Elastomeric epoxy nanocomposites: Nanostructure and properties

In polymer layered silicate nanocomposites, significant differences have been reported between the effects of the nano-reinforcement on rigid and elastomeric nanocomposites. In this paper, we have studied elastomeric nanocomposites based upon DGEBA epoxy resin filled with montmorillonite (MMT) and cured with a long-chain polyoxypropylene diamine, for comparison with analogous rigid nanocomposites. Ultrasonic mixing was used to disperse the MMT in the matrix to improve homogeneity and decrease the agglomerate size. Two different methods of nanocomposite preparation were used in which the MMT was first swollen with either the curing agent or the epoxy before the addition of, respectively, DGEBA or diamine. A better dispersion of the nanoclay in the matrix and a greater amount of intercalation occurred when the MMT was first swollen with the diamine. The effect of MMT concentrations up to 8 wt.% on the mechanical behaviour of the epoxy/MMT nanocomposites was investigated. It was found that the addition of MMT increased the tensile strength and modulus, although SAXS and TEM indicated that a significant fraction of the clay layers were not exfoliated. Nevertheless, the addition of the clay resulted in changes in the fracture surfaces, as indicated by SEM, consistent with the tensile results and indicative of toughening.     

Thermal properties of PMMA/montmorillonite clay nanocomposites

Polymer/Clay offer tremendous improvement in wide range of physical and engineering properties for polymers with low filler loading. In nanotechnology polymer/clay nanocomposites use smectitetype clays that have layered structures. In this work, Poly (methyl methacrylate) (PMMA) was synthesized by free radical addition polymerization in the presence of high power ultrasound. The Poly (methyl methacrylate) (PMMA)-Montmorillonite (MMT) clay nanocomposites were synthesized by two different techniques viz., ultrasonic mixing and magnetic stirring. An analysis of the XRD data confirms that the composites are in the nanometer scale. The FTIR spectra show that there is strong interaction between the clay and the polymer that enhances the thermal stability. The thermal stability of the experimental nanocomposite prepared by the two processes is compared. Further analysis of XRD data shows that intercalation as well as exfoliation has taken place in both the types of nanocomposites preparation. An analysis of the TG, DTG curves reveal that the thermal stability is found to increase by nearly 30% for ultrasonic mixing than that of magnetic stirring.     

Improving the mechanical properties of thermoplastic starch/poly(vinyl alcohol)/clay nanocomposites

Thermoplastic starch/poly(vinyl alcohol) (PVOH)/clay nanocomposites, exhibiting the intercalated and exfoliated structures, were prepared via melt extrusion method. The effects of clay cation, water, PVOH and clay contents on clay intercalation and mechanical properties of nanocomposites were investigated. The experiments were carried out according to the Taguchi experimental design method. Montmorillonite (MMT) with three types of cation or modifier (Na⁺, alkyl ammonium ion, and citric acid) was examined. The prepared nanocomposites with modified montmorillonite indicated a mechanical improvement in the properties in comparison with pristine MMT. It was also observed that increases in tensile strength and modulus would be attained for nanocomposite samples with 10%, 5% and 4% (by weight) of water, PVOH and clay loading, respectively. The clay intercalation was examined by X-ray diffraction (XRD) patterns. The chemical structure and morphology of the optimum sample was also probed by FTIR spectroscopy and transmission electron microscopy (TEM).     

Effect of processing parameters and clay volume fraction on the mechanical properties of epoxy-clay nanocomposites

The influence of processing parameters and particle volume fraction was experimentally studied for epoxy clay nanocomposites. Nanocomposites were prepared using onium ion surface modified montmorillonite (MMT) layered clay and epoxy resin (DEGBF). Two different techniques were used for dispersing the clay particles in the epoxy matrix, viz. high-speed shear dispersion and ultrasonic disruption. The volume fraction of clay particles was systematically varied from 0.5 to 6%, and mechanical properties, viz. flexural modulus and fracture toughness, were studied as a function of clay volume fraction and the processing technique. The flexural modulus was observed to increase monotonously with increase in volume fraction of clay particles, while, the fracture toughness showed an initial increase on addition of clay particles, but a subsequent decrease at higher clay volume fractions. In general, nanocomposites processed by shear mixing exhibited better mechanical properties as compared to those processed by ultrasonication. Investigation by X-ray diffraction (XRD) revealed exfoliated clay structure in most of the nanocomposites that were fabricated. Morphologies of the fracture surfaces of nanocomposites were studied using a scanning electron microscopy (SEM). Presence of river markings at low clay volume fractions provided evidence of extrinsic toughening taking place in an otherwise brittle epoxy.     

Effects of modified Clay on the morphology and thermal stability of PMMA/clay nanocomposites

The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/clay nanocomposites prepared with clay containing an organic modifier was investigated. Pristine sodium montmorillonite clay was modified using cocoamphodipropionate, which absorbs UVB in the 280–320 nm range, via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. PMMA/clay nanocomposites were synthesized via in situ free-radical polymerization. Three types of clay with various cation-exchange capacities (CEC) were used as inorganic layered materials in these organic–inorganic hybrid nanocomposites: CL42, CL120, and CL88 with CEC values of 116, 168, and 200 meq/100 g of clay, respectively. We characterized the effects of the organoclay dispersion on UV resistance, effectiveness as an O₂ gas barrier, thermal stability, and mechanical properties of PMMA/clay nanocomposites. Gas permeability analysis demonstrated the excellent gas barrier properties of the nanocomposites, consistent with the intercalated or exfoliated morphologies observed. The optical properties were assessed using UV–Visible spectroscopy, which revealed that these materials have good optical clarity, UV resistance, and scratch resistance. The effect of the dispersion capability of organoclay on the thermal properties of PMMA/clay nanocomposites was investigated by thermogravimetric analysis and differential scanning calorimetry; these analyses revealed excellent thermal stability of some of the modified clay nanocomposites.     

Thermal, mechanical and vibration characteristics of epoxy-clay nanocomposites

Diglycidyl ether of bisphenol-A (DGEBA) epoxy resin system filled individually with organoclay (OC) and unmodified clay (UC) were synthesized by mechanical shear mixing with the addition of diamino-diphenylmethane (DDM) hardener. The unmodified clay used was Na⁺-Montmorillonite (MMT) and the organoclay was alkyl ammonium treated MMT clay. The reinforcement effect of OC and UC in the epoxy polymer on thermal, mechanical and vibration properties were studied. X-ray diffraction (XRD) and Transmission electron microscopy (TEM) were used to study the structure and morphology of nanocomposites. Curing study shows that the addition of OC in epoxy resin aids the polymerization by catalytic effect, and UC addition does not show any effect in the curing behavior of epoxy polymer. Thermogravimetry analysis (TGA) shows enhanced thermal stability for epoxy with OC fillers than that of epoxy with UC fillers. The epoxy with OC fillers shows considerable improvement on tensile and impact properties over pure epoxy polymer and epoxy with UC fillers. The improvement in tensile and impact properties of nanocomposites is supported with the fracture surface studies. Epoxy with OC fillers shows enhanced vibration characteristics than that of the pure epoxy polymer and epoxy with UC fillers.     

Preparation and characterization of poly (styrene-acrylonitrile) (SAN)/clay nanocomposites by melt intercalation

Poly (styrene-acrylonitrile) (SAN)/clay nanocomposites have been prepared by melt intercalation method from pristine montmorillonite (MMT), using hexadecyl trimethyl ammonium bromide (C16) and hexadecyl triphenyl phosphonium bromide (P16) as the reactive compatibilizers between polymer and clay. The influence of the reactive compatibilizers proportion relative to the clay on the structure and properties of the SAN/clay nanocomposites is investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), high-resolution electron microscopy (HREM), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The effects of the two different clays (MMT and organic modified MMT) on the nanocomposites formation, morphology and property are also studied. The results indicate that the SAN cannot intercalate into the interlayers of the MMT and results in microcomposites. In the presence of the reactive compatibilizers, the dispersion of clay in SAN is rather facile and the SAN/clay nanocomposites reveal an intermediate morphology, an intercalated structure with some exfoliation and the presence of small tactoids. The appropriate proportion with 3 wt% reactive compatibilizers to 5 wt% MMT induces well-dispersed morphology and properties in the SAN matrix. The TGA analyses show that the thermal stability properties of the SAN/clay nanocomposites have been improved compared with those of the pristine SAN. The DMA results show that the storage modulus and glass transition temperature (Tg) of the SAN/clay nanocomposites have remarkably enhancements compared with the pristine SAN. At last the intercalation mechanism of the technology is discussed.     

Dielectric properties of montmorillonite clay filled poly(vinyl alcohol)/poly(ethylene oxide) blend nanocomposites

Organic–inorganic nanocomposites of poly(vinyl alcohol) (PVA)–poly(ethylene oxide) (PEO) blend filled with montmorillonite (MMT) nanoclay up to 10 wt.% concentration were synthesized by aqueous solution-cast technique. The complex dielectric function, electrical conductivity, electric modulus and impedance spectra of the nanocomposites were measured in the frequency range 20 Hz–1 MHz at ambient temperature. A direct correlation was observed between the real part of dielectric function and the mean relaxation time of the polymer chain segmental dynamics, with the exfoliated and intercalated MMT clay structures, and the extent of miscibility between PVA and PEO due to hydrogen bonded bridging through exfoliated MMT clay nanosheets. The large increase of dielectric relaxation time revealed that the dispersed exfoliated nanoscale MMT clay in the polymers blend matrix produces a large hindrance to the polymer chain dynamics. Results confirm that the real part of dielectric function of the nanocomposites can be tailored by varying amount of MMT clay filler for their use as nanodielectric materials in the microelectronic technology.     

Organophosphorus and DGEBA resins containing clay nanocomposites: flame retardant,thermal, and mechanical properties

Flame-retardant nanocomposites were prepared from diglycidylphenylphosphate (DGPP) and modified montmorillonite (MMT) clay blended with DGEBA in different ratio. T _g of all formulations increased with increasing clay content in the respective series while decreasing with increasing DGPP content. The TGA, LOI, and UL-94 data of all nanocomposites indicated that the materials were thermally stable with high flame retardancy resulting from synergetic effect of phosphorus and inorganic clay. The XRD analysis of the nanocomposites with 1 and 2% of clay indicated the intercalation of clay while rest of the samples displayed exfoliation at high clay content. As compared to neat epoxy system, a maximum increase of 59.3, 45.5, and 93% of tensile, flexural, and impact strengths were observed for the prepared nanocomposites. The SEM analysis of the failure surfaces of all DGPP containing samples showed rough with ridge patterns and river markings on the fracture surface that serves in improving the mechanical properties.     

熔融挤出插层制备聚丙烯/蒙脱土纳米复合材料的探讨(Ⅰ)

通过双螺杆挤出机熔融挤出法制备出插层型聚丙烯/蒙脱土纳米复合材料。利用有机蒙脱土的预凝胶测试,复合材料的透射电子显微镜(TEM)观察,熔体流动指数测试(M I),力学性能测试,耐热性测试等方法进行了表征。结果表明,通过本方法制备的聚丙烯/蒙脱土复合材料是典型的插层型纳米复合材料。该复合材料在有机蒙脱土质量分数仅为4.0%时缺口冲击强度提高了103%,耐热性有所提高,而屈服强度、刚性基本不变,为研制PPR管等同时具有高韧性和高耐热性的聚丙烯产品开辟了一条崭新的途径。     

Synergistic effect of montmorillonite–clay and gamma irradiation on the characterizations of waste polyamide copolymer and reclaimed rubber powder nanocomposites

A study on the mechanical properties and thermal evolution of waste polyamide copolymer/waste rubber powder and montmorillonite–clay (WPA/RRP/MMT) nanocomposites exposed to gamma-rays (0–200 kGy) has been carried out. TGA and DSC were used to investigate the influence of the exposure dose and the incorporation of montmorillonite–clay on the thermal parameters of the prepared composites. It was observed that both parameters were highly affected by the incorporated clay and dose. The structural and morphological studies were done by means of EDX and SEM to investigate the structural change imputed by the clay incorporation and irradiation. The chemical absorption behavior of MMT nanocomposites in HCl and NaOH media was investigated. The results show that irradiation markedly magnified the thermal stability and the tensile strength of the nanocomposite.     

Environmentally friendly polymer hybrids Part I Mechanical, thermal, and barrier properties of thermoplastic starch/clay nanocomposites

As an attempt to develop environmentally friendly polymer hybrids, biodegradable thermoplastic starch (TPS)/clay nanocomposites were prepared through melt intercalation method. Natural montrorillonite (Na⁺ MMT; Cloisite Na⁺) and one organically modified MMT with methyl tallow bis-2-hydroxyethyl ammonium cations located in the silicate gallery (Cloisite 30B) were chosen in the nanocomposite preparation. TPS was prepared from natural potato starch by gelatinizing and plasticizing it with water and glycerol. The dispersion of the silicate layers in the TPS hybrids was characterized by using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). It was observed that the TPS/Cloisite Na⁺ nanocomposites showed higher tensile strength and thermal stability, better barrier properties to water vapor than the TPS/Cloisite 30B nanocomposites as well as the pristine TPS, due to the formation of the intercalated nanostructure. The effect of clay contents on the tensile, dynamic mechanical, and thermal properties as well as the barrier properties of the nanocomposites were investigated.     

Synthesis and biological evaluation of PMMA/MMT nanocomposite as denture base material

Inorganic-polymer nanocomposites are of significant interest for emerging materials due to their improved properties and unique combination of properties. Poly (methylmethacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization with dodecylamine used as MMT-modifier. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the structures of the nanocomposites. Cytotoxicity test, hemolysis test, acute systemic toxicity test, oral mucous membrane irritation test, guinea-pig maximization test and mouse bone-marrow micronucleus test were used to evaluate the biocompatibility of PMMA/MMT nanocomposites. The results indicated that an exfoliated nanocomposite was achieved, and the resulting nanocomposites exhibited excellent biocompatibility as denture base material and had potential application in dental materials.     

聚氨酯/蒙脱土纳米复合弹性体材料--(Ⅱ)结构及性能的表征

借助锥体磨的研磨剪切外力，将聚醚多元醇插层进入蒙脱土片层中，使其片层间距扩大并发生部分剥离，从而利用本体插层聚合法制备了综合性能优异的聚氨酯／蒙脱土纳米复合弹性体材料。当有机蒙脱土添加量仅为1％时，其拉伸强度比纯聚氨酯弹性体高30％．达到30．2MPa，断裂伸长率也略有增加。TGA及吸水实验分析表明聚氨酯／蒙脱土纳米复合材料有更高的热失重温度和更低的吸水率．研究了蒙脱土含量对聚氨酯／蒙脱土纳米复合材料各项性能的影响。     

Chlorinated polyethylene nanocomposites: thermal and mechanical behavior

Chlorinated polyethylene (CPE) nanocomposites prepared with natural and organically treated montmorillonite (MMT) clays by solution intercalation method were investigated. X-ray diffraction and transmission electron microscopy techniques showed separation of organically modified clay MMT layers and indicated formation of exfoliated nanocomposites. Fourier transform infrared spectroscopy results showed interaction between the CPE matrix and the clay intercalants of Cloisite^® 30B and Cloisite^® 15A (natural MMT modified with quaternary ammonium salts). Organically treated MMT clays were found to be better dispersed in CPE in comparison to natural MMT clay. Mechanical testing showed enhanced tensile strength, Young’s modulus, and storage modulus of chlorinated-polymers/organically treated MMT clay nanocomposites. Significant improvements in the above properties were obtained with Cloisite^® 15A nanoclay. The temperature, at which maximum degradation occurred, was higher for the nanocomposite having 5 wt% Cloisite 15A than that of neat CPE. Differential scanning calorimetric results revealed that the same composition also absorbed more heat during the heating, indicating better thermal stability. CPE rubber nanocomposite could be a promising heat resistant polymeric material.     

Morphological and thermomechanical characterization of thermoplastic starch/montmorillonite nanocomposites

A combination of starch and clay for the preparation of nanocomposite materials is proposed. In this work, starch was plasticized by pequi (Caryocar brasiliense) oil, and thermoplastic starch (TPS)/montmorillonite (MMT) nanocomposites were analyzed by X-ray diffraction (XRD), thermogravimetry (TG), thermomechanical analyses (TMA) and scanning electron microscopy (SEM). Exfoliated and intercalated nanocomposites were found to be dependent on MMT content. Exfoliation is the predominant mechanism of clay dispersion for low filler loading. Increase of the clay loading (>5 wt.%) causes intercalation. The introduction of low content (?5 wt.%) of MMT improves the thermal stability and the stiffness of the materials. There is a limit content of clay that can be added to improve the thermal and thermomechanical properties of the composites. Beyond that value the composite presents properties below the original polymer.     

Preparation and characterization of poly(methyl methacrylate)-clay nanocomposites via melt intercalation: Effect of organoclay on thermal, mechanical and flammability properties

The PMMA nanocomposites were prepared by melt processing method. The influence of organoclay loading on extent of intercalation, thermal, mechanical and flammability properties of poly(methyl methacrylate) (PMMA)-clay nanocomposites were studied. Three different organoclay modifiers with varying hydrophobicity (single tallow vs. ditallow) were investigated. The nanocomposites were characterized by using wide angle X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. The intercalation of polymer chain within the silicate galleries was confirmed by WAXD and TEM. Mechanical properties such as tensile modulus (E), tensile strength, percentage elongation at break and impact strength were determined for nanocomposites at various clay loadings. Overall thermal stability of nanocomposites increased by 16-17 °C. The enhancement in T_g of nanocomposite is merely by 2-4 °C. The incorporation of maleic anhydride as compatibilizer further enhanced all the properties indicating improved interface between PMMA and clay. The flammability characteristics were studied by determining the rate of burning and LOI.     

PBAT based nanocomposites for medical and industrial applications

Poly(butylene adipate-co-terephthalate) (PBAT) based nanocomposites were prepared by melt blending PBAT with 5 and 10 wt.% of clay nanoparticles (unmodified and modified montmorillonites, unmodified and modified fluoro-hectorites, and unmodified sepiolites). All nanocomposites showed a good level of clay distribution and dispersion into PBAT, especially nanocomposites with high clay chemical affinity with the polymer matrix. DSC results showed that addition of layered silicates slightly hindered kinetics and extent of crystallization of PBAT; however, sepiolite particles were able to promote polymer crystallization kinetics and the transformation of the PBAT crystal structure to a more ordered form.Similar increases in the thermal stability of PBAT in nitrogen and air were obtained upon addition of all clays, due to a barrier effect of the clays toward polymer decomposition product ablation.Preliminary biocompatibility tests indicated that PBAT based materials with 10% clay content have good biological safety and display almost no cytotoxicity.The addition of all nanofillers increased the hardness of PBAT matrix. The DMA analysis showed that all nanocomposites presented higher E′ values than neat PBAT, indicating that addition of clays improved the mechanical properties of PBAT. For layered silicate nanocomposites, the main influencing factors on the thermo-mechanical properties appeared to be the aspect ratio and dispersion of clay nanoplatelets, rather than polymer/clay chemical affinity. The highest E′ values of sepiolite based nanocomposites make this nanoparticle the most attractive material for tissue engineering and environmental industrial applications.     

Study on fracture behavior of surface treated montmorillonite/epoxy nanocomposites

It is known that the mechanical properties of clay-reinforced nanocomposites are significantly affected by the dispersion of clay particles in the matrix. In this study, the effect of surface-treatment of Montmorillonite (MMT) on the fracture behavior of MMT/epoxy nanocomposite was investigated. For this purpose, fracture tests were performed using samples with three different clay concentration level. After fracture tests, SEM analysis was made on the fracture surfaces to examine the fracture mechanism. It was found that the MMT treatment using 3-aminopropyltriethoxysilane enhanced the fracture toughness increased of the MMT/epoxy nanocomposite. This is due to the improved intercalation effect and interfacial strength between MMT and epoxy matrix.     

Enhanced ductility and tensile properties of hybrid montmorillonite/cellulose nanowhiskers reinforced polylactic acid nanocomposites

Montmorillonite (MMT)/cellulose nanowhiskers (CNW) reinforced polylactic acid (PLA) hybrid nanocomposites were prepared by solution casting. CNW were isolated from microcrystalline cellulose using a chemical swelling method. An initial study showed that the optimum MMT content, for mechanical properties, in a PLA/MMT nanocomposite is five parts per hundred parts of polymer (phr). Various amounts of CNW were added to the optimum formulation of PLA/MMT to produce PLA/MMT/CNW hybrid nanocomposites. FT-IR analysis indicated the formation of some polar interactions, resulting in enhanced tensile properties of the hybrid nanocomposites. The highest tensile strength for the hybrid nanocomposites was obtained for a 1 phr CNW content. Young’s modulus was also found to increase with an increasing CNW content. Interestingly, the strain to failure (or ductility) of the hybrid nanocomposites increased significantly from ~10 to ~90 % with the addition of 1 phr CNW. This increase in ductility was proposed to be due to the nucleation of crazes and the formation of shear bands in the PLA.