Layered silicate nanocomposites based on various high-functionality epoxy resins. Part II: The influence of an organoclay on the rheological behavior of epoxy prepolymers

The effect of an organically surface modified layered silicate on the viscosity of various epoxy resins of different structures and different functionalities was investigated. Steady and dynamic shear viscosities of the epoxy resins containing 0-10 wt% of the organoclay were determined using parallel plate rheology. Viscosity results were compared with those achieved through addition of a commonly used micron-sized CaCO3 filler. It was found that changes in viscosities due to the different fillers were of the same order, since the layered silicate was only dispersed on a micron-sized scale in the monomer (prior to reaction), as indicated by X-ray diffraction measurements. Flow activation energies at a low frequency were determined and did not show any significant changes due to the addition of organoclay or CaCO3. Comparison between dynamic and steady shear experiments showed good agreement for low layered silicate concentrations below 7.5 wt%, i.e. the Cox-Merz rule can be applied. Deviations from the Cox-Merz rule appeared at and above 10 wt%, although such deviations were only slightly above experimental error. Most resin organoclay blends were well predicted by the Power Law model, only concentrations of 10 wt% and above requiring the Herschel-Buckley (yield stress) model to achieve better fits. Wide-angle X-ray measurements have shown that the epoxy resin swells the layered silicate with an increase in the interlayer distance of approximately 15 Angstrom, and that the rheology behavior is due to the lateral, micron-size of these swollen tactoids.

Layered silicate nanocomposites based on various high-functionality epoxy resins: The influence of an organoclay on resin cure

The influence of an organically modified clay on the curing behavior of three epoxy systems widely used in the aerospace industry and of different structures and functionalities, was studied. Diglycidyl ether of bisphenol A (DGEBA), triglycidyl p-amino phenol (TGAP) and tetraglycidyl diamino diphenylmethane (TGDDM) were mixed with an octadecyl ammonium ion modified organoclay and cured with diethyltoluene diamine (DETDA). The techniques of dynamic mechanical thermal analysis (DMTA), chemorheology and differential scanning calorimetry (DSC) were applied to investigate gelation and vitrification behavior, as well as catalytic effects of the clay on resin cure. While the formation of layered silicate nanocomposite based on the bifunctional DGEBA resin has been previously investigated to some extent, this paper represents the first detailed study of the cure behavior of different high performance, epoxy nanocomposite systems.

Rheological Properties of Organoclay Suspensions in Epoxy Network Precursors

This paper deals with the evolution of the state of dispersion of organically modified montmorillonites in epoxy or amine precursors. The epoxy prepolymer is a diglycidyl ether of bisphenol A (DGEBA) and the curing agent is an aliphatic diamine with a polyoxypropylene backbone (Jeffamine D2000). The clay dispersion is evaluated at the platelet scale (nanoscopic scale) from X-ray spectrometry [wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS)] and at the aggregates scale (microscopic scale) from rheological analysis. The organoclays used form gels in the monomers above the percolation threshold if no shear is applied and present a mechanical gel/sol transition when shear stress increases. Gel strength and viscosity at high shear rates are linked to the nanometric state of dispersion and reveal the existence of two different organizations depending on organoclay/monomer interactions: (i) When the clay shows good interactions with the monomer, a significant swelling of the clay galleries by the monomer is obtained. These swollen particles lead to formation of weak gels which after shearing give high relative viscosity fluids. (ii) When the clay develops poor interactions with the monomer, the clay tends to reduce its exchange surface with the monomer and leads to a strongly connected gel. Shear breaks down this physical network leading to a very low relative viscosity fluid composed of nonswollen particles keeping a high aspect ratio. (C) 2003 Elsevier B.V All rights reserved.

Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends - Effect of filler content and polymer matrix composition

We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HDPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organomodified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep increasing the organoclay content eventually results in a high degree of PA6 phase continuity. Rheological analyses reveal that the filler loading at which the polyamide assembles in a continuous network corresponds to the critical threshold for its rheological transition from a liquid- to a gel-like behaviour, which is indicative of the structuring of the filler inside the host PA6. On the basis of this finding, a schematic mechanism is proposed in which the role of the filler in driving the space arrangement of the polymer phases is discussed. Finally, we show that the synergism between the reinforcing action of the filler and its ability to affect the blend microstructure can be exploited in order to enhance relevant technological properties of the materials, such as their high temperature structural integrity.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co-continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low-density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X-ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co-continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with droplets/matrix and co-continuous morphologies. In addition to the expected reinforcing action of the filler, the resulting fine microstructure plays an important role in enhancing the mechanical properties of the blends. This is essentially because of a good quality of stress transfer across the interface between the constituents, which also seems to benefit for a good interfacial adhesion promoted by the filler. Our results provide the experimental evidence for the capabilities of nanoparticles added to multiphase polymer systems to act selectively as a reinforcing agent for specific domains of the material and as a medium able to assist the refinement of the polymer phases during mixing.

Influence of the Type of Quaternary Ammonium Salt Used in the Organic Treatment of Montmorillonite on the Properties of Poly(Styrene-co-Butyl Acrylate)/Layered Silicate Nanocomposites Prepared by In Situ Miniemulsion Polymerization

Hybrid latices of poly(styrene-co-butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer-MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 3658-3669, 2011

Toluene and naphthalene sorption by iron oxide/clay composites

Commercial bentonite (BFN) and organoclay (WS35), as well as iron oxide/clay composite (Mag_BFN) and iron/oxide organoclay composite (Mag_S35) were prepared for toluene and naphthalene sorption. Mag_BFN and Mag_S35 were obtained, respectively, by the precipitation of iron oxide hydrates onto sodium BFN and S35 clay particles. The materials were characterized by powder X-ray diffraction (XRD), X-ray Fluorescence (XRF), and TG and DTA. From XRF results and TG data on calcined mass basis, a quantitative method was developed to estimate the iron compound contents of the composites, as well as the organic matter content present in WS35 and Mag_S35.

Interfacial interactions and structure of organic-inorganic nanohybrids

Understanding the interfacial interactions and structure is important to better design and application of organic-inorganic nanohybrids. This paper presents our recent molecular dynamic studies on organoclays and polymer nanocomposites, including the layering behavior of organoclays, structural and dynamic properties of dioctadecyldimethyl ammoniums in organoclays, and interfacial interactions and structure of polyurethane nanocomposites. The results demonstrate that the layering behaviors of organoclays are closely related to the chain length of quaternary alkyl ammoniums and cation exchangeable capacity of clays. In addition to typical layered structures such as monolayer, bilayer and pseudo-trilayer, a pseudo-quadrilayer structure was also observed in organoclays modified with dioctadecyldimethyl ammoniums (DODDMA). In such a structure, alkyl chains do not lie flat within a single layer but interlace, and also jump to the next layer or even the next nearest layer. Moreover, the diffusion constants of nitrogen and methylene atoms increase with the temperature and methelene towards the tail groups. For polyurethane nanocomposite, the van der Waals interaction between apolar alkyl chains and soft segments of polyurethane predominates the interactions between organoclay and polyurethane. Different from most bulk polyurethane systems, there is no distinct phase-separated structure for the polyurethane.

Preparation and characterisation of biodegradable starch-based nanocomposite materials

Different formulations of biodegradable starch-polyester blend nanocomposite materials have been film blown on a pilot scale film blowing tower. The physical properties of different films have been examined by thermal and mechanical analysis and X-ray diffraction. The results show that the addition of an organoclay (from 0 to 5 wt%) significantly improves both the processing and tensile properties over the original starch blends. Wide angle X-ray diffraction (WAXD) results indicate that the best results were obtained for 30wt% starch blends, and the level of delamination depends on the ratio of starch to polyester and amount of organoclay added. The crystallisation temperature of the nanocomposite blends is significantly lower than the base blend. This is probably due to the platelets inhibiting order, and hence crystallisation, of the starch and polyester. The mechanical and thermal properties of the blends are also sensitive to the way the clay particles are dispersed. (C) 2003 Society of Chemical Industry.

Nanocompósitos ternários de amido termoplástico e poli(Butadieno maleatado)

Liquid polybutadiene (PBLH) was modified with maleic anhydride (MA). The material (PBLHM) was characterized and used to prepare hybrid materials by blending with glycerol-plasticized cassava starch (TPS) and an organophilic clay at 5 wt% content. Processing was performed by extrusion under mild conditions and led to TPS/PBLHM/clay hybrids, at 95/5 to 85/15 TPS/PBLHM compositions, which were characterized by contact angle measurements, X-ray diffraction and mechanical analysis. The results revealed a reduction in the hydrophilicity and the reinforcement of the hybrid materials. Biodegradability tests showed that the addition of clay and of PBLHM led to materials with high biodegradability.

Rubber-Layered Clay Nanocomposites

Department of Polymer Science and Rubber Technology,Cochin University of Science and Technology

The effect of hydrophobic and hydrophilic fumed silica on the rheology of magnetorheological suspensions

We investigate magnetorheological fluids (MRFs) prepared with carbonyl iron powder and different types of hydrophobic and hydrophilic fumed silica. The rheological properties of the MRF suspensions were investigated with and without an applied magnetic field. The MRF samples prepared with hydrophobic silicas presented a more pronounced thixotropic effect and a higher recovery rate than those prepared with hydrophilic silicas. The application of a magnetic field to all the MRFs samples investigated leads to an increase in the viscosity and the thixotropic effect. MRF prepared with hydrophobic silicas presented smaller values of the viscosity than those prepared with hydrophilic silicas. At low applied magnetic fields, the type of the silica used to prepare the MRF leads to noticeable differences in the shear stress. However, these differences disappear at high magnetic fields. The results obtained showed that MRF samples prepared with the hydrophobic silica with the biggest particle diameter presented better characteristics for magnetorheological fluids, with higher values of yield stress, recovery rate, and elastic modulus. (C) 2009 The Society of Rheology. [DOI: 10.1122/1.3086870]

Obtenção de emulsões asfálticas convencionais e modificadas com argilas e nanoargilas

The increasing demand for asphalt leads to the development of techniques that can improve the quality of products and increase the useful working life of pavements. Consequently, there is a growing application of asphalt emulsions, which are produced from a mixture of petroleum asphalt cement (CAP) with an aqueous phase. The main advantage of asphalt emulsions is its cold application, reducing energy costs. Conventional emulsions are obtained using asphalt, water, solvent, and additives. The modified asphalt emulsion is developed by adding a modifying agent to conventional emulsions. These modifiers can be natural fibers, waste polymers, nanomaterials. In this work modified asphalt emulsion were obtained using organoclays. First, it was prepared a conventional asphalt emulsion with the following mass proportion: 50% of 50/70 penetration grade CAP, 0.6% of additives and 3% of emulsifier, 20% of solvent and 26.4% of water. It was used bentonite and vermiculite (1% and 4%) to obtain the modified asphalt emulsion. Bentonite and vermiculite were added in its raw state and as an organoclay form and as an organoclay-acid form, resulting in 26 experimental runs. The methodology described by Qian et al. (2011), with modifications, was used to obtain the organoclay and the organoclay-acid form. infrared spectroscopy (IR)) were used to characterize the clays and nanoclays. The emulsions were prepared in a colloidal mill, using 30 minutes and 1 hour as mixing time. After, the emulsions were characterized. The following tests were performed, in accordance with the Brazilian specifications (DNER- 369/97): sieve analysis, Saybolt Furol viscosity, pH determination, density, settlement and storage stability, residue by evaporation, and penetration of residue. Finally, it can be concluded that the use of nanoclays as asphalt modifiers represent a viable alternative to the road paving industry