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of this nanocomposite from about 10

5

to 10

2

S/cm (Mehrota and Giannelis, 1992).

The effect of the Fe(III) localisation in iron-rich smectites on the electrical behaviour

of clay mineral–PPy nanocomposites doped with I

was recently reported (Letaı

et al., 2005). As expected, the electrical conductivity here also shows a highly aniso-

tropic character imposed by the 2D geometry of the clay mineral particles.

The electrical conductivity of montmorillonite-PNVC systems (Biswas and Ray,

1998) is about 10

6

S/cm, which is higher than that of pure PNVC but lower than

that of montmorillonite alone. Nonetheless, future investigations should be carried

out on the potential behaviour of clay mineral–PNVC nanocomposites as photo-

conductors based on charge transfer between these materials and electron acceptors

such as 2,4,7–trinitro–9–ﬂuorenone (Schaffert, 1971).

As ind icated above, heating clay mineral–PAN nanocomposites gives rise to car-

bonaceous-clay materials which can be used as electrodes for electrochemical devices

(Duclaux et al., 2000; Ferna

ndez-Saavedra et al., 2004). To clarify the mechanisms

involved in the different steps of PAN transformation into graphitised materials was

applied the in situ EIS technique has been applied simultaneously with FTIR and

XRD analyses (Ferna

ndez-Saavedra et al., 2004). This will provide means of con-

trolling the structural and textural characteristics of the resulting carbonaceous ma-

terials and their relationship with the electrical and electrochemical behaviour of the

nanocomposites.

As shown above, the intercalation of chitosan in smectites gives clay mineral–bio-

polymer nanocomposites having an anion-exchange capacity. Based on this property,

PANI-clay nanocomposite

(NH

)

: Na+,..

-clay

Fig. 10.3.10. Formation of Na

-montmorillonite-PANI nanocomposites.

10.3.5. Clay-Polymer Nanocomposites: Properties and Applications 609

these materials could be used as active elements in electrochemical sensors for selective

detection of ions in solution: they should easily discriminate monovalent from poly-

valent species (Darder et al., 2005).

D. Gas and Water Permeation

Low gas permeation of nanocomposites was long considered as one of their most

important technological advantages. The simple tortuous model (Nielsen, 1967)does

explain many experimental results but many new models were recently developed,

most of which can explain the low permeability, and the high modulus of nanocom-

posites. (Beall, 2001; Bonner et al., 2001; Swannack et al., 2002; Drozdov et al., 2003).

It is interesting to note that total exfoliation with random orientation of the in-

dividual clay mineral particles may not be favourable to low permeability; the more

favourable morphology should be that of intercalated compounds, where the particles

are well oriented, and remain parallel to each other, even in the ﬁnal part.

The application of polymers in ﬁlms, such as nylon in food packaging, where

reduced permeability is valued, is a very complex subject, which cannot be simpliﬁed

without missing important points. The mechanical properties of the ﬁnished ﬁlm are

an intricate function of the characteristics and processing history of the product.

For example, clay–nylon nanocomposites show improvements in transparency,

gas barrier properties and modulus, but none in elongation at break and tear re-

sistance compared with typical nylons used in such applications. If the nanocom-

posite ﬁlm is made with a reduced ﬁlm thickness (to take advantage of the higher

modulus and lower gas permeability), the potential applications of this new product

will be limited to the few cases, where its lower tear resistance will be acceptable. The

permeability of nylon and organoclay–nylon nanocomposites is a function of crys-

tallinity, and hence of the processing conditions. For example if colder than normal

roller temperature have to be used during extrusion, the ﬁlm will show sub-optimal

permeability.

In two-layered ﬁlms, organoclay–nylon nanocomposites may cause waviness and

curling because the ﬁlm is asymmetric, hence exacerbating the difference in prop-

erties between the two materials. These issues are not uncommon and can be easily

resolved, but usually, the solutions reduce the advantages of the nanocomposites

versus the neat polymer.

Besides the organoclay–EVOH nanocomposites (Lucciarini et al., 2002), and the

patented butyl based coatings (Feeney, et al., 1998), the best barrier properties ob-

tained so far with nanocomposites are with the aromatic-aliphatic polyamide nano-

composites (Imperm

)(Bagrodia et al., 2001).

In one article by Bureau et al. (2001), an organoclay–polyamide 6 nanocomposite

having a low vapour transmission rate, absorbs at equilibrium as much water as the

neat polymer. This result, if not unexpected, is in contradiction with published data.

The permeability and the solvent uptake of organoclay–PP nanocomposites is lower

than for the neat polymer (Manias et al., 2001). For example a PP nanocomposite

Chapter 10.3: Clay Mineral– and Organoclay– Polymer Nanocomposite610

containing 6% organoclay shows about half the oxygen transmission rate of the neat

PP (Qian et al., 2001).

E. Other Properties

Polymer Crystallization

It is generally accepted, that the degree of crystallisation of organoclay–nylon 6

nanocomposites does not vary with organoclay content. However, the presence of

the organoclay may change the crystal form, from alpha (normally present in neat

nylon 6) to predominantly gamma (Kojima et al., 1993c). The organoclay has a

strong nucleation effect, and increases the crystallisation rate (Liu et al., 1998). As a

result, the melting point of the clay mineral–nylon nanocomposites is slightly re-

duced compared to the neat nylon, and the crystallisation temperature is increased.

The reduction in melting temperature is usually associated with the smaller size of

the crystallised nylon, whereas the higher crystallisation temperature is associated

with the nucleation effect of the c lay mineral. Stretching during processing promotes

the formation of the alpha phase at all temperatures for organ oclay–nylon 6 nano-

composites ( Ergungor et al., 2002).

In microcomposites, the degree of crystallisation of PP decreases with increasing

ﬁller volume fractions, while some ﬁllers such as talc are known to be powerful

nucleating agents for PP (Varga and Schulek-To

th, 1991). Organoclays apparently

do not change the crystallinity of PP in the nanocomposites. Nevertheless, if PP

normally forms spherulites, apparently PP nanocomposites form ﬁbres at 142 1C, a

temperature at which the PP alone does not crystall ise (Kodgire et al., 2000).

By contrast, a significant reduction in the degree of crystallinity of organoclay–PE

nanocomposites is observed, which tends to work against the reinforcement effect of

the organoclay (Gopakumar et al., 2002).

Degradation During Nanocomposite Processing

A problem with clay–polymer nanocomposi tes is associated with degradation during

processing. There is an obvious need for more studies regarding additional stab-

ilisation of the polyme rs.

During melt blending of an organoclay–nylon 6 nanocomposite, in a tw in screw at

240 1C, the organic modiﬁer degrades to an extent correlated with the residence time

in the extruder (Davis et al., 2002). Further, this nanocomposite significantly de-

grades during injection moulding, even if it was thoroughly dried. The authors

conclude that small amounts of water adsorbed by the clay mineral are respo nsible

for the degradation of the nanocomposite. Here again new stabilisation techniques

need to be worked out.

Other issues are associated with the chemicals used to modify the clay: Hoffman

degradation of the tetraalkylammonium ions in some organoclays is apparently

responsible for the broadening of the polydispersity of the polymer matrix during

processing (Gilman et al., 2000). It is interesting to note that the additive used for

10.3.5. Clay-Polymer Nanocomposites: Properties and Applications 611

compatibilising the clay mineral, may represent from 20 to almost 50% by weight

relative to the clay (Usuki et al., 1996 ; Kodgire et al., 2000).

Clays are derived from natural products, thus containing impur ities as organic

matter from soils and oxyhydroxides mainly of iron or aluminium. These are nor-

mally eliminated by appropriate techniques during clay puriﬁcation. These impu-

rities and structural transition metals, such as iron, titanium, if not completely

removed, are known to promote degradation of the organoclay–PP nanocomposite

by UV, for example. Possible solutions include the use of adeq uate UV additives, or

synthetic clay minerals, but the mechanical properties of the resulting nanocom-

posites are inferior to those prepared from natural clay (Wang and Pinnavaia, 1998).

In the majority of the organoclay–polymer nanocomposites described in the lit-

erature there is an ionic bond between the swelling agent and the clay mineral. If the

swelling agent is accidentally released (in a reverse ion exchange reaction), the or-

ganoclay itself may separate from the polymer (Moet and Akelah, 1993; Messersmith

and Giannelis, 1995).

Until now, little value was attached to organoclays as sole reinforcing agent. For

example, the relatively high heat deformation temperatures characteristic of the

nylon nanocomposites are largely insufﬁcient compared to actual market require-

ments, especially in automotive applications. Organoclays can however partially

replace oth er reinforcing agents, like glass ﬁbre.

10.3.6. CONCLUSIONS

Clay minerals and polymers can be used to prepare almost tailor-made clay min-

eral–polymer nanocomposites, having interesting physical properties and, in some

instances, commercial applications.

It is obvious that the information is extensive, but the quality of published papers

is uneven. In such an emerging ‘‘new science’’, much needs to be learned. Every step,

every experiment takes the scientist into the exciting ﬁeld of the unknown and un-

expected innovation. Many statements are made that contradict previous ideas.

These are sometimes partially ‘‘revisited’’.

Even if the vast majority of people involved in clay mineral–polymer nanocom-

posite research rightfully believe in the future of these new materials, few products

reached industrial application. In some papers on nanocomposites, the polymer

science aspects are not well considered, but most often, it is the understanding of the

peculiar properties of the clay minerals that is rather limited. Clearly, nanocomposite

developments would beneﬁt from a stronger cooperation between polyme r and clay

scientists.

Suggestions are made to explore new routes, such as using kaolinite and sepiolite

as clay mineral components instead of the widely used montmorillonite. Similarly,

the co-hydrolysis route to compatibilise the clay mineral with the polymer was not

fully investiga ted, although the results are promising.

Chapter 10.3: Clay Mineral– and Organoclay– Polymer Nanocomposite612

Current commercial nanocomposites were not reall y optimised, and their me-

chanical and functional perfor mance could still be vastly improved. In this respect,

knowledge of clay mineral properties, as well as clay mineral conditioning by con-

trolled modiﬁcation, and polymer chemistry should be more integrated into the fast-

growing ‘‘nanoﬁeld’’ programs.

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Chapter 10.3: Clay Mineral– and Organoclay– Polymer Nanocomposite618