-phase diffraction peak (curve b). As the saponite
of the α-form to the γ-form is evident. This is a content increases to 5 wt%, the X-ray diffraction
very interesting observation because the polymer pattern exhibits a sharp γ-crystalline peak and small
would undergo significant changes in crystalline traces of two α-crystalline peaks (curve c). However,
structure, depending on the processing temperature these diffraction patterns are very different from the
and the residence time at that temperature, during one obtained with montmorillonite clay. Here, the
moulding. X-ray diffraction pattern for 2.5 wt% clay content

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 19

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

Figure 8. Variation of crystallinity as a function of crystallisation temperature in PA-6/montmorillonite

nanocomposites25

Figure 9. X-ray diffraction scans for (a) PA-6, (b) 2.5 wt% saponite in PA-6/clay nanocomposites, (c) 5 wt% saponite in
PA-6/clay nanocomposites, (d) 2.5 wt% montmorillonite in PA-6/ clay nanocomposites and (e) 5 wt% montmorillonite
in PA-6/clay nanocomposites after being hot pressed into films and slowly cooled to room temperature33

shows only one sharp α-crystalline peak at 2θ=24° 2.3.2 Organo-Modification

and traces of another α-crystalline peak at 2θ=20.5°.
There is no γ-crystalline peak. However, as soon as Montmorillonite is hydrophilic, which makes
the montmorillonite content increases to 5 wt%, an exfoliation very difficult. Modification of the
additional γ-crystalline peak also appears at 2θ=21.5° clay with organic agents is therefore needed to
on the X-ray diffraction pattern. enlarge the interlayer spacing of the silicate sheets

20 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

and to introduce hydrophobicity, giving better PA-6 and may be reflected in the high mechanical
compatibility with the polyamide. strength of the nanocomposites.

The very first step in nanocomposites fabrication is Extensive X-ray diffraction studies have been
thus the hydrophobation of the clay. The sodium ions carried out to investigate structural changes arising
are replaced by alkyl ammonium salts by means of out of blending clay with PA-625,38. It has been
a cation exchange process. As a result, intercalation found that montmorillonite shows a well-defined
or delamination of the clay is achieved 35,36. diffraction pattern, as presented in Figure 1125. On
During the processing of nanocomposites, these organic modification of montmorillonite, the peak
montmorillonite silicate layers are exfoliated and shifts to lower value (4.6°). Once montmorillonite
are dispersed into the matrix homogeneously at the (10 wt%) is added to PA-6, the intercalated matrix
nanometre scale. Some of the organic substances used shows a diffraction peak shifting to a lower
to form organo-clays by ion exchange with sodium angle (2θ=1.85°). With a subsequent decrease in
montmorillonite are presented in Figure 1037. The montmorillonite content to 5%, the diffraction
ammonium ion usually has one or more alkyl “tails”, peak for montmorillonite disappeared completely,
formed from naturally occurring oils. These tails suggesting that the intercalated silicate layers are
have a low level of unsaturation. The other groups exfoliated into nanoscale layers and are randomly
on the nitrogen atom may be methyl, hydroxyethyl dispersed in the PA-6 matrix.
or benzyl, etc.
So the key task is not only to design these
Another amine, 12-aminodecanoic acid nanomaterials for various applications, but to monitor
(ADA), which is suitable for direct food contact structural changes within the matrix, which play a
applications, has been used as the surface crucial role in the ultimate product characteristics.
modifier in nanocomposite preparation by in-situ The modifying agent in montmorillonite can affect
polymerisation6. It is claimed that the additive offers the ultimate nanocomposite structure. Ma et al39
additional advantages in terms of the “tethering investigated the influence of organo-modification
effect”, which enables the nanoclay’s organically using n-dodecylamine, 12-aminolauric acid and
modified surface to link up with the polyamide 1,12-diaminodecane. Based on X-ray diffraction
chain during polymerisation. This is an attractive and differential scanning calorimetry (DSC), it
feature of the ADA additive, because this enhances was observed that these materials are intercalated
the compatibility of the montmorillonite with the into the nanocomposites and they influence the

Figure 10. Structure of some organic amines used to form organo-clay by ion exchange with sodium montmorillonite
(C = cocoa (C12), T = tallow (C18), R = rapeseed (C22))37

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 21

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

Figure 11. X-ray diffraction patterns for montmorillonite Figure 12. DSC second heating scans for (a) PA-6, (b)
(a), organically modified montmorillonite (b), PA-6/ 2.5 wt% saponite in PA-6/clay nanocomposites, (c) 5
montmorillonite 90/10 (c) and 95/5 (d)25 wt% saponite in PA-6/clay nanocomposites, (d) 2.5 wt%
montmorillonite in PA-6/ clay nanocomposites and (e)
5 wt% montmorillonite in PA-6/clay nanocomposites
after cooling from 300 °C to room temperature at 10 °C/
min33

As the amount of saponite increases to 5 wt%, the

DSC thermograms are altered. Two melting peaks
corresponding to the α and γ-crystalline forms appear.
However, the presence of 5 wt% montmorillonite in
crystallization process. The increase in clay content the nanocomposites still leads to a single melting
led to a decrease in the nanocomposite crystallinity, peak, corresponding to the α-crystalline form of PA-
perhaps because the clay inhibits chain mobility, as 6. These observations are in agreement with those
evident from the crystallinity decrease (from 35% from the X-ray diffraction patterns suggesting that
to 26%) observed when organo-clay was added. the saponite induces heterogeneous nucleation of
PA-6. Other research groups have, on the other hand,
The two phases of PA-6 are known to have different observed a single peak thermogram for virgin PA in
thermal histories, as the α-phase of PA-6 melts the DSC scan, comprising of the α-form. However,
at a higher temperature (221 °C) than the γ-form the addition of montmorillonite clay to the PA-6
(215 °C). Therefore, critical information regarding changes the melting pattern of the polymer42. These
the microstructure of nanocomposites may also be authors observed that the single melting peak of the
achieved from DSC investigations7,33,36, which can α-crystalline form at 221 °C was transformed into
quite often be correlated to the X-ray diffraction a dual peak endotherm where the predominant
patterns33. Variation in the structure of PA and its first peak at 213 °C and a smaller peak at 220 °C
nanocomposites has been reported by different correspond to the melting of the crystalline γ and
authors, which may be due to the large differences α-crystalline forms, respectively41,42.
in processing conditions40-42. DSC heating scans
of PA-6 and montmorillonite- and saponite-based
2.3.3 Compatibilisers
PA-6 nanocomposites are presented in Figure 12.
The virgin PA-6 has two melting peaks; the highest The interfacial adhesion between the clay surface
temperature peak corresponds to the α-crystalline and PA-6 is an important aspect of nanocomposite
form and the lowest to the γ-crystalline form. fabrication. The PA-6/clay nanocomposites (PA-6CN)
The addition of montmorillonite or saponite clay show some brittleness induced by the addition of filler
(2.5 wt%) to PA-6 leads to the elimination of the to the polymer. Therefore, a compatibiliser that would
low temperature peak and leaves behind only one be able to improve interfacial interaction between the
high temperature peak corresponding to the α-form. two components may be thought to lead to a final

22 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

product having the desired properties. Liu et al43 have 2.5 wt%. Interestingly, for the higher clay contents
investigated PA-6/clay nanocomposites containing of 5 and 7.5 wt%, the onset temperature remained
polypropylene-g-maleic anhydride (PP-g-MAH) as unchanged. It is supported by the studies of Liu et
the compatibiliser. Although those nanocomposites al45 who observed distinct clay agglomeration in
with a compatibiliser showed slightly lower tensile nanocomposites with high clay contents, whereas
strength and tensile modulus, the impact strength was a well-exfoliated structure was observed with
improved significantly and furthermore it increased 2.5 wt% clay.
with the compatibiliser content to as high as 30%.
As an example, it increased from 23 J/m with no It seems that morphological and interactive features
compatibiliser to 129 J/m for 30% compatibiliser in play a crucial role in the degradation behaviour
the nanocomposite (Table 2). of the nanocomposite. At low clay contents of
2.5 wt%, the nanocomposite exhibits an interactive
2.4 Thermal Degradation structure with an exfoliated matrix. At higher
contents, the clay undergoes agglomeration and
Thermal degradation during the processing of does not participate in homogeneous interactive
nanocomposites is a common problem. The bonding with PA-6. Studies of Kashiwagi et al46
polymer/clay nanocomposite preparation is have also shown that the thermal stability of PA-6
carried out at high temperatures, irrespective of nanocomposites does not differ much from that of
the fabrication route. If the processing temperature virgin PA-6. Using clay contents of 2 and 5 wt%,
is higher than the thermal stability of the organic hardly any appreciable change in the degradation
substances, decomposition of the constituent will behaviour was observed, except for a very little
take place. weight loss in the nanocomposite at a temperature
of about 350 °C. This could arise from the thermal
Thermogravimetric analysis (TGA) coupled with degradation of the organic component in the clay.
Fourier Transform Infrared Spectroscopy is a
powerful tool for investigating thermal degradation Forne et al47 have carried out an interesting study on
patterns44, which change completely after organo- the degradation of the polymer matrix during melt
modification of the clay. The major difference processing. An excellent review of the degradation
between the two configurations lies in the of alkyl ammonium montmorillonite organo-clay
temperature range of 200-500 °C, where the organo- has been made by Xie et al48. The thermogravimetric
clay undergoes maximum degradation whereas analysis (TGA) shows that the organic component of
virgin clay loses little weight. This suggests that the the organo-clay begins to break down at temperatures
organic components in the modified clay are highly as low as 180 °C in an inert atmosphere. This leads
vulnerable to thermal degradation. This needs to be to chemical changes in the additive, and may affect
considered during the processing of polyamides at the polymer melt intercalation and interfacial
elevated temperatures. The evolution of the cyclic bonding between the two components. It has been
monomer (caprolactam) and other volatile gases found that the extent of degradation depends on
like carbon dioxide or ammonia were observed in both the type of PA-6 and the nature of the organo-
these materials. However, the onset temperature clay49. High molecular weight PA-6 was found to
(for 5% weight loss) of the nanoclay composite experience more matrix degradation, as well as
was slightly enhanced to 404 °C compared with colour formation. The degradation stems from a
virgin PA (400 °C) but only for clay contents of chemical reaction between the organo-clay surface

Table 2. Properties of the PA6CN/PP-g-MAH alloys43

Properties of PA6CN/PP-g-MAH (wt:wt) = 100/0 90/10 80/20 70/30 0/100
Tensile strength (MPa) 88.60 85.06 81.51 74.42 22.83
Tensile modulus (GPa) 2.52 2.39 2.22 2.14 0.91
Flexural strength (MPa) 138.60 128.90 123.35 115.04 28.90
Flexural modulus (GPa) 2.87 2.67 2.58 2.41 0.74
Elongation at break (%) 36 66 101 122 230
Notched Izod impact strength (J/m) 23 61 90 129 49

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 23

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

and the polyamide. Therefore, any processing water that can also hydrolyse the polyamide at
that offers greater dispersion of the organo-clay in higher temperatures when processed. Davis et al50
the base polymer will lead to higher degradation. have observed that the melt processing of PA-6 at
This is believed to arise from increased exposure around 300 °C leads to significant degradation of the
of the organo-clay surface to the PA-6 as a result nanocomposites, attributed mainly to bound water or
of increased platelet exfoliation. The chemical to the dehydroxylation of the clay itself. Therefore,
nature of the organo-clay is extremely important nanocomposite degradation during processing
in introducing polymer degradation, depending can be envisaged the cumulative effect of thermal,
on the level of unsaturation present in the organic hydrolytic and induced decompositions.
component. The higher the number of double
bonds, the greater the degradation and the deeper
the colour formation. The molecular weight can 3. PROPERTIES AND APPLICATION
decrease significantly, sometimes as high as 32%. A AREAS
mechanism for clay degradation has been suggested Some of the most promising applications of
and is presented in Figure 1347. nanocomposites are currently found in the
automotive industry and in the deployment of
The alkyl ammonium organo-clay decomposes high thermo-mechanical behaviour polymers,
to produce α-olefins, amines and other products barrier films for the packaging industry and fire
where the elimination of the ammonium modifier resistant materials and textiles. There are also some
takes place by substitution with a H-atom on the interesting developments in medical products,
β-carbon. This mechanism has been supported by abrasion resistant materials and UV protection
Davis et al as well50. The organic part on the clay systems (Figure 14). Although the addition levels
is more destructive when it is based on natural are less than 10 wt%, for every 1 wt% addition,
products such as coco, which have long unsaturated a property improvement of about 10% is usually
chains. This organo-clay degradation seems to induced. This filler content to performance ratio is
be a regular feature, irrespective of the nature of known as the nano-effect18.
the base polymer, and has been observed in other
nanocomposites as well51. However, the degradation 3.1 Automotive Parts
can be minimised by using certain antioxidants. The
crucial properties, such as the mechanical strength, Nanocomposites made of polymers reinforced
are not much affected and colour formation in with exfoliated clay or carbon nanotubes are being
stabilised nanocomposites is almost the same as, or a considered for interior and exterior automotive
little less than it is in unstabilized nanocomposites. parts. Although most of the current automotive
Organo-clays contain a small amount of absorbed market involves PP nanocomposites, PA-6 ones

Figure 13. Proposed Hoffmann elimination reaction for organically modified montmorillonite (MMT)47

24 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

are slowly gaining acceptability in this sector. is increased by 100 °C in montmorillonite-based

Toyota opened up the use of nanocomposites in nanocomposites, whereas only a slight improvement
the automotive industry, and the resulting new is observed in the saponite-based nanocomposites.
materials are capable of achieving 40% higher tensile This confirms the essential role of the clay in the
strength, 68% higher tensile modulus, 60% higher structural development of the two nanocomposites.
flexural strength, 126% higher flexural modulus, Liu et al52 have reported a significant and sharp
than unfilled resins, while also having increased improvement (from 3 GPa to ~7 GPa) in the tensile
heat distortion temperatures (raised from 65 °C to modulus with the increase in clay content from zero
152 °C). The water permeability also decreases by up to 17 wt% (Figure 15).
40%13. These property improvements are attributed
to the fact that a significant volume of polymer
The mechanical deformation of PA-6 is controlled by
chains exfoliated clay lamellae, which have a high
its orientation and by the slippage of the crystalline
aspect ratio.
regions past each other along the plane53. It is still
an open question whether the crystallinity or
The advantages of PA-6/clay nanocomposites (2.5 or crystalline form developing during the processing
5 wt% clay) over virgin PA-6 are evident from Table 3. and fabrication of the nanocomposites has any
In general, montmorillonite-based nanocomposites influence over the mechanical properties of the
have slightly better mechanical strength and material. The crystallinity of the polymer changes
modulus than saponite-based nanocomposites. only marginally on the addition of clay to PA-
The major difference lies in the elongation. PA- 652. (It is only the polymorphism that changes in
6/saponite nanocomposites are characterised the nanocomposites). Earlier discussion in this
by elongations over 100%, whereas that of PA- paper reveals that the addition of clay leads to
6/montmorillonite nanocomposites is less than variations in the α- and γ-forms of the crystalline
10%. The heat distortion temperature of the matrix phase. However, the tensile modulus keeps on

Figure 14. Application areas of nanocomposites

Table 3. Mechanical and thermal properties of PA-6 and PA-6 nanocomposites33

PA-6 PA-6/montmorillonite PA-6/saponite
Clay content (wt%) 0 2.5 5 2.5 5
Tensile strength (MPa) 69 87 82 75 65
Tensile modulus (GPa) 1.1 4.48 5.85 3.38 3.8
Flexural modulus (GPa) 2.9 4.2 5.25 3.27 3.6
Notched Charpy impact strength (kJ/m2) 6.2 6.2 5.9 6.1 5.9
Heat distortion temperature (1775.5 MPa) 65 152 169 65 77
Elongation at break (%) >100 <10 <5 >100 >100

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 25

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

Figure 15. Effect of montmorillonite clay content on tensile modulus of PA-6 nanocomposites52

showing an improvement as the amount of clay Figure 16. Tensile stress vs. strain curves of the regular,
increases in the nanocomposites. It is therefore quenched and annealed PA6 and the regular PA6/
suggested that neither the overall crystallinity nor montmorillonite clay with strain scales: (a) enlarged for
the polymorphism has any influence on the tensile low strains and (b) complete curves40
strength improvements. It is the reinforcing effect
of the clay fillers that plays a key role in improving
the tensile strength of the nanocomposites. This
viewpoint is also strengthened by the studies of
Bureau et al40. These authors prepared various
samples by altering the processing conditions so
that specimens with different crystalline forms
and crystallinity levels were obtained. The
samples were quenched PA-6, annealed PA-6,
regular PA-6 and PA-6/clay nanocomposite (2 wt%
organo-clay montmorillonite intercalated with ω-
aminododecanoic acid). Surprisingly, neither the
quenched nor the annealed samples showed any
α-crystalline peak. The regular PA-6 had two peaks
at 20° and 24°, suggesting a high percentage of the
α-crystalline form, and the nanocomposite had peaks
for γ-phase as well. The tensile properties of these
materials are presented in Figure 16 and Table 4.
The quenched sample shows ductile behaviour
and undergoes very high deformation (670%) along
with significantly lower Young’s modulus and
yield stress. The annealing enhances the modulus
and reduces the elongation to 120% besides being
credited with a much higher level of crystallinity.
The regular sample shows a still higher modulus
but the yield stress is almost identical to that of the
annealed one. This means that the higher content of
the α-phase of the annealed sample does not alter
the tensile strength. The higher modulus therefore
is ascribed to the high crystallinity of the sample.

26 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

Table 4. Tensile test results for PA-6 and PA-6/ 2 wt% montmorillonite clay40
Materials Moulding Young’s Modulus Yield Stress Cold Drawing Strain at Break Crystallinity
conditions (GPa) (MPa) stress (MPa) (%) (%)
PA6 Quenched 2.4 ± 0.2 69 ± 2 32 ± 2 670 ± 60 7
Annealed 2.8 ± 0.1 91 ± 2 51 ± 2 120 ± 30 21
Regular 4.0 ± 0.3 93 ± 1 66 ± 2 140 ± 40 31
PA6/clay 4.7 ± 0.2 106 ± 3 - 3.0. ± 0.3 25

The nanoclay-based composite shows the highest chain carbonyl groups with the exfoliated clay
rigidity and its elongation also goes down to 3% in lamellae.
spite of lower crystallinity, indicating the reinforcing
effect of the nanofiller in the PA composite. The
Impact strength is an important characteristic of
contribution of boechmite clay as reinforcing agent
composites for laminated structures. The impact
in PA nanocomposites has been explored by Ozdilek
strength of nanocomposites remains similar to that
et al as well54.
of virgin PA-6 up to 5 wt% clay content (Table 3) and
thereafter tends to decrease significantly. At 20 wt%
Liu et al55 have also reported that the mechanical clay the material becomes very brittle19. The notched
properties are further improved if the montmorillonite Izod impact strength of PA-6 at different organo-clay
clay is co-intercalated with a quaternary ammonium contents is reported on Figure 17 as a function of
compound and an epoxy resin together. These temperature. As the temperature is increased to reach
authors explain that the exfoliation is much the PA-6 glass transition temperature region, a brittle
better in the epoxy containing organophilic clay, to ductile transition takes place. This brittle-ductile
which is associated with the strong interaction transition temperature is significantly enhanced by
between epoxy resin and amide end groups of the increase in clay content. Above the glass transition
PA-6. However, Shelley et al56 have noticed a temperature, the nanocomposites are super-tough,
200% increase in the tensile modulus and a 175% indicating high ductility. However, the advantages
improvement in yield stress in stretched sheets of in thermo-mechanical properties are still frequently
5 wt% clay nanocomposites, and have attributed overshadowed by the deteriorating impact behaviour.
these variations to the reinforcement of PA-6 by Clearly, this is an issue that requires consideration
clay particles, involving the complexation of mid- wherever resistance to impact loading is required.

Figure 17. Notched Izod impact strength of polyamide-6/organoclay nanocomposites as a function of temperature
and clay content (0 to 20 wt%)19

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 27

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

The above-mentioned results clearly show that recent 3.2 Barrier Layers in Packaging
developments in PA-6/clay nanocomposites have led
The major application focus of PA-6 nanocomposites
to improvements in short-term thermo-mechanical
today is in high barrier packaging. The plastic food
behaviour (tension, bending) with a relatively
packaging sector actually requires specific film
limited influence on impact behaviour. However,
characteristics. A great deal of attention is therefore
plastic parts are often subjected to long-term loading,
directed to nanocomposites that demonstrate
especially in the automotive industry. It is thus of
improved oxygen and carbon dioxide barrier
prime importance to pay attention to the static and
properties.
dynamic fatigue behaviour of the nanocomposites
as well. Bellemare et al57 have characterized the
effect of clay nanoparticles on the dynamic fatigue The gas permeability of a film is the product of the
crack initiation and propagation mechanisms and diffusion coefficient and of the solubility of gas
on the fatigue properties of PA-6/montmorillonite molecules within the polymer material. Adding
nanocomposites (fatigue life S-N curve measurement any kind of impermeable fillers improves the
and crack growth monitoring, based on fracture barrier properties of the materials. This effect is all
mechanics). Dispersing sheet-like inorganic the more pronounced when the fillers have a high
nanoparticles in a PA-6 matrix increases the dynamic aspect ratio that increases the effective diffusion
fatigue life of axial fatigue specimens subjected to a path length encountered by the gas molecules
given tension-tension stress amplitude, but decreases (increasing tortuosity) and thus reduces the diffusion
the fatigue life at a given strain amplitude. Therefore, coefficient (this effect is named “passive barrier
the effect of nanoparticles on the fatigue life appears effect”). The solubility decreases when the filler
to be similar to the one reported for inorganic fillers content increases, following a relation that depends
having dimensions in the microscale. This increase on orientation. The quality of the exfoliation and
in fatigue life at given stress amplitude is thought to the dispersion in the matrix are also key issues (the
be a consequence of an increase in intrinsic resistance existence of aggregates tends to overwhelm the
to crack initiation, as suggested by the tendency positive effect on permeability reduction).
of nanoparticles to increase Young’s modulus and
decrease the displacement amplitude during cycling.
That is why, with their very high aspect ratio,
On the other hand, compared with unfilled PA-6,
nanocomposites based on platy nano-fillers such
resistance of nanoclay filled PA-6 to fatigue crack
as clay show barrier performances much higher
propagation decreases, which is attributed to an
than those of micro-composites based on brittle
indirect effect of the nanoparticles’ tendency to
inorganic fillers such as mica. This means that it is
increase the yield stress, favouring the formation
possible to reach the same level of impermeability
of microvoids ahead the crack tip. These authors
with much lower filler contents. It is thus possible
conclude that most of the effect of nanoparticles
to divide by a factor of two the gas permeability for
on the fatigue behaviour probably results from the
2 wt% montmorillonite and by a factor of 10 for
mechanical reinforcement of the microstructure and
8 wt% montmorillonite. For example (Figure 18)
its effects on the yield stress and Young’s modulus,
Liang et al18 have used 12-aminododecanoic acid
rather than from the fact that the inorganic filler acts
modified montmorillonite in PA-6 composites and
as a stress concentrator.
they observed that the oxygen transmission rate
(OTR) at 65% RH falls by about 40% or 80% when
Finally, as far as under-the-hood automotive parts the clay content reaches 2 wt% or 8 wt%.
are considered, it is important to investigate the
influence of prolonged contact with automotive
The orientation of the clay particles within PA-6
fluids (such as oil, grease, and ethylene glycol)
matrix is important, and may influence certain
and pollutants (such as NOx) on the mechanical
properties of the nanocomposites. In particular,
properties and environmental stress cracking of
highly oriented particles may be more effective
the nanocomposites.
in improving the barrier properties. Using a
combination of FT-IR and Transmission Electron
Meanwhile, some concrete applications of PA-6/clay Microscopy (TEM), it was observed that the –NH
nanocomposites can already be found in automobiles bonds in nanocomposites are less preferentially
such as the Toyota timing-gear housing (raw material oriented along the plane of the film surface than
supplied by Ube) or the Mitsubishi Motors engine in the PA-6 films35.
hood (raw material from Unitika)9.

28 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

Figure 18. Oxygen transmission rate at 65% RH of PA-6/montmorillonite prepared by in situ polymerisation for
different clay contents18

OTR (cc-mil/100in2.day)
2.5
2.0
1.5
1.0
0.5
0.0
0 2 4 6 8 S1
Clay content (Nanomer 1.24TL) (%)

As far as commercially available materials further improvements in the barrier properties have
are concerned, a PA-6 based compound that been reported in the form of an "active-passive
incorporates organo-clay hybrids (2 to 8 wt%) by a barrier" system, with clay as the passive barrier and
compounding process has been developed for film a proprietary PA-6-specific oxygen scavenger as
and sheet extrusion (supplied by RTP). It is said to the active agent (supplied by Honeywell)58. Such a
exhibit properties as good as or better than those material is claimed to achieve a 100-fold reduction
of typical mineral-filled composites with 20-30%- in the oxygen transmission rate compared with
wt filler content. The significance of this product PA-6 (Figure 19). Following such characteristics,
lies in the four-fold improvement in the oxygen this active-passive barrier PA-6 nanocomposite
transmission rate over unmodified PA-63. Moreover, has been projected as the barrier system for beer
good transparency is achieved in the thermoformed storage58. One further step would be the development
structures, which is an important criterion for the of "active barriers", based on nanofillers modified
packaging industry when it is desirable to be able so as to interact with the various gas molecules
to view the packaged contents. considered.

Other PA-6 nanocomposites containing surface It is also worth mentioning the results obtained with
modified montmorillonite minerals (supplied by another polyamide challenging PA-6 (Figure 20)59.
Nanocor, a leading clay manufacturing company) This polyamide is produced by the polymerisation of
are commercially available from different suppliers
(Bayer and Honeywell)3. It is claimed that PA-6 with
2 wt% nanoclay has barrier properties three times Figure 19. Oxygen transmission rate at 80% RH of PA-6
better than those of PA-6 and 4 wt% nanoclay confers nanocomposites58
a six-fold improvement in the barrier properties.
Unmodified Nylon
Unfortunately, it is not possible at present to produce
2.0
barrier nanocomposites based on nano-platelets
OTR (cc-mil/100in3.day)

using the only tortuosity effect, that is to say with

80% RH
matrix materials which do not already exhibit 1.5
barrier properties on their own. This means that
nanocomposites cannot fully replace traditional
packaging solutions (such as multi-layer films) 1.0 Nylon-6
but they can enlarge the application areas of some nanocomposite
polymers.
0.5
While most of the past developments and current Active-passive Nylon-6
commercial materials are based on the above nanocomposite
0
mentioned “passive barrier” effect (tortuosity effect),

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 29

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

Figure 20. Chemical structure of the aromatic polyamide layered containers for beer, juice and single-served
N-MXD6 (Mitsubishi)59 carbonated soft drinks60. Such nanocomposites are
reported to exhibit three to six times the barrier to
oxygen and carbon dioxide of typical polyamides.
It is forecast that the market will rise to 1360 tonnes
in 2006 and 45310 tonnes by 2011 for soft drinks,
beer and food packaging61.

3.3 Flame Retardancy

In addition to their excellent thermal and mechanical
properties, nanocomposites also offer flame
m-xylenediamine and adipic acid, so that it results in retardant materials for construction, textile and wire
a resin with m-xylene units. The aromatisation of the or cable coating applications, especially when there
PA structure provides the matrix with considerable are constraints encouraging the use of a number of
changes in physical properties with respect to PA-6. traditional flame-retardants (such as brominated or
This aromatic polyamide (supplied by Mitsubishi) halogen-based additives)62. Nanocomposites show
has excellent gas barrier properties especially in high improvements in flammability over virgin polymers
humidity conditions. The polymer is a static barrier, and offer alternatives to ordinary flame-retardants
thereby offering a permanent barrier to all gases such in terms of their compatibility with the base matrix.
as oxygen, carbon dioxide and even hydrocarbon As the clay does not improve the decomposition
fuel vapour. The nanocomposites based on this temperature or reduce the decomposition rate
aromatic polyamide have already offered excellent of PA-6 in the nanocomposites, as observed by
materials for the barrier systems for bottles (made thermogravimetric analysis (TGA), the nanoclay
of blends with PET). The haze is similar to that of in the composite seems to follow the general
the un-reinforced material because of the good clay mechanisms of flame retardancy in polymers63. One
dispersion within the PA matrix. Comparative data mechanism is based on the char formation, which
on the nanocomposites and the virgin polyamide creates a protective barrier or an insulation layer, and
is presented in Table 559. The oxygen transmission hence reduces the heat release in the system64,65. This
rate (OTR) of the aromatic PA nanocomposite is far marked reduction in flammability results in self-
lower than that of regular PA for relative humidities extinguishing characteristics for the material. The
in the range 50-100%RH, and is in line with the radical trapping mechanism has also been postulated
tortuous path impedance concept. where radicals are trapped by paramagnetic iron in
the clay and helps in the improvement in the flame
Regarding concrete applications in the packaging resistance66. Globally, a decrease in the heat release
industry, ultra-high barrier PA-based nanocomposites rate (HRR) makes possible to assume a reduction in
have already been designed as the core layer in multi- the fire propagation rate. Moreover, the barrier effect

Table 5. Material properties of aromatic PA and aromatic PA/ nanocomposite cast films59
Property Units Aromatic PA Aromatic PA
(N-MXD6) nanocomposite (M9)
Density g/cm3 1.19 1.22
Glass transition temperature °C 85 85
Melting point °C 237 237
Haze % 1.4 1.5
Tensile strength MPa 85 83
Tensile elongation % 3.3 2.9
Tensile modulus GPa 3.1 3.5
OTR/23 °C , 60%RH * cc.mm/m2.day.atm 0.09 0.02
CO2TR/23 °C , 60%RH * cc.mm/m2.day.atm 0.30 0.15
WVTR/40 °C , 90%RH * g.mm/m2.day 1.36 0.58
* OTR, CO2TR, WVTR stand for oxygen, carbon dioxide, water vapour transmission rates respectively

30 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

brought by the nanofillers reduces the diffusion rate been pushed by numerous rising bubbles coming
of the gases resulting from decomposition within from the degradation products and associated with
the material. This means that the risk is limited the connective flow in the melt from the interior of
after the fire has begun. the sample towards the sample surface. It seems that
particles with large surface area or a large aspect
ratio tend to form a net like structure as compared to
The heat release has become an index to optimise
the particles with low surface area or a small aspect
the flammability characteristics of nanocomposites.
ratio46,69. This protective surface layer is also a barrier
Gilman et al67 have shown that a 63% reduction
against oxygen and is perfectly in correlation with
in the heat release rate of PA-6/montmorillonite
the observations in the flame retardancy mechanism
nanocomposites is achieved for a 5 wt% clay
for polypropylene/carbon nanotubes system70. Wang
content. These authors have observed a significant
et al38 investigated the flammability characteristics
difference in the ignition time, which is 40s for
of PA-6/clay hybrid using ammonium bearing long
intercalated nanocomposites compared with 80s
alkyl chains and observed that the nanocomposite
for the delaminated sample68. Studies of Kashiwagi
has a lower heat release rate peak and higher thermal
et al46 on the flammability characteristics of PA-6
stability than the unmodified PA-6.
nanocomposites have shown that it is indeed the
heat release rate of the nanocomposite that relates to
the flame resistance of the material. The reduction in Inorganic compounds such as magnesium hydroxide
heat release is obtained by the formation of protective (MH) and red phosphorus (RP) have been the
floccules on the sample surface, which shields the traditional fire retardant for polymers. However, a
PA-6 from the external thermal radiation and heat combination of such compounds with organoclay has
feedback from the flame, thus acting as a thermal been observed to provide a synergistic effect71. The
insulation layer (Figure 21). An analysis of the Limiting Oxygen Index (LOI) values of the different
protective floccules on the surface shows that up to PA-6 compositions are presented in Table 6. Virgin
80 wt% of the floccules consists of the clay particles. PA-6 has an LOI of 21, indicating its high flammability.
These authors propose that flame retardancy may The montmorillonite organoclay (OMT) modification
be due to a combination of two factors. The first is led to a slight improvement in the LOI. However, the
the recession of the polymer resin from the surface combination of MH and the RP with OMT enhances the
by pyrolysis with de-wetted clay particles, which LOI to 31 from the 29 obtained with MH and RP alone.
subsequently tend to aggregate and stack against It has been proposed that the thermal decomposition
each other. Secondly, the clay particles may have of montmorillonite at around 200 °C leads to protons

Figure 21. Effects of montmorillonite clay content on heat release rate of PA-6 (8 mm thick) at 50 kW/m2 46

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 31

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

Table 6. Tensile strength and LOI values of the PA-6 multi-filaments, using a two-step process that leads
and PA-6/montmorillonite clay nanocomposites71 to the yarn with 80 trilobal continuous filaments of
approximately 2000 dtex. The subsequent knitting
Composition Tensile LOI
Strength of the multi-filaments led to a fabric that showed
(MPa) 40% reduction in heat release rate relative to the
Neat PA-6 80.5 21 virgin PA-6. The char appearance was also quite
uniform in the nanocomposites, in contrast to the
PA-6 + OMT 2% 103.4 21.5
porous structure in PA-6. These investigations are
PA-6 + MH 8wt% + RP 5wt% 71.1 29
supportive of other studies carried out by different
PA-6 + OMT 2wt% + MH 98.2 31 authors42. Measuring the smoke release, CO and
8wt% + RP 5wt%
CO2 evolution, it has been observed that the PA-
OMT = montmorillonite organo-clay 6/nanocomposite evolves smoke with a peak at
MH = magnesium hydroxide
0.012 m3/s (and a flat plateau between 75 and 200s)
RP = red phosphorus
whereas PA-6 evolves smokes at 0.018 m3/s (peak
at 180s) as observed in Figure 22. The quantity
of smoke evolved, in terms of volume of smoke
production (VSP) peak, is lower than that of pure
that promote the endothermic decomposition of MH: PA-6. Although these investigations show a bright
(Mg(OH)2 → MgO + H2O). At the same time, the silicate future for the textile industry, a more optimistic
layers of montmorillonite retard the release of water approach is needed.
vapour from the decomposition of MH. The water
vapour and the acid accelerate the decomposition
Regarding commercially available materials, flame
of RP and then lead to the formation of highly
retardant formulations have been developed for the
crosslinked polyphosphoric acid derivatives in the
wire and cable applications using platy synthetic
flame. At the same time, the decomposition products
silicates (Dow Wire and Cable Compounds). Tests
of these additives form a glassy coating and behave
have revealed that this material provides flame
as insulators, thereby enhancing the flame resistance
and mechanical properties comparable to those
of the material.
obtained with the mineral montmorillonite3. A line
of organo-clay products for polymer nanocomposites
The scenario with the flame retardant textile (Nanofil®, Süd-Chemie) also offers flame resistance
materials has been different because the additives properties that delay ignition, reduce smoke
must be stable against repeated washing operations. emissions and eliminate dripping of the molten
Bourbigot et al72 have carried out a study of PA-6/ polymer by the formation of a strong and stable
montmorillonite nanocomposite textiles by melt char. Inan et al73 also agree with these observations,
spinning the nanocomposite and then drawing the as a 58% lower peak heat release rate was observed

Figure 22. Volume of smoke production (VSP) curves of PA-6/montmorillonite fabrics at 35 kW/m2 72

32 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

in a nanocomposite compared with the pure PA-6. from being porous to dense and non-ionic to the ion
This strengthens the view that a nanocomposite exchange type. Membranes are becoming important
char helps in reducing the heating rates of the in the separation of gases and liquid mixtures by
underlining material. Both clays (saponite and reverse osmosis and pervaporation, offering a highly
montmorillonite) showed identical behaviour, but energy-efficient alternative to the conventional
laponite showed an 11% lower peak heat release separation methods. Pervaporation in particular
rate than montmorillonite74. has been effective for the separation of azeotropic
compositions and temperature sensitive mixtures75.
In this process, the liquid permeates across the
As for barrier performances, despite all those
membrane under the driving force of low pressure
very positive effects and a slow burning rate, the
on the downstream side. This is where the separation
above nanocomposites are not able to pass UL
factor becomes very important in establishing the
(Underwriter’s Laboratories) furnace tests yet. Their
performance of the membrane.
whole surface burns, to very limited depth, before
they extinguish. Nanofillers alone are therefore
not sufficient to avoid flammability. However, The critical requirements for separation are the nature
their association with traditional flame retardant of the membrane, its permeability and its selectivity.
additives enables them to improve their flame This is where the separation factor of membranes in
retardancy and UL test classification, while reducing a system becomes very important. Wang et al76 have
the global demand for flame-retardants. separated a water-ethanol mixture by pervaporation
using polyamide/clay nanocomposite membranes.
The nanocomposites were prepared by direct
3.4 Membranes polycondensation of 4,4’-methylenedianiline and
Membranes also constitute a very interesting 4,4’-hexafluoro isopropylidenedibenzoic acid in
aspect of polymer technology. A membrane is a the presence of organo-modified montmorillonite.
thin interface, which allows selective transport of a The clay was modified by sodiumdodecylsulphate
component across its matrix from a mixture of two (SDS). The clay content affects the pervaporation
or more components. The application domains of performance for a 90 wt% ethanol aqueous solution
membranes are numerous, such as microfiltration, through the polyamide/SDS-clay nanocomposite
ultrafiltration, electrodialysis, dialysis, and fuel membranes (Figure 23). The clay content influences
cells. Therefore the nature of membranes varies the pervaporation performance of the membranes.

Figure 23. Effect of montmorillonite clay content on pervaporation performance of polyamide/SDS-clay nanocomposite
membrane: (•) permeation rate; (o) separation rate. Feed solution: 90 wt% ethanol aqueous solution; Feed solution
temperature: 25 °C76

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 33

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

The permeation rate decreases and the separation regions remain inaccessible to the dye molecules
factor increases as 2 wt% clay is added in the and it is the amorphous region that contributes
membrane. However, the separation factor decreases to the dye diffusion and its interaction with the
sharply when the clay content increases beyond ionic sites within the polymer. Recent studies have
2%. It seems that it is the structural development shown that nanocomposite filaments can be dyed
in the membranes with increasing clay content that with different classes of dyes such as acidic dyes,
plays a significant role in the permeation kinetics. complex dyes and disperse dyes79. The dyeing with
The microphase separation takes place during the acidic and metal complex dyes is the result of the
membrane fabrication process beyond 2 wt%. At interaction between the amino group and the dye
the same time, there is a strong adverse effect of clay molecules. However, disperse dyeing is related to
content on the membrane swelling, and this may be the amorphous volume within the monofilament,
instrumental in producing the observed behaviour without any consideration of the ionic content
of the membrane in the system. within the filament. Experience shows that the
dyeing of nanocomposite filaments with acidic dyes
shows a significantly lower initial rate of dyeing than
3.5 Textiles the one that can be achieved with virgin PA-6 ones
Finally, nanocomposites have been getting (Figure 24). These observations are related to the
enormous attention in the area of textiles as well. blocking of amino groups by the montmorillonite
It is not only the development of the filament but ion exchangers79. However, the contributions of the
also the subsequent processes such as mechanical
and chemical processing that are an integral part
of material development. The use of nanoclay in
PA-6 leads to several interesting characteristics, Figure 24. Kinetic study of the dyeing of PA6 and PA6/
as discussed in the previous sections, where high montmorillonite nanocomposite. (a) Acid dye, (b) 2:1
strength retention and flame resistance are the key metal complex dye and (c) disperse dye79
gains of the nanocomposites. The most obvious
requirement of textiles is mechanical strength and
dyeability with existing classes of dyes. Although
PA-6 filaments have been prepared commercially
by the traditional route of melt spinning, wet
spinning has also been used by some authors77.
Electrospinning is the most recent development
and innovative process. It has been used to produce
nanofibres based on PA-6 and montmorillonite.
This opens up a floodgate for the construction of
nanoscale objects from the PA nanocomposites.
The most appropriate development has been the
construction of a non-woven fabric from these
nanofibres where the fibre diameter varies in
the range 100-500 microns. In the melt spinning
process, it has been observed that the physical
properties of the fibres are strongly influenced by the
spinning temperature, take up speed and drawing
conditions78. The post-spinning processing is carried
out in such a way that the required orientation and
the crystallinity are achieved in the filaments.

The commercial dyeing of PA-6 is carried out with

acidic dyes. In that case the anionic dye is ionically
bonded to the protonated amino (-NH2) groups.
However, the dyeing chemistry would be expected to
change significantly once the PA-6 is blended with
the clay to produce nanocomposite filament. Both the
fibre orientation and the crystallinity significantly
affect the dyeability of the fibre. The crystalline

34 Polymers & Polymer Composites, Vol. 14, No. 1, 2006

 Polyamide-6/Clay Nanocomposites: A Critical Review

matrix rigidity and the mobility of chains, which almost the same as with the virgin polymers
would influence the diffusion coefficient of the dye while the gas barrier property is enhanced a
within the filament, need to be considered. Here lot because of the tortuosity effect brought
one can draw some conclusions from the enhanced by the addition of nano-platelets acting as
barrier properties of the nanocomposites. The a passive barrier. The challenge in this area
permeability and hence diffusivity of a permeant would be to develop real active barriers based
is significantly reduced by a tortuous pathway and on nanofillers modified so as to interact with
the same should hold truth when the dye diffusion gas molecules.
across the fibre matrix takes place prior to its binding • In textiles, where dyeability is an important
with ionic sites. This study opens up an interesting issue for the commercialisation of fibres, it has
area where non-traditional disperse dyeability can been shown that the filament produced from
be achieved in these fibres. the PA/clay nanocomposites can be dyed with
different classes of dyes such as acidic, metal
4. CONCLUSIONS AND OUTLOOK complex and disperse dyes. This opens up
significant prospects for these fibres to be used
Nanocomposites are gradually gaining wide in combination with other fibres so that the
acceptance in the mainstream of global plastics dyeing can be achieved in a single dye bath.
processing, and are being promoted as the way of the
future. The production of these nanomaterials with There are also several other areas where
particles measuring tens of a nanometre has almost nanocomposites could be of interest, such as in
revolutionised the plastic industry with respect to protection against radiation, or conducting materials
its production and applications. Among the various for electronic parts. The improved mechanical
nanomaterials that are currently being developed, strength also makes it possible to visualize several
the polyamide/clay nanocomposites have already other applications in medical technology and
proved their great potential in automotive parts, biomaterials. The rehabilitation of a patient, or
barrier layers for packaging industry and flame artificial organ support using these high strength
retardant materials. Using clay nanoparticles in nanocomposites, would certainly replace the
PA matrix composite materials enhance their currently available heavy structures made out
mechanical performances, and therefore reduces of steel. Even surgeons may think of using these
the part weight, while increasing their chemical and nanocomposite plates instead of steel plates for
heat resistance and change their interaction with orthopaedic surgeries. These application areas still
gas, light and radiation. One of their most attractive need to be investigated.
features is that these materials acquire their desired
characteristics with a much lower filler content (2-6
wt%) than when using the conventional fillers. The Nevertheless the low number of effective
big applications are coming slowly because of the applications and the fact that acceptance of
need to validate cost-effectiveness: nanocomposites has been relatively slow up to
now confirms that the promise of a dream material
for the 21st century still needs to be fulfilled. The
• Apart from heat and mechanical resistance key issue for making nanocomposite technology
for under-the-hood applications, the current broadly useful is to understand how to select
challenging automotive applications are anti- elaboration routes, materials and processing
scratch and anti-mist coatings, as well as surface conditions that achieve optimum performance
enhancement for both internal and appearance
for specific systems. Further research is therefore
parts, and external parts (such as body panels).
necessary to develop a proper understanding of
• The fabrication of flame retardant polymers
the formulation/structure/property relationship in
and textiles based on nanoclay fillers is also
polymer nanocomposites.
an extremely interesting area where significant
success has been reported. The flame
retardancy is achieved without sacrificing ACKNOWLEDGEMENT
the tensile strength of polymers, contrary
to traditional blending operations using The authors wish to acknowledge the financial
commercial standard chemicals. assistance of Conseil Régional Nord-Pas-de-Calais,
• The development of barrier films for France to Bhuvanesh Gupta, for carrying out the
packaging is another attraction of PA/clay present work at Ecole des Mines de Douai. Thanks
nanocomposites, where the clarity remains are also due to E.U. (Feder).

Polymers & Polymer Composites, Vol. 14, No. 1, 2006 35

 Bhuvanesh Gupta, Marie-France Lacrampe and Patricia Krawczak

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