Novel preparation and properties of EPDM/montmorillonite nanocomposites

This article reports on a novel route to develop ethylene–propylene–diene rubber (EPDM)/montmorillonite nanocomposites Modification of the MMT was carried out with maleic anhydride (MA), which acts as the intercalation agent for MMT and the vulcanizing agent for EPDM matrix, as well as the compatibilizer for the EPDM and MMT phases. The effect of MA‐modified MMT in nanocomposites was investigated by focusing on three major aspects: structural analysis, thermal properties, and material properties. The d‐spacings of both the MA modified MMT and exfoliated nanocomposites were investigated by X‐ray diffraction (XRD), and the morphology of these nanocomposites was examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Dynamic mechanical analysis confirms the constraint effect of exfoliated MMT layers on EPDM chains, which benefited the increased storage modulus, increased glass transition temperature. Thermogravimetric analysis indicates that there is some enhancement in degradation behavior between the nanocomposites and EPDM matrix. The nanocomposites exhibit great improvement in tensile strength and modulus, as well as elongation‐at‐break. The effects of MA addition on the formation of nano‐metric reinforcement and on the mechanical properties of nanocomposites are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2578–2585, 2006     

A novel method to prepare chitosan powder and its application in cellulase immobilization

In this study, chitosan microspheres and sponges with uniform spherical and porous morphologies were prepared by coiling the stretched chains of chitosan with addition of salt and choosing different kinds of organic solvents as evaporation solvents. Cellulase was immobilized to the support by a covalent method. The enzyme exhibited a considerable affinity to the support, and the protein loading of 145.5 mg g^?1 support was fairly high. The immobilized cellulase had a higher K_m than free cellulase and had better stability with respect to pH, thermal stability, reuses and storage stability than free cellulase. Copyright © 2005 Society of Chemical Industry     

高性能丁基橡胶/有机黏土纳米复合材料的新型制备方法

采用一种新型制备方法--预膨胀有机黏土与机械共混的方法制备丁基橡胶（IIR）/有机黏土纳米复合材料。实验结果表明,当有机黏土为10 phr时,采用预膨胀有机黏土（S-OC）与机械共混的方法制备的IIR/有机黏土纳米复合材料（IIR/S-OCNs）的拉伸强度和撕裂强度,明显优于采用熔体法制备的IIR/有机黏土（OC）纳米复合材料（IIR/OCNs）的相应性能,较纯丁基橡胶分别提高了4.96倍、0.22倍;当有机黏土为5 phr时,采用预膨胀有机黏土与机械共混的方法制备的IIR/S-OC纳米复合材料的气体渗透率,分别较纯IIR、熔体法制备的IIR/OC纳米复合材料下降了21.88%和12.50%。这种新型制备方法是将溶液制备方法的优点与熔体制备方法的优点有机地统一在了一起。该材料有可能在高级无内胎轮胎气密层以及其他要求高性能弹性体材料的领域获得应用。     

Synthesis and characterization of sPS/montmorillonite nanocomposites

The present work analyzed the possibility of obtaining and producing syndiotactic polystyrene (sPS)–based nanocomposites. The work first focused on possible technology to use for intercalation from solution and melt intercalation. Using a blend of sPS with atactic polystyrene (aPS) as the matrix was also considered. Thermal analysis techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), were used to study the thermal properties and stability of the nanocomposites obtained and to select the most appropriate nanocharges. The effect of the introduction of nanofillers on these properties also was evaluated. X–ray diffraction was used to investigate the degree of clay exfoliation. Finally, mechanical characterization of the nanocomposites obtained was performed and compared to that of the pure material. The tests demonstrated that nanodispersion of phyllosilicate layers improved the mechanical behavior of the polymers analyzed, especially the annealed sPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4957–4963, 2006     

Resol/montmorillonite nanocomposites obtained by in situ polymerization

Nanocomposites based on resol resin and layered silicates were obtained by in situ polymerization. An increment in the viscosity and in the content of free formaldehyde in the prepolymer with the addition of clay was observed. It could be attributed to the entrance of small phenol molecules into the galleries modifying the concentration of reagent enabled to react outside the clay galleries. The composites were cured by temperature and it was observed that the type of clay affect their dispersion in the polymer. The unmodified Cloisite^® Na⁺ montmorillonite (CNa) was the best dispersed in the polymeric matrix, whereas the modified montmorillonites (MMTs) showed an interlayer contraction after curing. It seems to be due to the loss of modifiers from the clay or to the different rate of curing inside and outside the galleries. In addition, the composite containing CNa presented higher crosslinking density than the others with modified MMTs. More adhesive strength was observed in that composite as well. It was related with the void content and the polarity of the samples. These results were compared with the ones obtained when the nanocomposites were synthesized by mixing the clay with the prepolymer. The nanocomposites with the addition of CNa showed similar properties independent of the way of synthesis used. However, it seems that the modified clays are better dispersed by mixing with the prepolymer than by in situ polymerization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Elaboration of superparamagnetic cobalt–ferrite nanocomposites from films of chitosan chelates

Cobalt–ferrite nanocomposites were synthesized from polymeric films of chelates of Co(II) and Fe(III) ions within a chitosan matrix by a solid‐state coprecipitation reaction with weight content ratios of chitosan to cobalt–ferrite of 50/50 and 25/75 w/w. Morphological and crystalline studies of the composites were performed by high‐resolution transmission electron microscopy, X‐ray diffraction, and selected area electron diffraction with a nanobeam diffraction probe. The results show nanoparticles around 4 nm with a spinel structure, consistent with the cobalt–ferrite phase. The magnetic behavior was evaluated with curves of the applied‐field‐dependent magnetization [M(H)] and the temperature‐dependent magnetization [M(T)]. Both the M(H) and M(T) curves showed typical superparamagnetic behavior, depicting an absence of hysteretic characteristics and the characteristic peak at blocking temperature in the zero‐field‐cooled curve. There was also evidence of strong interparticle and intraparticle interactions, which suggested magnetic frustration in the particle magnetic moment alignment with the applied field. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure‐properties relationship in resol/montmorillonite nanocomposites

Polymer/layered silicate nanocomposites were prepared, adding modified, and nonmodified montmorillonites to a resol resin. It was observed that the composites exhibited an intercalated disordered structure by means of X‐ray diffraction (XRD) and transmission electronic microscopy. The crosslinking density of the resol network was greatly influenced by the presence and type of clay that was added to the resin. The composites filled with the modified montmorillonites showed a lower glass transition temperature value as well as a higher degradation peak at ～ 400°C, which is characteristic of the degradation of methylene bridges, indicating a decrease in the crosslinking density of the resol network when modified clays are added. Resol/unmodified montmorillonite composites exhibited different behavior comparing to the other composites and the resol. A higher thermal resistance was observed in the fragmentation zone and a different tan δ response was seen in the DMA analysis. These differences in the behavior of the composites could be because of the interaction between the resol prepolymer and the clay modifiers and as a result of their chemical compatibility. The hardness and elastic modulus of the resol were improved with the addition of clays. However, higher values were obtained for the composite made with the more dispersed montmorillonite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Crystallization behavior of poly(L‐lactic acid)/montmorillonite nanocomposites

In this study, we modified montmorillonite (MMT) with dilauryl dimethyl ammonium bromide (DDAB) and then exfoliated the structures in a poly(L ‐lactic acid) (PLLA) matrix. We used polar optical microscopy and X‐ray diffraction (XRD) to examine the morphologies of the resulting composites, differential scanning calorimetry to study the melting and crystallization behavior, and Fourier transform infrared (FTIR) and Raman spectroscopy to measure the influence of the intermolecular interactions between PLLA and MMT on the isothermal crystallization temperature. We found that the DDAB‐modified MMT was distributed uniformly in the PLLA matrix. At temperatures ranging from 130 to 140°C, the crystalline morphology resembled smaller Maltese cross‐patterned crystallites; at temperatures from 150 to 170°C, however, the number of crystallites decreased, their sizes increased, and they possessed ringed spherulite structures. In the XRD spectra, the intensity of the diffraction peaks of the 200/110 and 203 facets of the PLLA/MMT nanocomposites decreased as the crystallization temperature increased. In the FTIR spectra, the absorption peak of the C?O groups split into two signals at 1748 and 1755 cm^?1 when the isothermal crystallization temperature was higher than 140°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005     

Phase morphology and clay distribution of poly(trimethylene terephthalate)/polypropylene/montmorillonite nanocomposites

Poly(trimethylene terephthalate) (PTT)/polypropylene (PP) blend nanocomposites were prepared by melt mixing of PTT, PP, and organically modified clay. The phase morphologies of the PTT/PP nanocomposites and the distribution of the clay in the nanocomposites were investigated using scanning electron microscopy, transmission electron microscopy (TEM), and wide angle X‐ray diffraction. When PP is the dispersed phase, the domain size of the PP phase is decreased significantly with increasing the clay content from 0 to 5 wt %. In contrast, when PTT is the dispersed phase, the dimension of the PTT phase is a little larger in the presence of 2 wt % clay compared with the case of without clay. TEM observations indicate that the clay is mainly distributed at the phase interfaces along the phase borderlines. In addition, some intercalated clay tactoids (multilayer particles) are observed in the PTT matrix whereas no discernable clay particles can be found in the PP phase, indicating that the affinity of clay with PTT is higher than with PP. In the presence of 5 wt % PP‐graft‐maleic anhydride, the phase morphology is much finer, and most clay is exfoliated and distributed at the phase interfaces forming phase borderlines in polygonal shape. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Bio‐hybrid nanocomposite coatings from sonicated chitosan and nanoclay

Nanocomposite films and coatings with improved properties were produced from ultrasonic dispersed chitosan and hydrophilic bentonite nanoclay. Bio‐hybrid coatings were applied onto argon–plasma‐activated LDPE coated paper. The intercalation of chitosan in the silicate layers was confirmed by the decrease of diffraction angles as the chitosan/nanoclay ratio increased. Nanocomposite films and multilayer coatings had improved barrier properties against oxygen, water vapor, grease, and UV‐light transmission. Oxygen transmission was significantly reduced under all humidity conditions. In dry conditions, over 99% reduction and at 80% relative humidity almost 75% reduction in oxygen transmission rates was obtained. Hydrophilic chitosan was lacking the capability of preventing water vapor transmission, thus total barrier effect of nanoclay containing films was not more than 15% as compared with pure chitosan. Because to very thin coatings (≤1 μm), nanoclay containing chitosan did not have antimicrobial activity against test strains. All coating raw materials were “generally recognized as safe” (GRAS) and the calculated total migration was in all cases ≤6 mg/dm², thus the coatings met the requirements set by the packaging legislation. Processing of the developed bio‐hybrid nanocomposite coated materials was safe as the amounts of released particles under rubbing conditions were comparable with the particle concentrations in a normal office environment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New method for the synthesis of clay/epoxy nanocomposites

A new liquid–liquid method for the synthesis of epoxy nanocomposites was developed. This new method improved the dispersion and exfoliation of the organoclay in the polymer matrix, thus improving the end‐use properties. The microstructure and physical properties of the clay/epoxy nanocomposite synthesized by the new method were studied. Rheological tests of the uncured epoxy–organoclay system demonstrated that this method resulted in a great increase in viscosity, much more than the most commonly used direct‐mixing method. The Krieger–Dougherty model successfully described the dispersion of the clay layers in the uncured epoxy. In the 5 wt % organoclay nanocomposite, compressive tests on the cured samples showed that there was a 45% increase in the maximum strength, a 10% increase in the yield strength, and a 26% increase in the modulus over the pure epoxy–amine cured system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4286–4296, 2006     

聚合物/蒙脱土纳米复合材料的研究进展

聚合物/蒙脱土纳米复合材料是近十年来研究最为广泛的复合材料之一,优异的热力学性能,独特的气 液阻隔性及阻燃性赋予它广泛的工业应用前景。本文就该复合材料在蒙脱土的有机改性处理、制备、制备条件对性能的影响、表征方法及手段、材料性能特征及应用等方面作一些简单总结。     

Epoxy/montmorillonite nanocomposites: influence of organophilic treatment on reactivity, morphology and fracture properties

Two different alkylammonium modified montmorillonites have been dispersed in epoxy network precursors in order to study the influence of the organophilic treatment on the reactivity and cure behavior of the networks, on the morphology of the final composites and on their elastic and fracture properties. An increase in the interplatelet distance during curing of the network (in addition to the initial swelling by the network precursors) is possible when the competition between cure kinetics, diffusion kinetics and interactions between network precursors and organophilic montmorillonite allows it. Network structure is not modified and a catalytic effect of the organoclays has been demonstrated. Correlation between morphologies and mechanical properties reveals that exfoliated nanocomposites lead to interesting stiffness improvements. However, intercalated nanostructures can lead to very interesting stiffness/toughness balance for glassy epoxy networks without lowering their glass transition temperature. This suggests that stiffness and toughness improvements might not be ruled by the same kind of morphologies.     

The effect of pigments on the stability of silicone/montmorillonite prosthetic nanocomposites

The purpose of this investigation was to evaluate the protection provided to silicone by pigments, such as dry earth pigments. In addition, the effect of nanostructured and organically modified montmorillonite fillers on the overall behavior of reinforced systems was explored. To obtain relevant data and, furthermore, to reveal possible mechanisms of structural changes that could influence silicone stability, pure and reinforced silicon elastomers were mixed with various colorants and studied for their stability to accelerating aging, during the exposure to UV radiation and humidity. A number of tests were run such as, Attenuated Total Reflectance, Fourier Transform Infrared Spectroscopy (ATR‐FTIR), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and Tensile measurements. Swelling in toluene and color tests were also carried out. The experimental results showed that the UV aging of silicone elastomers results in chain scission and cross‐linking rather than formation of oxygen containing groups. The main conclusion of this work is montmorillonite acts as a significant reinforcement and protects silicone against degradation during exposure to UV irradiation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rapid synthesis of poly(p-dioxanone)/montmorillonite nanocomposites under microwave irradiation

A rapid and “green” synthesis of poly(p-dioxanone) (PPDO)/montmorillonite (MMT) nanocomposites was carried out smoothly and effectively nder constant microwave powers of 30, 60, 90, and 120 W in a microwave oven at a frequency of 2.45 GHz. The temperature of polymerization was in the range 103–224°C. PPDO, with a viscosity-average molecular weight of 111,000 g/mol and a conversion of 85%, was obtained at 60 W for 10 min, in which the ratio of p-dioxanone to AlEt₃ was 300/1 (mol/mol). The intercalated structure of PPDO/MMT nanocomposites was confirmed by X-ray diffraction and transmission electron microscopy. Thermogravimetry data showed that the thermal stability of the nanocomposites prepared under microwave irradiation was improved with respect to those prepared via conventional heating. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of organophilic montmorillonite on polyurethane/montmorillonite nanocomposites

Different kinds of organophilic montmorillonite cotreated by cetyltrimethyl ammonium bromide (CTAB) and aminoundecanoic acid (AUA) were synthesized and applied to prepare polyurethane/montmorillonite nanocomposites via solution intercalation. The results of wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy showed that, for the montmorillonite modified with CTAB and CTAB/AUA (molar ratio of 1/2), an ordered intercalated nanostructure was derived, while for the montmorillonite treated with AUA, a disordered nanostructure was derived. The tensile properties of the polyurethane (PU) nanocomposites showed higher enhancement relative to PU matrix. TG showed that there is some enhancement in degradation behavior between the nanocomposites and PU matrix. DMTA results showed that nanocomposites from some organophilic montmorillonites showed a much higher storage modulus below and above glass transition temperature, while the nanocomposites from montmorillonite treated by AUA show an even lower storage modulus. The loss curves showed that the main glass transition temperature of PU was improved to some extent for the nanocomposites. The water absorption of PU and nanocomposites was also studied and the difference in reduction was thoroughly analyzed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2536–2542, 2004     

Synthesis of resol–layered silicate nanocomposites by reaction exfoliation with acid‐modified montmorillonite

Resol–layered silicate nanocomposites were prepared by the intercalative polymerization of phenol and formaldehyde in the presence of acid‐modified montmorillonite (HMMT). The nanocomposites were studied by means of X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), and rheological measurements. The exfoliation of HMMT was promoted by the intragallery reactions catalyzed by protons in the galleries of the clay, whereas the extragallery polymerization catalyzed by ammonia went on simultaneously. The nanocomposites showed higher glass‐transition temperatures in the DMA diagram compared with the resol counterparts. The impact strength was improved significantly by the incorporation of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 791–797, 2004     

Preparation of polyethylene–clay nanocomposites directly from Na+ montmorillonite by a melt intercalation method

Polyethylene (PE)/clay nanocomposites were prepared directly from Na⁺ montmorillonite by a melt intercalation technique, using hexadecyl trimethyl ammonium bromide (C16) as a reactive compatibilizer. Three other polymer–clay nanocomposites were also prepared by this new technique. Their structures were characterized by X‐ray diffraction and transmission electron microscopy. The mechanism of this new method was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2583–2585, 2003     

Biodegradable nanocomposites based on starch/polycaprolactone/compatibilizer ternary blends reinforced with natural and organo‐modified montmorillonite

In this article, biodegradable polymer/clay nanocomposites were prepared. The matrices used were based on blends of Polycaprolactone (PCL) and Anhydride‐Functional Polycaprolactone (PCL‐gMA) with Thermoplastic Starch (TPS). Nanocomposites films based on PCL/TPS and PCL/PCL‐g‐MA/TPS blends reinforced with 1 and 3 wt % of natural montmorillonite and two organo‐modified ones were prepared by melt intercalation followed by compression molding. The study was designed focusing on packaging applications. Grafting maleic anhydride onto PCL was efficient to improve PCL/TPS compatibility but did not modify matrix/nanoclay interaction. Matrix compatibilization and nanoclays increased the Youn?s modulus and slightly decreased the maximum stress of the TPS/PCL matrix. Nanoclay functionalization improved nanoclay dispersion in the blends but it was not reflected in mechanical properties improvements. The water adsorption of the compatibilized matrix was reduced after clay incorporation. A slight decrease in the biodegradation rate was observed with the addition of nanoclay. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44163.