Clay Delamination Research Articles

Swelling and delamination of inorganic homoionic montmorillonite clay in water-polar organic mixed solvents.

The smectite group of clay minerals (smectites) consists of negatively charged clay layers and interlayer exchangeable cations. They are spontaneously delaminated in water to form single clay layers when the interlayer cations are small alkaline cations such as Na+ or Li+. This phenomenon known as osmotic swelling has fundamental importance in constructing novel clay-based nanomaterials. However, osmotic swelling of smectites has not been systematically investigated in organic solvents although this phenomenon should be useful for developing novel clay-organic nanocomposites. We report herein that montmorillonite, a typical smectite, with monovalent and divalent inorganic interlayer cations shows osmotic swelling accompanied by delamination of clay layers in water-acetonitrile and water-2-propanol mixed solvents, although inorganic interlayer cations have been believed to be inappropriate for delamination of smectites in organic solvents. The delamination is confirmed by a combination of macroscopic sample appearances, XRD patterns, and SEM images. Montmorillonite with interlayer Na+ or Li+ ions shows osmotic swelling in pure water and the mixed solvents but not in pure organic solvents. Montmorillonite with alkaline earth dications in the interlayer spaces is swollen in water-organic mixed solvents but not in either pure water or organic solvents alone. Partial delamination in several systems can be clarified from SEM images even though the sample appearances and XRD patterns do not give firm evidence. Such non-uniform swelling behavior of montmorillonite is related to the disordered stacking of the aluminosilicate layers with different morphologies in the clay powders as observed by SEM.

Prospects and limitations of a clay-enabled pre-concentration method for spectrophotometric quantification

The width of applicability of a pre-concentration protocol for quantifying analytes from dilute aqueous solutions, relying on adsorbate loading onto Bentone LT and subsequent clay delamination, was studied. The applicability of the protocol was investigated on seven organic (cetyltrimethylammonium bromide (CTAB), diclofenac, topotecan, methyl red) or inorganic (iron(ΙΙΙ) chloride, cobalt(ΙΙ) nitrate, copper(II) acetate) molecules. The study verified that Bentone LT adsorbed all studied analytes from dilute aqueous solutions. The relationship between adsorbate concentration in loading medium and adsorbate availability in supernatant upon delamination was investigated. A behaviour approximating a linear relationship with either a single or two linear ranges was observed for most adsorbates at low loading concentrations. For diclofenac and Fe(III) this relationship was described by a logistic regression model. Concentrations in the linear portion of the quasi-desorption curves correspond to environmental levels for certain analytes tested. High pre-concentration factors were achieved for many adsorbates (about 71-fold, 34-fold, and 29-fold for Co(II), Cu(II), and methyl red, respectively). Lower pre-concentration factors (about 12-fold, 8-fold, and 2-fold) were obtained for topotecan, Fe(III), and CTAB, respectively. For those adsorbates where pre-concentration was significantly successful, the lowest adsorbate concentration that could be reliably detected decreased by a factor ranging between 46- and 5-fold, when compared to the limit of quantitation (LOQ) of the hyphenated quantification assay not supplemented by a pre-concentration step. Pre-concentration of specific analytes in the presence of mixtures of chemicals, at environmentally-relevant levels or above, was equally successful. Limitations of the pre-concentration methodology were studied: The methodology works poorly when hyphenated to assays that depend on negatively charged compounds for ion-pair formation. Low pH values that may be required to favour adsorption, limit quasi-release efficiency. Adsorbate release, in the latter cases, is effective though upon pH increase, without delamination.

How clay delamination supports aseismic slip

Abstract Aseismic slip is a stable fault slip, which allows strain to be relieved smoothly. Aseismic slip prevents the earthquake propagation, but it could nucleate an earthquake elsewhere. Understanding the mechanism of aseismic slip is promising in revealing the seismic cycle. Experimental evidence showed clay-rich fault gouge bears a low-friction strength, and the friction is strengthened with slip velocity (velocity-strengthening), which was thought to support aseismic slip. Clay minerals are comprised of platy crystalline layers with water intercalated between them, which may act as a lubricant. Sliding between clay layers was suspected to support aseismic slip but lacked a clarified mechanistic insight. We use non-equilibrium molecular dynamics simulations to show that shear-induced interlayer sliding is frictionally weak and velocity-strengthening, which evidences the role of clay minerals in aseismic slip. We find that interlayer water is a viscous fluid at most times, which explains the shear response of interlayer sliding. Depending on temperature and pressure conditions, intercalated water can be monolayer or bilayer, fluidic or ice like. Shear induces ice-like water to transform into fluidic water, which happens as a stick-slip phenomenon reflecting a first-order transition. Increased pore fluid pressure leads to the transformation from monolayer to bilayer intercalated water, resulting in a lower friction strength and enhanced velocity-strengthening behavior. Our work suggests that disclosing the hydration state of a clay mineral is preliminary when studying fault mechanics.

Insight into the aqueous Laponite® nanodispersions for self-assembled poly(itaconic acid) nanocomposite hydrogels: The effect of multivalent phosphate dispersants

HypothesisWe hypothesize, that physical network between Laponite® nanoparticles and high molecular weight polyelectrolyte formed by mixing of Laponite® nanodispersion (containing multivalent phosphate dispersant) and polyelectrolyte solution is strongly influenced by the type and content of dispersant, which forms electric double layer (EDL) closely to the Laponite® edges. Thus, optimum dispersant concentration is necessary to overcome clay-clay interactions (excellent clay delamination), but should not be exceeded, what would result in the EDL compression and weakening of attractions forming clay-polyelectrolyte network. Thus, deeper investigation of Laponite® nanodispersions is highly demanded since it would enable to better design the self-assembled clay-polyelectrolyte hydrogels. ExperimentsTo study clay interparticle interactions in the presence of various multivalent phosphates, complementary methods providing wide nanodispersion characterization have been applied: zeta potential measurement and SAXS technique (electrostatic interactions), oscillatory rheology (nanodispersion physical state) and NMR experiments (ion immobilization degree). FindingsIt was found that multivalent phosphates induce and tune strength of clay-polyelectrolyte interactions forming hydrogel network in terms of varying EDL on the Laponite® edges. Moreover, phosphate dispersing efficiency depends on the molecular size, chemical structure, and valence of the anion; its potential as efficient dispersant for hydrogel preparation can be evaluated by estimation of anion charge density.

Polypropylene/clay nanocomposites: An innovative one-pot process

This work discloses a novel one-pot preparation method of polypropylene (PP)/clay nanocomposites with high degree of clay delamination and improved thermal, mechanical and rheological properties. The in situ simultaneous synthesis of carboxylate clay from native clay and ionomer of PP-graft maleic anhydride (PP-g-MA) through trihydrate sodium acetate addition, combined with water injection in the extrusion process, appears to be a valuable alternative to the use of organoclay for producing PP/PP-g-MA/clay nanocomposites. The influence of PP-g-MA graft content, and of its ionomer form, onto the clay dispersion has been especially investigated. PP-g-MA of low graft content is compared to a home-made highly grafted PP-g-MA synthesized in the presence of N-bromosuccinimide (NBS). The nanocomposites prepared by combining the use of NBS-mediated PP-g-MA, trihydrate sodium acetate and water injection exhibit the highest clay dispersion. Thermal, rheological, and mechanical properties of the nanocomposites have been measured. POLYM. COMPOS., 36:644–650, 2015. © 2014 Society of Plastics Engineers

Reinforcement of the Gas Barrier Properties of Polyethylene and Polyamide Through the Nanocomposite Approach: Key Factors and Limitations

In this study, polyamide 6 (PA6) and polyethylene (PE) nanocomposites were prepared from melt blending and a detailed characterization of the nanocomposite morphology and gas barrier properties was performed. The choice of the organoclay was adapted to each polymer matrix. Exfoliated morphology and improved gas transport properties were obtained by melt mixing the polar PA6 matrix and the organoclay, whereas a microcomposite with poor barrier properties was formed from the binary PE/organomodified clay mixture. Different modified polyethylenes were examined as compatibilizers for the polyethylene/organoclay system. The effect of compatibilizer molar mass, polarity and content was investigated on the clay dispersion and on the gas barrier properties. The optimal compatibilizer to clay weight ratio was found to be equal to 4 whatever the compatibilizer. However, a high degree of clay delamination was obtained with the high molar mass compatibilizer whereas highly swollen clay aggregates resulted from the incorporation of the low molar mass interfacial agents. Contrary to the PA based system, the barrier properties of PE nanocomposites were not directly related to the clay dispersion state but resulted also from the matrix/clay interfacial interactions. Oxidized wax was identified as a very promising interfacial agent and a step by step study was performed to optimize the gas transport properties of the systems based on PE, oxidized wax and organoclay. In particular, an interesting combination of oxidized wax and high molar mass maleic anhydride grafted polyethylene allowing dividing the gas permeability by a factor 2 in comparison with neat PE was proposed.

Effect of water‐assisted extrusion and solid‐state polymerization on the microstructure of PET/Clay nanocomposites

An melt‐mixing process has been used to prepare Poly(ethylene terephthalate) (PET)/clay nanocomposites with high degree of clay delamination. In this method, steam was fed into a twin‐screw extruder (TSE) to reduce the PET molecular weight and to facilitate their diffusion into the gallery spacing of organoclays. Subsequently, the molecular weight (MW) reduction of the PET matrix due to hydrolysis by water was compensated by solid‐state polymerization (SSP). The effect of the thermodynamic compatibility of PET and organoclays on the exfoliated microstructure of the nanocomposites was also examined by using three different nanoclays. The dispersion of Cloisite 30B (C30B) in PET was found to be better than that of Nanomer I.28E (I28E) and Cloisite Na+. The effect of feeding rate and consequently residence time on the properties of PET nanocomposites was also investigated. The results reveal more delamination of organoclay platelets in PET‐C30B nanocomposites processed at low feeding rate compared to those processed at high feeding rate. Enhanced mechanical and barrier properties were observed in PET nanocomposites after SSP compared to the nanocomposites prepared by conventional melt‐mixing. POLYM. ENG. SCI., 54:1723–1736, 2014. © 2013 Society of Plastics Engineers

A novel approach to control thermal degradation of PET/organoclay nanocomposites and improve clay exfoliation

Thermal degradation of polyethylene terephthalate (PET) is accelerated in the presence of commercial organoclays, and this remains a challenge for the industry. While a high level of clay delamination is required in polymer nanocomposites, thermal degradation increases furthermore for highly exfoliated morphologies due to an increased exposure of the polymer matrix to silicate nanoplatelets. In this work, two different types of organomodified clay were melt blended with PET in the presence of a multifunctional epoxy-based chain extender, Joncryl® ADR-4368F (Joncryl), to compensate for molecular weight reduction during processing. The chain extender was added via a master-batch approach in order to promote clay delamination before molecular weight increase. The morphological, rheological, mechanical, thermal, and gas barrier characteristics of the nanocomposites were studied using several characterization techniques. A remarkable improvement in viscoelastic properties was observed for samples containing the chain extender due to recoupling of degraded chains. A better clay dispersion, enhanced barrier properties and increased Young modulus were also obtained for nanocomposites containing the chain extender. Compared to neat PET films, the oxygen permeability of nanocomposite films containing 4 wt% Cloisite® 30B and 1 wt% Joncryl decreased by 46%, whereas the corresponding permeability decrease for the Nanomer® I.28E nanocomposite was 40%. A 66% improvement in Young modulus was obtained for nanocomposite films containing 4 wt% Nanomer® I.28E and 1 wt% Joncryl. The improvement of the tensile modulus for the corresponding Cloisite® 30B nanocomposite was slightly less.

Influence of the layered silicate type on the structure, morphology and properties of cellulose acetate nanocomposites

This paper deals with the effect of different montmorillonite source clays, including pristine and organophilic montmorillonites, on the structure, morphology and properties of cellulose acetate (CA)/clay nanocomposites. In this study, the nanocomposites were prepared by melt extrusion in the presence of the environmentally friendly triethyl citrate plasticizer. The structure and morphology of the materials were analysed by X-ray diffraction and scattering (SAXS), X-ray microtomography and energy filtered transmission electron microscopy (EFTEM). SAXS and EFTEM results indicated that the nanocomposite morphologies were made up of tactoids together with exfoliated clay platelets in different proportions depending on the clay type. It can be concluded that well distributed clay tactoids and platelets can be achieved in CA nanocomposites prepared by melt extrusion and consequently property improvements can be found by using pristine or organophilic clays. In this case, the addition of a plasticizer, able to intercalate in the clay gallery, seems to be sufficient to promote the clay delamination mechanism under shearing inside the cellulose acetate matrix.

Tuning the functionalization chemistry of polypropylene for polypropylene/clay nanocomposites

New polypropylene (PP)-graft-maleic anhydride (PP-g-MA) samples have been successfully synthesized by adding N-bromosuccinimide (NBS) during the reactive extrusion process. These NBS-mediated PP-g-MAs possess higher graft content than classic PP-g-MAs (i.e. without NBS) while they keep acceptable molar masses. NBS-mediated PP-g-MAs were used as matrices in model PP-g-MA/organoclay nanocomposites and compared with commercial and home-made classic PP-g-MAs in order to evaluate their ability to disperse the clay. Significantly better degrees of clay delamination and dispersion were reached using NBS-mediated PP-g-MAs than with classic PP-g-MAs. As expected, PP-g-MAs having high graft content showed the best clay dispersion. Within the examined range of molar masses, the PP-g-MA molar mass had no influence on the clay dispersion. However PP-g-MAs exhibiting important reduction of crystallinity lead to poor clay dispersion whatever the graft content. The PP-g-MA/organoclay nanocomposite prepared using the selected “optimized” NBS-mediated PP-g-MA exhibited the best improvement of thermal properties and one of the best clay dispersions. PP/PP-g-MA blends were prepared to evaluate the miscibility between PP and selected PP-g-MAs. No problem of miscibility between the selected NBS-mediated PP-g-MA and PP was noticed. Finally the PP/organoclay prepared using the selected NBS-mediated PP-g-MA as compatibilizer showed much better clay dispersion and thermal stability than the one prepared with the corresponding classic PP-g-MA, thus establishing the interest to use such new NBS-mediated PP-g-MAs as compatibilizers.

Water-assisted extrusion of polypropylene/clay nanocomposites: A comprehensive study

Water-assisted extrusion process has been used to successfully prepare polypropylene (PP)/clay nanocomposites with high degree of clay delamination and markedly improved rheological, thermal and mechanical properties. PP-graft-maleic anhydride (PP-g-MA)-based nanocomposites and masterbatches were synthesized from untreated clay and organoclay, respectively, and fully characterized. The effects of using high-shear rates and water injection during the melt-compounding were examined. A mechanism explaining the formation of such nanocomposites is then proposed. The best clay dispersion and properties improvements of PP-g-MA/organoclay nanocomposites and masterbatches were obtained using high-shear rates and water injection (synergy effect). PP-based nanocomposites were then synthesized by dilution of PP-g-MA-based masterbatches into neat PP. For comparison, nanocomposites were also prepared by a one-pot process where PP, PP-g-MA and organoclay are directly melt-blended with or without water injection. The nanocomposites prepared by dilution into PP of a masterbatch prepared through water-assisted extrusion showed the highest clay dispersion and consequently the best thermal, mechanical and rheological properties.

Influence of maleic anhydride grafted polypropylene on the dispersion of clay in polypropylene/clay nanocomposites

This paper investigates the specific effect of the maleic anhydride (MA) grafting content of MA-grafted polypropylene (PP-g-MA) compatibilizer on the morphology of PP/clay nanocomposites (PPCNs) without the interference of molecular weight (MW) changes of the compatibilizer. To do this, PP-g-MA with different grafting contents and approximately the same MW was prepared using MA and styrene by melt extrusion on a twin-screw extruder. The two prepared series of PP-g-MA were used, respectively, in two series of PPCN based on PP homopolymer and impact copolymer to match the melt flow rate of the compatibilizer with that of the PP matrix. The morphology observations from X-ray diffraction and transmission electron microscopy, as well as rheological measurements, showed that the grafting content of PP-g-MA in the range of 0.2–1.4wt% has no appreciable influence on the dispersion of organoclay, whereas the loading of PP-g-MA can effectively influence the intercalation and delamination of clay. The intercalation and exfoliation mechanism of prepared PP-g-MA is discussed and compared with that of PP-g-MA oligomer. Maleic anhydride grafted polypropylene (PP-g-MA) with different grafting contents and approximately the same molecular weight was prepared. The grafting content of PP-g-MA in the range of 0.2–1.4 wt% shows no appreciable influence on the dispersion of organoclay, whereas the loading of PP-g-MA can effectively influence the intercalation and delamination of clay. The intercalation and exfoliation mechanism of prepared PP-g-MA is discussed and compared with that of PP-g-MA oligomer.

Synthesis of polystyrene/polybutylacrylate/layered silicate nanocomposites in aqueous medium

Synthesis of nanocomposites based on polystyrene/polybutylacrylate with layered silicates using emulsion polymerization procedure in aqueous medium allowed obtaining stable nanolatexes with sodium dodecyl sulfate as surfactant. Monomer and layered silicate nature influences the average diameter of the particles and the zeta potential appeared on the particle-disperse medium interface, as it was shown by dynamic light scattering analyses. In order to evidence the layered silicate structure, two structural evaluation methods were used. A new approach was used based on Fourier transform infrared analyses as a method to asses the clay delamination. The method was followed in conjunction with X-ray diffraction patterns and showed the pronounced delamination of the clay in the polymer matrix. The thermal stability was investigated by thermogravimetric analyses and the morphologies in solid state observed by environmental scanning electron microscope measurements.

Development of poly(vinyl chloride)/montmorillonite nanocomposites using chelating agents

Different chelating agents such as poly(ethylene glycol), propylene glycol monooctadecanoate and palm oil were used for modification of the surface-treated montmorillonite (MMT). The work also included the development of a technique for mixing chelating agents with MMTs using different methods and different proportions of MMT/chelating agent/ethanol. Evaluation of the result of mixing was performed by thermogravimetric analysis, X-ray diffraction and high-resolution scanning electron microscopy (HR-SEM). The results showed that the chelating agents used were intercalated in MMT, increasing the interlayer spacing. The OMMT was used in the manufacture of composites with rigid PVC using a microcompounder. The master batch concept turned out to be promising in terms of dispersion and delamination of clay, as observed in HR-SEM photographs. However, despite good dispersion and exfoliation of MMT, poor compatibility between clay platelets and PVC matrix remains to be solved to enable full exploitation of its engineering potential. Despite this drawback, good thermal stability and mechanical properties have already been achieved.

Effect of the degree of clay delamination on the phase morphology, surface chemical aspects, and properties of hydrolyzable polyurethanes for periodontal regeneration

AbstractIn recent years, there has been increased interest in biodegradable polyurethanes for use in regenerative medicine because of their versatility and biocompatibility. Nevertheless, these polymers are usually produced using organic solvents that can lead to the release of toxic components. In this work, polyurethane/montmorillonite nanocomposites were designed to work as guided tissue regeneration membranes to treat periodontal diseases. Polyurethanes were synthesized in an aqueous environment. The composition, morphology, and mechanical properties of the biomaterials were evaluated. The cellular viability, proliferation, and morphology changes of rat culture cementoblasts were also investigated using a montmorillonite assay. Small‐angle X‐ray scattering, X‐ray diffraction, and infrared spectroscopy results showed that the degree of clay delamination within the polymer was able to tailor the phase morphology of the polymer, the chemical aspects of the surface, the mechanical properties, and the kinetics of hydrolysis of the materials. The produced scaffolds provided a good environment for the adhesion and proliferation of cementoblasts and thus can be considered suitable biomaterials for participating in procedures associated with periodontal regeneration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Influence of the compatibilizer polarity and molar mass on the morphology and the gas barrier properties of polyethylene/clay nanocomposites

AbstractIn this study, different modified polyethylenes with different molar masses and different modification rates were examined as compatibilizers to prepare high density polyethylene/organoclay nanocomposites. Nanocomposites having 5 wt % organo‐modified clay and 20 wt % interfacial agent were prepared by melt blending. The effect of compatibilizer molar mass and polarity was investigated on the clay dispersion and on the gas barrier properties. It was observed that the amount of large and dense fillers aggregates was considerably reduced by introduction of an interfacial agent. The nanocomposite final morphology was governed by a diffusion/shear mechanism. A high degree of clay delamination was obtained with the high molar mass compatibilizers, whereas highly swollen clay aggregates resulted from the incorporation of the low molar mass interfacial agents. In the investigated nanocomposites series, the barrier properties could not be directly related to the clay dispersion state but resulted also from the matrix/clay interfacial interactions. A gas transport mechanism based on these both parameters was proposed to explain the barrier properties evolution in these low polar nanocomposites series. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2593–2604, 2008

Poly(caprolactone)/clay masterbatches prepared in supercritical CO2 as efficient clay delamination promoters in poly(styrene-co-acrylonitrile)

Poly(styrene-co-acrylonitrile) (SAN)/clay nanocomposites with a high degree of clay exfoliation were prepared upon melt blending of pre-exfoliated poly(e-caprolactone) (PCL)/organoclay masterbatches in a Brabender-type internal mixer. These highly filled masterbatches were synthesized by a one-pot process using supercritical carbon dioxide as a polymerization medium. During their dispersion into SAN, PCL is expected to act as a compatibilizer at the polymer–clay interface as it is miscible with the host matrix under these conditions. Reference nanocomposites based on direct melt mixing of the commercial organoclay were also prepared for the sake of comparison. The superiority of the masterbatch route in term of clay delamination efficiency has been evidenced by XRD analysis, visual and TEM observations. The effect of the nanocomposite morphology on the polymer properties was then investigated. A substantial improvement of the fire behaviour and a decrease in gas permeability have been observed for the nanocomposite containing the highest level of clay exfoliation, accompanied with a higher brittleness as evidenced by traction and impact tests.

Chlorinated polyethylene/layered silicate nanocomposites: Poly(ε-caprolactone)-based “masterbatch” approach

Chlorinated polyethylene (CPE)/organophilic-montmorillonite (Cloisite ®30B (CL30B)) nanocomposites have been prepared by melt intercalation using (poly(ε-caprolactone), (PCL)) as CPE/clay compatibilizer. Actually, a high clay content masterbatch-based on PCL was first produced and then dispersed by melt blending within CPE. CPE/CL30B nanocomposites was also prepared by direct blending of CPE with CL30B for sake of comparison. All the composites were characterized by wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). The thermal stability of the nanocomposites was analyzed by thermogravimetric analysis (TGA) while the mechanical properties were assessed by tensile testing. When using low molecular mass PCL chains as compatibilizer, the nanocomposites displayed a rather intercalated structure but their ultimate properties remained unchanged whereas with high molecular weight PCL chains, clay delamination was favoured and led to an increase of both thermal and mechanical properties of the resulting nanocomposites.

Effects of processing parameters on the preparation of nylon 6 nanocomposites

An experimental study was carried out to investigate the effects of the following parameters: (1) organic modifier and nylon 6 molecular weight, (2) processing conditions, and (3) pressure, with and without supercritical fluids, on the dispersion of clays for nylon 6/montmorillonite nanocomposites. A novel experimental setup was designed that physically separated the melting and mixing unit operations, and allowed control of the pressure using a pressure adjustable die. Exfoliated clay morphology was realized using a wide angle X-ray diffraction technique when both requirements of (1) selecting an organic modifier that was thermodynamically compatible with the polymer matrix and (2) applying sufficient degree of shear stress were fulfilled. Keeping the organic modifier constant, either longer residence time or the same level of shear stress did not improve the state of clay dispersion once a critical morphology was established. In the absence of supercritical fluids, pressure improved the clay delamination by reducing the free volume of the polymers and thereby increasing the interaction between the chains, and ultimately increasing the viscosity and, therefore, the level of wall shear stress. Using supercritical fluids such as either carbon dioxide or 1,1,1,2-tetrafluoroethane did not improve the clay dispersion for 95/5 N6-L/20A due to its role in increasing the free volume and decreasing the melt viscosity.

Processing–structure–properties relationships of mechanically and thermally enhanced smectite/epoxy nanocomposites

AbstractMechanically reinforced and thermally enhanced smectite/epoxy nanocomposites were synthesized using “direct” (without solvent) and “solvent” processing techniques. The molecular dispersion of smectite clay in the epoxy resin was investigated for its role in the rheology, structure formation, and properties of nanocomposites. The effects of three types of organic modifiers on the dispersion structure were compared. The use of solvent during processing assists in the enhancement of clay exfoliation. Rheology was used as a method to compare the degree of clay delamination in the resin matrix, as well as to estimate the suspension structure. The critical volume fraction (Φ*) and maximal packaging of smectites were determined and used for prediction of the viscosity. The qualitative changes in the nanostructure of suspensions above Φ*, due to flocculation of exfoliated clay layers, were compared with the alteration of the properties of nanocomposites, related to the structure formation and morphology. The curing kinetics were found to depend on both the organic modifier and solvent, but the extent of curing was roughly equivalent for the pure epoxy resin and the nanocomposites. The structure of the nanocomposites, either intercalated or exfoliated, produced by the direct processing technique was controlled by the organic modifier. By using solvent processing, the effect of the solvent dominates that of the organic modifier, presumably leading to exfoliated nanocomposites. The mechanical and thermal properties are strongly enhanced above the Φ* of smectites, and they are significantly dependent on the type of nanocomposite structure and the use of solvent. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2499–2510, 2005