Professional Documents
Culture Documents
Nanocomposites, Polymer-Clay
Nanocomposites, Polymer-Clay
POLYMERCLAY
Introduction
Polymer matrix nanocomposites are a fairly new class of engineered materials
which offer for a broad range of properties, an interesting and even radical alternative to more conventional lled polymers, yet at much lower ller loadings.
They can be dened as polymer matrix systems in which the dispersed inorganic
reinforcing phase has at least one of its dimensions in the nanometer range, which
is quite close to the scale of elementary phenomena at the molecular level. The
resulting unique combination of large interfacial area and small interparticle distance strongly inuences nanocomposite behavior.
Current status of research and industrial development of polymer nanocomposites clearly outlines the prominent position of clay nanocomposites and the
present review is mainly devoted to the latter materials.
From a general point of view, ller aspect ratio is a pertinent parameter to
distinguish between various types of nanocomposites. Table 1 summarizes typical dimensions of particles under concern. Spherical silica particles are an example of isotropic nanoparticles which either provide increased composite stiffness while retaining matrix transparency, or exhibit novel optical properties by
forming colloidal crystals. Although it is obviously critical to the optical behavior, it is generally observed that optimum mechanical properties are not achieved
in conjunction with the best state of dispersion (1). When only two dimensions
are in the nanometer range, ber-like structures, such as whiskers or carbon
nanotubes, with aspect ratios ranging between 50 and 1000 are dealt with. For
instance, cellulose whiskers extracted from tunicate shells have been shown to
dramatically improve composite stiffness in the case of poly(vinyl chloride) or
336
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
337
Shape
Typical dimensions
Silica particles
Cellulose whiskers
Carbon nanotubes
Layered silicates
Spheres
Rigid rods
Flexible tubes (multiwall)
Flexible discs
Diameter: 30150 nm
Diameter: 15 nm; length: 1 m
Diameter: 30 nm; length: 1050 m
Diameter: 50500 nm; thickness: 1 nm
338
NANOCOMPOSITES, POLYMERCLAY
Al or Mg;
Vol. 3
OH; O;
exchangeable cations.
the layer. Stacking of the layers leads to a regular van der Waals gap called
gallery or interlayer. Cations located in the galleries (eg Ca2+ , Na+ ) counterbalance the excess layer charges. They are usually hydrated. This negative surface
charge is quantied as the cation-exchange capacity (CEC), usually in the range
from 80 to 150 meq/100 g for smectites. The interlayer space can be penetrated
by organic cations or polar organic liquids as well. Exchange reactions with organic cations (aminoacids, alkylammonium ions, etc) enable to render the silicate
surface organophilic. A key parameter of the stacking is the basal spacing or
d-spacing, which ranges from 0.96 nm (ie, the layer thickness) in the fully collapsed state to about 2 nm, depending on the nature of the interlayer cation and
the amount of adsorbed water (7). Individual lamellae have a high aspect ratio,
with a diameter typically in the range 50500 nm. Primary crystals (also called
tactoids) consist of 810 lamellae, with usually disordered stacking. Their aggregation leads to a turbostratic structure. This organization is reected in the x-ray
diffraction (xrd) pattern where diffuse hk bands rather than sharp hkl reections
are observed. The basal reection (001) is of more interest since it is used to derive the d-spacing. It will be dependent on the amount and nature of intercalated
molecules in the galleries.
Characterization of Nanocomposite Microstructure. Mixing clay
with a polymer does not necessarily lead to a nanocomposite. Elaboration strategies are aimed at monitoring dispersion of the inorganic compound at the nanometer level, that is down to the elementary clay platelet. Figure 2 provides a
schematic illustration of the various microstructures readily achievable, namely
a conventional lled polymer with clay particles in the micrometer range, an
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
(a)
339
(b)
(c)
Fig. 2. Schematic representation of clay platelet dispersion as (a) primary crystals, (b)
intercalated, or (c) exfoliated structures.
340
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
II
6.0 nm
6.3 nm
(d)
5.0 nm
Intensity, a.u.
(c)
3.4 nm
Intensity, a.u.
(d)
5.7 nm
(c)
3.5 nm
(b)
(b)
2.1 nm
2.1 nm
(a)
0.5
3.5
5
6.5
2 -Cu, deg
9.5
(a)
0.5
3.5
5
6.5
2 -Cu, deg
9.5
oligomer (PP-MA). As the amount of the latter component is increased, the interlayer distance increases drastically (spectra Iad), indicating the efciency of the
intercalation process. Spectrum IIa reveals the lack of intercalation of C18 Mt by
pure PP. Spectra IIbd do not show any change in the state of intercalation assessed in Spectra I when the PP-MA intercalated organoclay is further dipersed
in a PP matrix. It is concluded that PP penetration in the galleries is not favored
in this particular case (9).
Whenever the xrd pattern becomes silent, meaning that the interlayer spacing is no longer accessible by conventional wide-angle x-ray diffraction, the need
still remains to have access to a mesoscale description of the spatial distribution
of the clay platelets. Small-angle x-ray scattering may provide some answers regarding average interparticle distance, and also about platelet orientation with
respect to process geometry (10).
Transmission electron microscopy has the great advantage to give a direct view of the microstructure. Typical micrographs reveal alternating dark and
bright bands refering to the silicate layers and polymer matrix respectively. The
illustrations of Figure 4 show exfoliated and intercalated-exfoliated structures in
the case of 1 and 5 mass% dimethylditallow ammonium-modied montmorillonite
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
500 nm
341
200 nm
100 nm
342
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
343
Intercalation in Solution. In the case of water-soluble polymers, it is possible to prepare solvent-cast nanocomposites by using water as a cosolvent. Pristine montmorillonite can be easily dispersed in water, owing to its hydrophilic character, and blending for instance with polymers such as poly(ethylene oxide) (PEO)
or poly(vinyl alcohol) (PVOH) is thus achievable (see eg (2426)). Intercalated
exfoliated structures are observed for PVOH-based nanocomposites. On the contrary, in the presence of PEO, intercalated silicate layers are organized as large
clay tactoids; this indicates that reaggregation of the initial silicate water suspension occurred during the lm casting process. A similar elaboration strategy
has also been developed, starting from an organoclay. In the examples of poly(caprolactone) and poly(l-lactide), chloroform was used as a cosolvent. In both situations no evidence of intercalation could be found but the clay tactoids displayed a
remarkable geometric arrangement, with their surfaces lying parallel to the cast
lm surface (27). These few illustrations are indicative of the high sensitivity of
the nal materials structure to the nature of the host matrix and to the interplay
of polymerpolymer and polymerclay interactions.
The above technique can be advantageously adapted to a situation where
the polymer of interest is not soluble in any solvent, as is the case for polyimides.
The polyimide precursor, ie, a poly(amic acid) solution in dimethylacetamide, is
prepared and blended to a dispersion of an organomodied montmorillonite in the
same solvent. Dimethylacetamide is then gradually removed, and upon heating
the poly(amic acid) lm at 300 C under nitrogen atmosphere the polyimideclay
hybrid is obtained. When an ammonium salt of dodecylamine is used in the ionexchange process, true exfoliation is achieved and furthermore the clay platelets
align parallel to the lm surface (28).
Emulsion Polymerization. Considering the high hydrophilic character
of sodium montmorillonite, it was anticipated that polymerization in an aqueous medium might provide an alternative route for polymerclay nanocomposite
preparation. The rst report dealing with such an approach concerned the emulsion polymerization of MMA dispersed in a water phase in the presence of Na+ montmorillonite. The structural analysis conrms intercalation of the PMMA in
the clay galleries. A PSclay nanocomposite has been elaborated according to the
same procedure, with the same resulting intercalated morphology. Intercalation
by the emulsion technique was also achieved for an epoxy system, again without
requiring any ion-exchange treatment (29).
Melt Intercalation. Although emulsion polymerization or in situ polymerization may be considered as viable routes for industrial-scale production, as exemplied for PA6 with the latter process, melt compounding remains the most
obvious route for cost-effective development of nanoreinforced polymers. The rst
industrial applications refer to the PA6clay hybrid in situ polymerization process
patented by Toyota (30), but growing interest in achieving clay nanodispersion by
melt compounding is observed worldwide (31). Patent literature is clearly indicative of the current trend with many references to polyamides and other polar
polymers such as polyesters or polyimides [see eg (32)]. Emphasis is put on the
nature of the surfactant and processing conditions. Nonpolar polymers such as
polyolens are also highly attractive candidates with research efforts primarily
driven by the automotive market. Polypropyleneclay hybrids have been prepared
by melt mixing an organoclay, maleic anhydride-modied PP oligomers (PP-MA),
344
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
and PP. The polar PP-MA intercalates in the clay galleries and the quality of clay
dispersion in the hybrids are clearly affected by the degree of miscibility of the
polar oligomers in PP (9,33).
Direct melt intercalation of PEO in pristine montmorillonite by static annealing of cold-pressed powder mixture slightly above the melting temperature of PEO
has been reported (34). The resulting d-spacing of the order of 1.8 nm indicates
that the PEO chains are constrained in a 0.8-nm interlayer space. Differential
scanning calorimetry studies reveal that the polymer is deprived of any thermodynamic transition. Neither the heat capacity jump characteristic of the glass
transition nor the melting endotherm is observed. Chain dynamics appear quite
peculiar in these systems. Thermally stimulated current results point at the essentially noncooperative nature of the motions of the conned chains. Intercalation
kinetics have also been followed by xrd monitoring of the basal spacing reection
in model systems consisting of monodisperse PS and organically modied uorohectorite. The most striking result is that the mobility of the polymer chains
in this conned environment seems larger than that in the bulk melt (34,35).
Spin-echo nmr experiments using deuterated PS suggest the coexistence of multiple environments, from solid-like to liquid-like, for intercalated chains. Molecular
dynamics simulations relate this complex dynamic behavior to strong density inhomogeneity normal to the surface [(36), and Refs. 45 to 49 therein].
An extensive investigation of nanocomposite preparation with the aid of a
swelling agent that is known to intercalate the clay provides some additional
interesting experimental ground on the phase behavior. The results underline
the inuence of the polymer/swelling agent miscibility (as assessed by a solubility parameter approach) on nanocomposite formation. The example of an epoxy
monomer as the swelling agent shows that either complete miscibility or strong
immiscibility are preferable (37).
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
345
some trends regarding phase morphology and stability for these systems. In particular, the calculations point at the key inuence of the surfactant chain length.
Polymer-like values lead to enhanced miscibility of the clay platelets and polymer
matrix (exfoliated structure), even at moderate level of interactions between the
grafted chains and polymer melt (39). The equilibrium behavior of a mixture of
functionalized and nonfunctionalized chains (taken chemically identical) in the
presence of two innite planar surfaces has alternatively been considered using
scaling theory. Functionalized chains have a telechelic architecture; ie, the active
groups are located at each end of the chain. Qualitative phase diagrams are derived with prime consideration of the respective inuences of interaction energy
between the surface and the end group, and volume fraction of functionalized
chains. Provided the interaction energy is high enough, exfoliation occurs more
easily as is increased, whereas low values result in an immiscible mixture
(40).
Nanocomposites Behavior
Thermal Stability. Thermal stability improvement was already recognized in the pioneering work by Blumstein on PMMA intercalated in
montmorillonite. Intercalated PMMA degraded at a temperature 50 C higher
than that of conventional unlled PMMA. In recent years, thermogravimetric
analysis of various polymerclay systems have conrmed this observation even
for low nanoller loadings [see eg (13,41), and references therein]. A particularly
striking example is that of cross-linked poly(dimethylsiloxane) incorporating 10
mass% exfoliated organomontmorillonite (42) for which thermal stability under
nitrogen ow is enhanced by 140 C. Overall, restricted thermal motion in silicate
interlayers and hindering of the diffusion of decomposition products are certainly
key factors, but polymer structure and nature of the degradation mechanisms
and degradation conditions are equally important to account for the disparities
observed in literature.
Owing to what has been said previously on the role of the organic modier of the layered silicate in elaboration and phase behavior of the polymerclay
nanocomposites, understanding of the key structural factors that inuence its
thermal degradation is of prime importance. Major concern is of course toward
processing conditions and re-retardant behavior as well. Recent work (43) on
alkyl quaternary ammonium montmorillonite by a combination of thermogravimetric analysis, Fourier transform infrared spectroscopy, and mass spectrometry
points at the complex degradation behavior of the organic surfactant. The initial
degradation temperature is insensitive to chain architecture and length, or exchange ratio. Compared to the parent alkyl ammonium, the thermal stability of
a fraction of the surfactant is substantially lowered because of catalytic sites on
the layered silicates. Polymer processing generally implying temperatures higher
than 180 C, chemical degradation of the surfactant is expected to occur. Many
questions remain regarding the role of the decomposition products on the melt
intercalation mechanism and subsequent nanocomposite phase stability. In this
respect the potential of nmr techniques to follow the fate of the organic modier
seems quite promising (44).
346
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
347
Nylon-6
Nylon-6clay 2%
delaminated
Nylon-6clay 5%
delaminated
PS
PSclay mix 3%
immiscible
PSclay 3%
intercalated
PP-g-MA
PP-g-MAclay 5%
intercalated
a After
Residue
yield,
%
Peak
HRR,
kW/m2
Mean
HRR,
kW/m2
Mean
Hc,
MJ/kg
Total
heat
released,
MJ/m2
Mean
SEA,
m2 /kg
Mean
CO
yield,
kg/kg
1.0
3.0
1011
686
603
390
27
27
413
406
197
271
0.01
0.01
5.7
378
304
27
397
296
0.02
0
3.2
1118
1080
703
715
29
29
102
96
1464
1836
0.09
0.09
3.7
567
444
27
89
1727
0.08
0
8.0
2028
922
861
651
38
37
219
179
756
994
0.04
0.05
Ref. 48.
1400
1200
1000
800
600
400
200
0
0
50
100
150
Time, s
200
250
300
Fig. 6. Kinetics of heat release rate for PS-based compounds. Reproduced from Ref. 48.
PS pure;
PS immiscible (3% silicate); PS intercalated (3% silicate).
348
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
enough of enhanced char formation and reduced mass loss rate in comparison to
pure PA6. The current interpretation of these results is that the nanocomposite
ame-retardant mechanism occurs through the build up of a reinforced char layer,
which acts as an insulator, and a mass transport barrier so as to slow down the
escape of the decomposition products. Developments according to this concept include the use of a PA6clay nanocomposite in intumescent formulations as in the
case of ethylenevinyl acetate copolymers with ammonium polyphosphate (50).
Enhanced ame-retardant performance is related to the formation of a thermally
stable phosphocarbonaceous structure in the char, and the blend even shows a
slight improvement in mechanical behavior.
Processing conditions also strongly inuence the ame-retardant behavior.
For example, in the case of PS-based nanocomposites, extrusion above 180 C under
partially oxidative conditions yields an intercalated nanocomposite but with no
ammability improvement, whereas the melt-extruded system at 170 C under
nitrogen or vacuum exhibits ame-retardant efciency (41). The way thermal
degradation of the organic modier alters the ammability reduction mechanism
has yet to be understood.
Barrier Properties. Early work in the Toyota Research group acknowledged the great potential of polymerclay nanocomposites to reduce moisture
absorption and decrease water and gas permeability, even at low clay loadings
(6). A further advantage for packaging applications lies in the fact that lowering
of permeability is achieved while preserving transparency, owing to the suitable
dispersion of platelets smaller than the wavelength of visible light.
The example of polyimide clay lms illustrates the dramatic decrease of
permeability coefcients. Only 2 mass% montmorillonite loading reduces the permeability by more than 50% of the pure polymer value for water vapor, oxygen,
or helium. Notwithstanding possible changes in diffusion and/or solubility, it has
been postulated that the major role of the clay platelets consists in substantially
increasing the path length of the permeant, that is by creating a highly tortuous
path, due to the high aspect ratio of the clay. A simple theory derived by Nielsen
expresses the relative permeability as follows:
Pc /Po = 1/[1+(L/2W)Vf ]
in which V f is the volume fraction of plates, L is the plate length, and W is the
thickness. Pc and Po stand for the nanocomposite and polymer permeability respectively.
Using equivalent loadings of clay but varying the aspect ratio yields results in
fairly good agreement with the theoretical prediction (28). In the same way, a signicant reduction in water vapor permeability was observed in the case of a poly(caprolactone)organomontmorillonite nanocomposite, showing a vefold reduction at only 4.8 vol% clay whereas it is only halved at best with a 20 vol% conventionally lled silicate composite (20). The tortuosity model shows discrepancies between actual aspect ratios measured by tem and values deduced from curve tting.
Among the reasons for that are the deviations from the ideal dispersion of platelets
parallel to the lm surface, and possible aggregation of individual platelets.
Although tortuosity plays a role in barrier enhancement, some other factors
ought to be taken into account (see BARRIER POLYMERS). Recent work on MXD6
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
349
PA6
97
32
1.9
0.6
69
27
1.1
0.2
143
33
89
12
4.3
1.2
18
6.1
152
2.0
0.3
21
6.2
65
a After
Ref. 5.
convert MPa to psi, multiply by 145.
c To convert GPa to psi, multiply by 145,000.
d To convert J/m to ftlbf/in., divide by 53.38.
e To convert kJ/m2 to ftlbf/in.2 , divide by 2.4.
b To
nanocomposites is indicative of an oxygen permeation reduction in humid environment far beyond what is expected from the increase in path length alone (51).
In the light of the ndings regarding chain packing and dynamics in such conned environments (36), models for the prediction of barrier properties ought to
take into account the changes induced in terms of solubility and diffusion. A conceptual model has been proposed (52). So far no general predictive approach is
available.
Mechanical Behavior. Being able to improve strength and stiffness with
limited alteration of toughness is a goal readily achievable with polymerclay
nanocomposites (see MECHANICAL PROPERTIES; REINFORCEMENT).
Table 3 gathers some key data of the original work by the Toyota group (5),
which show the dramatic inuence of organomontmorillonite on mechanical properties of PA6clay hybrids at low mineral loading (4.7 mass%). The improvement
in strength is claimed to have little or no inuence on impact properties as evaluated from Izod or Charpy tests. Increase in modulus is paralleled by a substantial
rise in heat distortion temperature. A concept of constrained polymer region related to the ion-bonding strength of clay and PA6 is introduced to account for the
observed behavior.
Linear Elastic and Rubber Elastic Behavior. Although stiffening is quite
noticeable in the glassy regime of the amorphous phase, the most spectacular effect is seen in the rubber elastic regime phase, as already evoked in the case of
reinforcement by cellulose whiskers (2). The PA6clay hybrids example presented
in Table 3 is quite representative of the situation encountered with semicrystalline
thermoplastics, but elastomeric networks benet as well of clay layer dispersion
with a two- to threefold increase in modulus for polyurethane or epoxy networks
350
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
BIBLIOGRAPHY
1. J. M. Jethmalani and W. T. Ford, Chem. Mater. 8, 2138 (1996); Z. Pu and co-workers,
Chem. Mater. 9, 2442 (1997).
2. L. Chazeau and co-workers, J. Appl. Polym. Sci. 71, 1797 (1999); V. Favier and
co-workers, Polym. Eng. Sci. 37, 1732 (1997).
3. J. J. Scobbo, in SPE Antec 98 Proceedings, 1998, p. 2468.
4. D. Quian and co-workers, Appl. Phys. Lett. 76, 2868 (2000); L. Jin, C. Bower, and
O. Zhou, Appl. Phys. Lett. 73, 1197 (2000).
5. A. Usuki and co-workers, J. Mater. Res. 8, 1174 (1993); Y. Kojima and co-workers,
J. Mater. Res. 8, 1185 (1993).
6. A. Okada and co-workers, Polym. Prep. 28, 447 (1987).
Vol. 3
NANOCOMPOSITES, POLYMERCLAY
351
352
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
NANOCOMPOSITES, POLYMERCLAY
Vol. 3
JEAN-MARC LEFEBVRE
Universite des Sciences et Technologies de Lille
NOVOLAKS.
NUCLEIC ACIDS.
NYLON.
See POLYNUCLEOTIDES.
See POLYAMIDES.
See POLYSULFONES.