Influence of Fe‐MMT on crosslinking and thermal degradation in silicone rubber/clay nanocomposites

In this article, silicone rubber (SR)/clay nanocomposites were synthesized by a melt‐intercalation process using synthetic Fe‐montmorillonite (Fe‐MMT) and natural Na‐MMT which were modified by cetyltrimethyl ammonium bromide (CTAB). This study has been designed to determine if the presence of structural iron in the matrix can result in radical trapping and then enhance thermal stability, affect the crosslinking degree and elongation. The SR/clay nanocomposites were characterized by X‐ray diffraction (XRD) patterns and transmission electron microscopy (TEM). Exfoliated and intercalated nanocomposites were obtained. Thermo gravimetric analysis (TGA) and mechanical performance were applied to test the properties of the SR/clay nanocomposites. The presence of iron significantly increased the onset temperature of thermal degradation in SR/Fe‐MMT nanocomposites. The thermal stability, gel fraction and mechanical property of SR/Fe‐MMT were different from the SR/Na‐MMT nanocomposites. So the iron not only in thermal degradation but in the vulcanization process acted as an antioxidant and radicals trap. Copyright © 2006 John Wiley & Sons, Ltd.     

Shear‐induced change of exfoliation and orientation in polypropylene/montmorillonite nanocomposites

For the improved dispersion of montmorillonite (MMT) in a polypropylene (PP) matrix, PP/MMT nanocomposites prepared via direct melt intercalation were further subjected to oscillating stress achieved by dynamic packing injection molding. The shear‐induced morphological changes were investigated with an Instron machine, wide‐angle X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The original nanocomposites possessed a partly intercalated and partly exfoliated morphology. A transformation of the intercalated structure into an exfoliated structure occurred after shearing, and a more homogeneous dispersion of MMT in the PP matrix was obtained. However, the increase of the exfoliated structure was accompanied by the scarifying of the orientation of MMT layers along the shear direction. Some bended or curved MMT layers were found for the first time by TEM after shearing. However, the orientation of PP chains in the PP/MMT nanocomposites became very difficult under an external shear force; this indicated that the molecular motion of PP chains intercalated between MMT layers was highly confined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1–10, 2003     

Isothermal crystallization behavior of exfoliated‐PP/IMMT nanocomposites via in situ polymerization

Highly exfoliated isotactic‐polypropylene/alkyl‐imidazolium modified montmorillonite (PP/IMMT) nanocomposites have been prepared via in situ intercalative polymerization. TEM and XRD results indicated that the obtained composites were highly exfoliated PP/IMMT nanocomposites and the average thickness of IMMT in PP matrix was less than 10 nm, and the distance between adjacent IMMT particles was in the range of 20–200 nm. The isothermal crystallization kinetics of highly exfoliated PP/IMMT nanocomposites were investigated by using differential scanning calorimeter(DSC) and polarized optical microscope (POM). The crystallization half‐time t_1/2, crystallization peak time t_max, and the Avrami crystallization rate constant K_n showed that the nanosilicate layers accelerate the overall crystallization rate greatly due to the nucleation effect, and the crystallization rate was increased with the increase in MMT content. Meanwhile, the crystallinity of PP in nanocomposites decreased with the increase in clay content which indicated the PP chains were confined by the nanosilicate layers during the crystallization process. Although the well‐dispersed silicate layers did not have much influence on spherulites growth rate, the nucleation rate and the nuclei density increased significantly. Accordingly, the spherulite size decreased with the increase in MMT content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2215–2225, 2009     

The influence of multiple modified MMT on the thermal and fire behavior of poly (lactic acid) nanocomposites

This work reported the preparation and physical properties of biodegradable nanocomposites fabricated using polylactic acid (PLA) and multiple organic modified montmorillonite (MMT). In order to improve the chemical compatibility between PLA and Na‐MMT, the surface of Na‐MMT was first organically modified by cetyl trimethyl ammonium bromide (CTAB) and resorcinol bis(diphenyl phosphate) (RDP) using ion‐exchange and adsorption technique. Both Fourier transform infrared and X‐ray diffraction (XRD) results indicated that CTAB and RDP molecules were intercalated into the galleries of MMT sheets to enlarge the interlayer spacing. Then, the PLA/MMT nanocomposites were prepared by a simple melt‐blending method. The XRD and TEM results of the nanocomposites indicated that the PLA polymer chains inserted into the galleries of co‐modified MMT (C‐MMT) and contained disorderedly intercalated layered silicate layers within a PLA matrix. The C‐MMT nanolayers were homogenously dispersed in PLA matrix, resulting in various property enhancement. The fabricated PLA/C‐MMT nanocomposites with 5.0 wt% addition showed significant enhancements (176%) in the storage modulus compared to that of neat PLA. The thermal stability and fire resistance were also remarkably improved. These improvements are probably because of both the physical barrier effect of the MMT nanosheets and charring effect of the C‐MMT. Copyright © 2015 John Wiley & Sons, Ltd.     

Layered silicate/epoxy nanocomposites: synthesis,characterization and properties

Novel epoxy‐clay nanocomposites have been prepared by epoxy and organoclays. Polyoxypropylene triamine (Jeffamine T‐403), primary polyethertriamine (Jeffamine T‐5000) and three types of polyoxypropylene diamine (Jeffamine D‐230, D‐400, D‐2000) with different molecular weight were used to treat Na‐montmorillonite (MMT) to form organoclays. The preparation involves the ion exchange of Na⁺ in MMT with the organic ammonium group in Jeffamine compounds. X‐ray diffraction (XRD) confirms the intercalation of these organic moieties to form Jeffamine‐MMT intercalates. Jeffamine D‐230 was used as a swelling agent for the organoclay and curing agent. It was established that the d₀₀₁ spacing of MMT in epoxy‐clay nanocomposites depends on the silicate modification. Although XRD data did not show any apparent order of the clay layers in the T5000‐MMT/epoxy nanocomposite, transmission electron microscopy (TEM) revealed the presence of multiplets with an average size of 5 nm and the average spacing between multiplets falls in the range of 100 Å. The multiplets clustered into mineral rich domains with an average size of 140 nm. Scanning electron microscopy (SEM) reveals the absence of mineral aggregate. Nanocomposites exhibit significant increase in thermal stability in comparison to the original epoxy. The effect of the organoclay on the hardness and toughness properties of crosslinked polymer matrix was studied. The hardness of all the resulting materials was enhanced with the inclusion of organoclay. A three‐fold increase in the energy required for breaking the test specimen was found for T5000‐MMT/epoxy containing 7 wt% of organoclay as compared to that of pure epoxy. Copyright © 2004 John Wiley & Sons, Ltd.     

Polyurethane/montmorillonite nanocomposites prepared from crystalline polyols, using 1,4-butanediol and organoclay hybrid as chain extenders

Polyurethane/montmorillonite (PU/MMT) nanocomposites were prepared via in situ polymerization from highly crystalline poly(butylene succinate)/poly(ethylene glycol) polyols and 4,4^′-dicyclohexylmethane diisocyanate, using both 1,4-butanediol and 1, 2, or 3 wt.% of a tris(hydroxymethyl)aminomethane-MMT hybrid, as chain extenders. The corresponding nanocomposites were designated PU-1MMT, PU-2MMT and PU-3MMT, respectively. The layered silicates were mostly intercalated in the nanocomposites. The distances between the individual silicate layers in the PU-1MMT and PU-2MMT were in the range of 2-10 nm, while those in the PU-3MMT were only about 2 nm. The inefficient exfoliation of the clay in this system was mainly due to the high crystallinity and polarity of the PBS polyol. There were no significant changes in the thermal properties of the pure PU and PU nanocomposites. However, the tensile modulus and elongation of the PU-2MMT at break were significantly greater than those of the pure PU and PU-3MMT.     

Synthesis of exfoliated isotactic polypropylene/functional alkyl-triphenylphosphonium-modified clay nanocomposites by in situ polymerization

Diphenyl (4-hydroxyphenyl) hexadecyl phosphonium bromide (POH) -modified montmorillonite (POHMMT) was used to prepare a novel TiCl₄/MgCl₂/POHMMT compound catalyst and exfoliated iPP/POHMMT nanocomposites were prepared by the in situ intercalative polymerization of propylene with the TiCl₄/MgCl₂/POHMMT compound catalyst. The POH surfactants don’t change the catalytic characteristic of the Z-N catalyst and the obtained PP presents high isotacticity, normal molecular weight and molecular weight distribution. The WAXD, SAXS and TEM results demonstrate the highly exfoliated iPP/POHMMT nanocomposites were produced by the in situ polymerization with this novel catalyst, while the intercalated iPP/Na⁺MMT nanocomposites were produced with the TiCl₄/MgCl₂/Na⁺MMT compound catalyst. Through this approach, in situ propylene polymerization can actually take place between the silicate layers and lead not only to PP with high isotacticity and molecular weight, but also to highly exfoliated PP nanocomposites.     

STRUCTURAL EVOLUTION AND COMPOSITION CHANGE IN THE SURFACE REGION OF POLYPROPYLENE/CLAY NANOCOMPOSITES ANNEALED AT HIGH TEMPERATURES

A model experiment was done to clear the formation mechanism of protective layers during combustion of polypropylene(PP)/organically modified montmorillonite(OMMT) nanocomposites.The investigation was focused on the effects of annealing temperature on the structural changes and protective layer formation.The decomposition of OMMT and degradation of PP/OMMT nanocomposites were characterized by means of thermogravimetric analysis(TGA).The structural evolution and composition change in the surface region of...     

Synthesis and Rheology of Intercalated Polystyrene/Na+‐Montmorillonite Nanocomposites

Polystyrene (PS)/clay nanocomposites were synthesized by the emulsion polymerization of styrene in the presence of sodium ion‐exchanged montmorillonite (Na⁺‐MMT), demonstrating that the strongly hydrophobic PS was intercalated into the hydrophilic silicate layers. The nanocomposites were examined by means of X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis. The rheological properties of the PS/Na⁺‐MMT nanocomposites were also studied to exhibit more pronounced shear thinning behavior with increasing clay content.     

Synergistic effect of organophilic Fe-montmorillonite on flammability in polypropylene/intumescent flame retardant system

Polypropylene/intumescent flame retardant/organophilic Fe-montmorillonite (PP/IFR/Fe-OMT) nanocomposites were prepared by melting intercalation. In order to investigate the effect of structural Fe³⁺ in the PP/IFR system, the corresponding PP/IFR and PP/IFR/Na-OMT composites were prepared under the same conditions. The thermo-gravimetric analysis data show that the PP/IFR/Fe-OMT nanocomposites have higher thermal stability than the PP/IFR and PP/IFR/Na-OMT composites. The flame retardant results indicate that the limiting oxygen index values of the nanocomposites with Fe-OMT are basically higher than those of the pure PP and the composites containing IFR or Na-OMT/IFR. And the addition of a suitable amount of Fe-OMT in PP/IFR composites can apparently favor UL94 test, and no dripping phenomenon was found. The cone calorimeter test indicates that the heat release rate (HRR) is significantly reduced by the formation of the nanocomposites, and the HRR of the PP/IFR/Fe-OMT nanocomposites are decreased in comparison with those of the PP/IFR/Na-OMT nanocomposites. It is noteworthy that Fe-OMT is helpful to smoke suppression by smoke density test.     

Kinetics of thermo-oxidative degradation of polypropylene/aluminum trihydroxide/organo Fe-montmorillonite nanocomposites

In the article, the thermal oxidative degradation kinetics of pure polypropylene/aluminum trihydroxide (PP/ATH) and PP/ATH/organo Fe-montmorillonite (Fe-OMT) nanocomposites were investigated using Kissinger, Friedman and Flynn–Wall–Ozawa methods. The results showed that thermal oxidative degradation of PP/ATH/Fe-OMT nanocomposites to PP/ATH were complex reaction: the whole process of thermal oxidative degradation were composed with the decomposition of ATH, the cracking and charring of the backbone chains of PP, and the oxidative degradation of char, which the curses of energy mutative with the process of thermal oxidative degradation. The control steps were different in each degradation stage. The activation energy was high in the original degradation stage. It was due to the molecular structure and may closely relate with onset temperature. In the intermediate process, the activation energy was low. In the last stage of the degradation, the activation energy was graveled because the carbon may be oxidized. In the whole process of thermal oxidative degradation, the activation energy of PP/ATH/Fe-OMT nanocomposite was higher than that of PP/ATH.     

插层聚合制备聚丙烯/蒙脱土纳米复合材料及其结构性能表征

将插层聚合的概念引入烯烃聚合,制备了聚丙烯／蒙脱土（PP／MMT）纳米复合材料。X射线衍射和TEM分析结果表明,蒙脱土在聚丙烯基体中达到了纳米级的分散,动态力学性能研究结果表明,在高于Tg的温度区域内PP／MMT纳米复合材料的储能模量（E′）成倍增加,加入8％的蒙脱土（MMT）,PP／MMT的E′提高近3倍。PP／MMT的玻璃化转变温度Tg有一定程度的提高,随蒙脱土含量的增加,PP／MMT的热分解温度和热变形温度（HDT）都有大幅度提高。     

Exfoliated high-impact polystyrene/MMT nanocomposites prepared using anchored cationic radical initiator-MMT hybrid

High-impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in-situ polymerization of styrene in the presence of polybutadiene, using intercalated cationic radical initiator-MMT hybrid. Incomplete exfoliation of the silicate layers in the HIPS nanocomposites was observed when a bulk polymerization was employed. On the other hand, the silicate layers were efficiently exfoliated in the PS matrix during a solution polymerization, due to the low extra-gallery viscosity, which can facilitate the diffusion of styrene monomers into the clay layers. The resulting exfoliated HIPS/MMT nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, particle size analysis, gel permeation chromatography, and dynamic mechanical analysis. The nanocomposites exhibited significant improvement in thermal and mechanical properties. For example, about 50% improvement in Young’s modulus was achieved with 5 wt% of clay, compared to the unmodified polymer counterpart.     

聚乙烯醇/氟基蒙脱土纳米复合材料的合成及性能研究

采用水热方法,在493 K条件下反应72小时,合成了氟基蒙脱土(F-MMT),在这种F-MMT中,硅酸盐结构中的一些OH-被F-取代。采用溶液插层方法,制备了聚乙烯醇/F-MMT纳米复合材料(PVA/F-MMT)。采用X 射线衍射、扫描电镜和透射电镜对F-MMT 和 PVA/F-MMT纳米复合材料进行了表征;结果表明,片状结构的F-MMT均匀分散于PVA中,形成了层离结构的纳米复合材料。热重分析、力学性能和紫外可见光谱的测试结果表明,在没有牺牲光学性能情况下,PVA/F-MMT纳米复合材料的热稳定性和力学性能都得到了提高。力学和热学性能的提高归功于F-MMT均匀而好的分散于聚合物基体中,以及PVA中的 OH- 和F-MMT 中F-之间强的氢键作用。     

Expansion distribution of basal spacing of the silicate layers in polyaniline/Na+‐montmorillonite nanocomposites monitored with X‐ray diffraction

Polyaniline/Na⁺‐montmorillonite (Na⁺‐MMT) nanocomposites synthesized by in‐situ intercalative polymerization of aniline into Na⁺‐MMT are reported. The expansion distribution of basal spacing of the silicate layers upon the increase of the amount of aniline relative to Na⁺‐MMT is, for the first time, estimated from the square of the full‐width at half‐maximum (FWHM²) of XRD patterns. According to the FT‐IR frequency shift of the C‐N stretching vibration, the change in the basal spacing of the silicate layers is closely related to the degree of hydrogen bonding between polyaniline and the silicate basal surface in a confined geometry.     

Isotactic Poly(propylene)/Monoalkylimidazolium‐Modified Montmorillonite Nanocomposites: Preparation by Intercalative Polymerization and Thermal Stability Study

Summary: Poly(propylene)/monoalkylimidazolium‐modified montmorillonite (PP/IMMT) nanocomposites were prepared by in situ intercalative polymerization of propylene with TiCl₄/MgCl₂/MMT catalyst. The PP synthesized possessed high isotacticity and molecular weight. Both wide‐angle X‐ray diffraction (XRD) and transmission electron microscopy (TEM) examinations evidenced the nanocomposite formation with exfoliated MMT homogeneously distributed in the PP matrix. A thermal stability study revealed that the nanocomposites possess good thermal stability.

X‐ray diffraction patterns of PP/IMMT (MMT = 2.2 wt.‐%) nanocomposite before and after processing.     

DISPERSION AND TENSILE BEHAVIOR OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES PRODUCED VIA MELT INTERCALATION

Most of the anicles on polymer nanocomposites focus on the importance of chemistry used to modify the surfaceof the clay, usually montmorillonite (MMT), and characterization of the nano-scale structure obtained. The role andimportance of processing were also discussed recently. However, few papers concerning the correlation between morphologyof MMT and mechanical properties were published. In order to understand the tensile behavior of PP/Montmorillonite(MMT) nanocomposites better, and to further improve the reinforcement efficiency, we first prepared the PP nanocompositesvia direct melt intercalation using conventional twin-screw extrusion. The dispersion and tensile property of the compositeswere then investigated by SEM, XRD, TEM and a video-controlled tensile set-up. The macroscopic and microscopicdispersion of MMT in PP matrix was verified by XRD and TEM, combined with SEM. The tensile properties were obtainedby video-controlled tensile set-up, which gives true stress-strain curve. It was found that a partly intercalated and partlyexfoliated structure (also called incomplete exfoliation) existed in the system. Though the tensile strength of PPnanocomposites is not much improved in engineering stress-strain curves, more than 20% increase of true stress was found ina true stress-strain experiment at high true strain, which indicates that only oriented silicate layers can have a big effect ontensile properties. Not only orientation of silicate platelets but also the degree of exfoliation is a key factor to determine thereinforcement efficiency. The reinforcement efficiency of MMT has been discussed based on the "continuum" Halpin-Tsaiequations. A good agreement was found between experimental data and theoretical prediction by changing N value (number of platelets per stack) which corresponding to different state of the dispersion of MMT in PP matrix.     

Structure and mechanical properties of poly(l-lactide)/layered silicate nanocomposites

Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σ_y and yield strain ε_y, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations.     

Characterization and thermal degradation studies on polyaniline‐intercalated montmorillonite nanocomposites prepared by a solvent‐free mechanochemical route

Polyaniline (PANI)‐montmorillonite (MMT) nanocomposites were prepared by direct intercalation of aniline molecules into MMT galleries, followed by in situ polymerization within the nano‐interlamellar spaces under solvent‐free conditions. The basal spacing of aniline‐intercalated MMT increased gradually up to 1.5 nm with increasing amounts of aniline loaded. This result suggests that aniline molecules were adsorbed by MMT clay and that intercalated aniline likely located perpendicular to the silicate sheets. After polymerization, X‐ray diffraction and Fourier transform infrared analyses confirmed the successful synthesis of PANI chains between the MMT nano‐interlayers. The scanning electron microscopy images indicated that the surface morphologies of PANI–MMTs were strongly different depending on the PANI content. The electrical conductivities of PANI nanocomposite particles in pressed pellets ranged in the order of between 10^?3 and 10^?2 S/cm. UV–vis spectroscopy and doping level measurement were further used to discuss the conductivities of nanocomposites. The thermal stabilities of PANI–MMT nanocomposites were examined by using thermogravimetric‐differential thermal analysis and derivative thermogravimetric analysis, and both analyses consequently demonstrated the improved thermal stabilities of the PANI chains in the nanocomposites as compared to pure PANI. The thermal stabilities of resulting nanocomposites were strongly related to the PANI content, which increased as the PANI content decreased in the nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2705–2714, 2005     

Synthesis and characterization of organosoluble,thermoplastic elastomer/clay nanocomposites

We synthesized organosoluble, thermoplastic elastomer/clay nanocomposites by making a jelly like solution of ethylene vinyl acetate containing 28% vinyl acetate (EVA‐28) and blending it with organomodified montmorillonite. Sodium montmorillonite (Na⁺‐MMT) was made organophilic by the intercalation of dodecyl ammonium ions. X‐ray diffraction patterns of Na⁺‐MMT and its corresponding organomodified dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) showed an increase in the interlayer spacing from 11.94 to 15.78 Å. However, X‐ray diffraction patterns of the thermoplastic elastomer and its hybrids with organomodified clay contents up to 6 wt % exhibited the disappearance of basal reflection peaks within an angle range of 3–10°, supporting the formation of a delaminated configuration. A hybrid containing 8 wt % 12Me‐MMT revealed a small hump within an angle range of 5–6° because of the aggregation of silicate layers in the EVA‐28 matrix. A transmission electron microscopy image of the same hybrid showed 3–5‐nm 12Me‐MMT particles dispersed in the thermoplastic elastomer matrix; that is, it led to the formation of nanocomposites or molecular‐level composites with a delaminated configuration. The formation of nanocomposites was reflected through the unexpected improvement of thermal and mechanical properties; for example, the tensile strength of a nanocomposite containing only 4 wt % organophilic clay was doubled in comparison with that of pure EVA‐28, and the thermal stability of the same nanocomposite was higher by about 34 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2065–2072, 2002