Preparation and characterization of ZnS nanoparticles deposited on montmorillonite

ZnS nanoparticles were prepared and deposited on montmorillonite (MMT) in the presence of cetyltrimethylammonium (CTA). UV spectrometry and transmission electron microscopy (TEM) proved the formation of nanoparticles with diameters ranging from 3 nm to 5 nm. Selected-area electron diffraction (SAED) patterns revealed the presence of romboedric ZnS. The band gap energy of nanosize ZnS was estimated at 3.89 ± 0.03 eV. Photoluminescence spectra exhibited a strong emission band between 300 nm and 600 nm explained by the vacant ZnS nanostructure. The prepared ZnS-montmorillonite nanocomposite (ZnS-MMT) was used for the photocatalytic reduction of CO(2) providing a considerably high efficiency that exceeded 5-6-fold the results of commercial TiO(2) Degussa P25. The main reaction products were hydrogen and methane. Methanol and carbon oxide were also observed in about 7-fold lower amounts. The stability of ZnS against oxidation was confirmed by the determination of sulphate using capillary isotachophoresis.     

热塑性淀粉/聚乙烯醇/蒙脱土三元纳米复合材料

用熔融挤出的方法制备了甘油塑化热塑性淀粉（TPS）/聚乙烯醇（PVA）/蒙脱土（MMT）纳米复合材料,添加蒙脱土和聚乙烯醇用以提高热塑性淀粉材料的力学性能。 在相对湿度50%的条件下,复合材料的XRD衍射谱图和透射电子显微镜测试表明,MMT以剥离状态均匀分布在TPS/PVA基体中;力学测试表明,当MMT的质量分数从0％增至5％时,复合材料的力学性能明显提高。 当蒙脱土的质量分数为3%时,复合材料最大抗张强度达到13.24 MPa,杨氏模量达到61.46 MPa。 这说明蒙脱土在复合材料中可以起到物理交联点的作用,提高了复合材料的力学性能。     

SYNTHESIS AND CHARACTERIZATION OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES VIA AN in-situ POLYMERIZATION APPROACH

Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).     

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。     

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.     

Structures and Mechanical Properties of PVC／Na^＋—Montmorillonite Nanocomposites

Poly(viyl chloride)/Na^ -montmorillonite(PVC/MMT)nanocomposites with different MMT contents were prepared via melt blending.Wide-angle X-ray diffraction(WAXD)and transmission electron microscopy(TEM)were used to characterize the structures.Effects of MMT content on the mechanical properties were also studied.It is found that PVC molecular chains can intercalate into the gallery of MMT layers during melt blending process,the stiffiness and toughness of the composites are inproved simultaneously within 0.5-7wt% MMT content,and the transparency and mechanical properties decrease as MMT conten further increases.     

One-pot synthesis of ZnS/polymer composites in supercritical CO2-ethanol solution and their applications in degradation of dyes

A facile method to decorate the polymeric hollow spheres with ZnS nanoparticles has been presented. In this method, the precursors, Zn(Ac)(2)H(2)O and CH(3)CSNH(2), were first adsorbed by the polymer substrate in supercritical CO(2)-ethanol solution at 35 degrees C. Followed by heating the mixture at 100 degrees C for 2 h, ZnS/polymer composites were obtained. The as-produced ZnS/polymer composites were characterized by means of IR spectra, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy. It was demonstrated that crystalline ZnS nanoparticles with size of 3-5 nm were uniformly decorated on the polymer spheres under suitable conditions. The resultant ZnS/polymer composites exhibited high efficiency for degrading eosin B, methyl orange and methylene blue under UV light irradiation.     

两性纳米复合高吸水性树脂的结构与性能

通过丙烯酸钠、阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)与钠蒙脱土原位溶液聚合成功地制备了具有插层结构的两性纳米复合高吸水性树脂. 其吸水性树脂吸水倍率和凝胶的抗压强度相对于聚丙烯酸钠基质均有较大提高. 吸水倍率最高可达2 380 g/g, 而凝胶的抗压强度提高到基质的180%左右. 由于复合材料结构上具有两性基团, 表现出对环境pH值特殊的应答性. 同时, 阳离子单体DAC的加入影响体系纳米结构的形成.     

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.     

Crystallization behavior and thermal stability of poly(trimethylene terephthalate)/clay nanocomposites

Poly(trimethylene terephthalate) (PTT)/montmorillonite (MMT) nanocomposites were prepared by the solution intercalation method. Two different kinds of clay were organomodified with an intercalation agent of cetyltrimetylammonium chloride (CMC). X‐ray diffraction (XRD) indicated that the layers of MMT were intercalated by CMC, and interlayer spacing was a function of the cationic exchange capacity of clay. The XRD studies demonstrated that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. From the results of differential scanning calorimetric analysis, it was found that clay behaves as a nucleating agent and enhances the crystallization rate of PTT. The maximum enhancement of the crystallization rate for the nanocomposites was observed in nanocomposites containing about 1 wt % organoclay with a range of 1–15 wt %. From thermogravimetric analysis, we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–10 wt % organoclay. According to transmission electron microscopy, the organoclay particle was highly dispersed in the PTT matrix without a large agglomeration of particles for a low organoclay content (5 wt %). However, an agglomerated structure did form in the PTT matrix at a 15 wt % organoclay content. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2902–2910, 2003     

Biodegradable poly(lactic acid)/chitosan-modified montmorillonite nanocomposites: Preparation and characterization

In this study, the biodegradable poly(lactic acid) (PLA)/montmorillonite (MMT) nanocomposites were successfully prepared by the solution mixing process of PLA polymer with organically-modified montmorillonite (m-MMT), which was first treated by n-hexadecyl trimethyl-ammonium bromide (CTAB) cations and then modified by biocompatible/biodegradable chitosan to improve the chemical similarity between the PLA and m-MMT. Both X-ray diffraction data and transmission electron microscopy images of PLA/m-MMT nanocomposites indicate that most of the swellable silicate layers were disorderedly intercalated into the PLA matrix. Mechanical properties and thermal stability of the PLA/m-MMT nanocomposites performed by dynamic mechanical analysis and thermogravimetric analysis have significant improvements in the storage modulus and 50% loss in temperature when compared to that of neat PLA matrix. The degradation rates of PLA/m-MMT nanocomposites are also discussed in this study.     

Structure and thermal stability of PMMA/MMT nanocomposites as denture base material

Poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization. MMT was previously organically modified by three different intercalating agents: methacrylatoethyl trimethyl ammonium chloride (DMC), dodecylamine (12CNH), and hexadecyl allyl ammonium chloride (HADC). The structures of the nanocomposites were investigated by X-ray diffraction and transmission electron microscopy, while the interaction between PMMA and MMT was characterized by Fourier transform infrared spectroscopy. The molecular mass of the extracted PMMA was measured by gel permeation chromatography. The thermal stability of PMMA/MMT nanocomposites was evaluated by thermogravimetric and differential scanning calorimetry. The results indicated that PMMA/MMT nanocomposites were successfully prepared and the interaction between PMMA and MMT of PMMA/MMT–HADC nanocomposites was the strongest. The thermal stability of the nanocomposites was improved and found to be optimal for PMMA/MMT–HADC with T ₁₀ increasing to 304 °C, 52 °C higher than that of neat PMMA.     

Swelling behavior of organoclays in styrene and exfoliation in nanocomposites

Organoclays were prepared by cationic exchange of montmorillonite (MMT) with three commercial surfactants: octadecylamine (ODA), hexadecyltrimethylammonium bromide (HTAB), benzalkonium chloride (BAC), and an in-house synthesized surfactant, vinylbenzylalkyldimethylammonium chloride (VDAC). The swelling behaviors of organoclays in styrene were compared by wettability and rheology measurements. VDAC-MMT had the slowest capillary rise rate in styrene. The Washburn equation was found not suitable for the swellable organoclay powders. All organoclay-styrene and organoclay-toluene mixtures demonstrated yield stress. However, VDAC-MMT-styrene and VDAC-MMT-toluene mixtures showed significant higher yield stresses than the other organoclay mixtures. The wettability and rheology measurements indicate that VDAC-MMT bearing a styryl functional group has the strongest interaction with styrene monomer and toluene. In order to further evaluate the extent of swelling and the microstructure, polystyrene (PS)-clay nanocomposites were prepared by in situ polymerization. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that ODA and HTAB-MMT led to intercalated PS-clay nanocomposites, while VDAC-MMT formed exfoliated PS-clay nanocomposites.     

Solvothermal synthesis and photoluminescent properties of ZnS/cyclohexylamine: inorganic-organic hybrid semiconductor nanowires

An inorganic-organic hybrid semiconductor, ZnS/CHA (CHA = cyclohexylamine) nanocomposites was successfully synthesized via a solvothermal method using CHA as solvent, which yielded uniform and ultralong nanowires with widths of 100-1000 nm and lengths of 5-20 microm. Changing the reaction conditions could alter the morphology and optical properties of the nanocomposites. The periodic layer subnanometer structures were identified by high-resolution transmission electron microscopy (HR-TEM) images, with thickness of approximately 2 nm. The composites exhibited a very large blue-shift in their optical absorption edge as well as an exciton excitation band due to a strong quantum confinement effect caused by the internal subnanometer-scale structures. The pure hexagonal wurtzite ZnS nanowires were also obtained by extracting the ZnS/CHA nanocomposites with dimethyl formamide (DMF). In addition, the luminescent properties of exciton and defect-related transitions in different samples of ZnS/CHA were discussed in detail.     

Morphological structures of poly(vinylidene fluoride)/montmorillonite nanocomposites

Poly(vinylidene fluoride) (PVDF)/montmorillonite (MMT) nanocomposites were prepared by melt blen- ding a kind of organically modified montmorillonite with PVDF. The morphological structures of the nanocomposites were studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC). The re- sults indicate that organically modified montmorillonites are in the form of intercalation, exfoliation, and fragments in the PVDF matrix. For the composites, the (001) peak position of MMT was found to shift to a lower angle in XRD patterns, and some MMT fragments could be observed under TEM. MMT loading was favorable to producing the piezoelectric β phase in the PVDF matrix and caused internal stress in α crystals. At the same time, the crystallinity and spherulite size of PVDF decreased with the MMT content. MMT induced β phase is stable even at high temperatures (160℃). For these changes in morphological structures, some possible explanations were proposed based on the experimental re- sults.     

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.     

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     

Layered nanoparticles modified by chain end functional PE and their nanocomposites with PE

Layered materials (MMT,LDH) were successfully modified by chain end functionalized polyethylene via an ion exchange method.The samples were characterized by using elemental analysis,Fourier transform infrared (FTIR) spectrum,X-ray diffraction (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and thermogravimetric analysis (TGA).The XRD results demonstrated that MMT was successfully exfoliated with the disappearance of [001] peak.For the LDH,the peak [003] moved to a low angle and greatly weakened,indicating that LDH was successfully functionalized and completely intercalated or exfoliated.HDPE/layered nanocomposites were obtained between HDPE and different content of functional layered materials.The SEM and TEM results of nanocomposites showed the layered materials were well dispersed in the HDPE matrix,with a particle size of 100-200 nm.     

PREPARATION AND CHARACTERIZATION OF SOY PROTEIN ISOLATE(SPI)/MONTMORILLONITE(MMT) BIONANOCOMPOSITES

 The bionanocomposites of soy protein isolate (SPI)/montmorillonite (MMT) have been prepared successfully via simple melt mixing, in which MMT was used as nanofiller and glycerol was used as plasticizer. Their structures and properties were characterized with X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), thermogravimetric analysis and tensile testing. XRD、TEM and SEM results indicated that the MMT layers could be easily intercalated by the SPI matrix even by simple melt processing. The exfoliated MMT layers were randomly dispersed in the protein matrix as MMT content was low (less than 5 wt%), an incomplete exfoliation was evident from SEM results, and some primary particles were observed as the MMT content was high (from 5 wt% to 9 wt%). A significant improvement of the mechanical strength and thermal stability of SPI/MMT nanocomposites has been achieved. Our work suggests that simple melt processing is an efficient way to prepare SPI/MMT nanocomposites with exfoliated structure.     

Zinc oxide prepared by homogeneous hydrolysis with thioacetamide, its destruction of warfare agents, and photocatalytic activity

Zinc sulfide (ZnS) nanoparticles were prepared by homogeneous hydrolysis of zinc sulfate and thioacetamide (TAA) at 80 degrees C. After annealing at a temperature above 400 degrees C in oxygen atmosphere, zinc oxide (ZnO) nanoparticles were obtained. The ZnS and ZnO nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and Brunauer-Emmett-Teller (BET)/Barrett-Joyner-Halenda (BJH) methods were used for surface area and porosity determination. The photocatalytic activity of as-prepared zinc oxide samples was determined by decomposition of Orange II dye in aqueous solution under UV irradiation of 365 nm wavelength. Synthesized ZnO were evaluated for their non-photochemical degradation ability of chemical warfare agents to nontoxic products.