十二烷基磺酸钠改性蒙脱土的制备与表征

利用阴离子表面活性剂十二烷基磺酸钠(SDS)改性天然蒙脱土，研究了反应介质的酸碱性对插层效果的影响。X射线粉未衍射（XRD）、红外光谱（FT-IR）、热重分析（TGA）表明SDS已插层到蒙脱土片层间，沉降实验和流变学性质研究表明改性后蒙脱土在有机介质中表现出很好的分散性、溶胀性和高触变性。这种改性效果优于目前常用的十六烷基三甲基溴化铵(CTAB)处理效果。解释了阴离子表面活性剂对蒙脱土的插层机理。     

基于胶束插层方法制备高热稳定性和大层间距有机化蒙脱土

采用不同方法制备了多种有机化蒙脱土,并分别采用X射线衍射仪、红外光谱分析仪、热重分析仪、电感耦合等离子体发射光谱仪、元素分析仪、扫描电子显微镜对产物进行了表征,并提出了有机物插层新方式——胶束插层.结果表明:适量钠基蒙脱土(Na-MMT)、十六烷基三甲基溴化铵(CTAB)和磷酸三苯酯(TPP)在丙酮/水的混合溶剂中进行溶液插层,得到的有机化蒙脱土具有更大的层间距,比单纯采用CTAB的插层效果显著.产物中含有约21.54%的CTAB和17.47±1.05%的TPP,插层机理为CTAB-TPP胶束插层.该有机化蒙脱土的初始热降解温度比单纯CTAB插层蒙脱土最多提高了17.4℃.采用该方法制备的改性蒙脱土既可以进一步提高蒙脱土的层间距,又可以封闭TPP于MMT的片层间,阻止TPP挥发;同时克服季铵盐改性蒙脱土的热稳定性低的问题,得到了层间距大、热稳定性高的有机化蒙脱土,为有机化蒙脱土在高熔点聚合物改性方面提供了条件.     

有机硅蒙脱土复合改性水性聚氨酯的研究

采用插层聚合制备了改性的水性聚氨酯乳液。X射线研究表明,蒙脱土以层间距5．19nm分散在水性聚氨酯基体中。硅烷和蒙脱土改性水性聚氨酯具有性能互补的效果,当有机蒙脱土和有机硅烷的质量分数分别为O．01及O．02时,聚氨酯乳液涂膜的拉伸强度和断裂伸长率比未改性时分别提高了70％、18％,吸水率降低了49％。     

利用荧光探针溶致变色效应研究有机改性蒙脱土的层间环境性质

利用荧光探针的溶致变色行为,研究了以不同阳离子表面活性剂处理过的化学修饰蒙脱土内腔的极性.清楚地观察到随所用表面活性剂长链碳原子数目的增多,荧光探针N,N-二甲氨基查尔酮在蒙脱土内的荧光光谱峰值波长移向短波,表明蒙脱土内腔的极性随活性剂疏水链长的增长而不断减小.本工作所得结果将对具体的插层材料(包括不同极性的聚合单体或聚合物分子)在插层时选择合适的表面处理剂有所帮助.     

羧甲基纤维素钠/蒙脱土纳米复合膜的制备及性能

用溶液插层法制备出了剥离型羧甲基纤维素钠 蒙脱土纳米复合物 .X射线衍射结果中蒙脱土d0 0 1 峰的消失证实了纳米复合物的生成 ,透射电镜观察表明硅酸盐片层在羧甲基纤维素钠基体中达到了纳米级的分散 .红外测试表明 ,羧甲基纤维素钠分子上的醚键和蒙脱土分子上的硅氧键、铝氧键之间强的作用力是插层的驱动力 .加入蒙脱土后 ,提高了羧甲基纤维素钠膜的拉伸强度、热稳定性 ,降低了其水蒸汽透过系数 .     

甲苯-2,4-二异氰酸酯修饰蒙脱土及聚苯乙烯蒙脱土纳米复合材料的制备与表征

用FTIR和WAXD法研究了甲苯-2,4-二异氰酸酯(TDI)的邻位和对位异氰酸酯基团与蒙脱土表面羟基的修饰反应,在此基础上提出了结构模型;用TDI修饰后的蒙脱土成功制备了插层型聚苯乙烯/蒙脱土纳米复合材料,并用WAXD和TEM进行了表征.实验结果表明,修饰后TDI与蒙脱土表面形成化学键,使蒙脱土的片层间距显著增大,十六烷基三甲基溴化铵(CTAB)在蒙脱土层间由双层平行排列转变为双层脂肪链倾斜方式排列.在苯乙烯插层聚合过程中,蒙脱土层间距进一步扩大,其初级粒子在聚苯乙烯基体中的厚度约20～50nm.     

聚偏氟乙烯/蒙脱土纳米复合材料的形态结构

采用有机改性的蒙脱土与聚偏氟乙烯熔融共混, 制备了聚偏氟乙烯/蒙脱土纳米复合材料. 利用X射线衍射分析、透射电子显微镜(TEM)和Molau实验研究了复合材料的微观结构. 通过X射线衍射、傅里叶变换红外光谱(FTIR)以及差热扫描(DSC)研究了有机改性蒙脱土对聚偏氟乙烯结晶结构的影响. 结果表明, 有机改性蒙脱土在聚偏氟乙烯中以插层、剥离和碎片的形式存在. 在X射线衍射谱中发现蒙脱土的(001)峰向低角方向移动, 在TEM中可见到剥离的片层碎 片.蒙脱土的引入改变了聚偏氟乙烯的结晶结构, 导致了具有压电性能的β相形成, 引起α相内应力的产生, 同时也导致了聚偏氟乙烯基体的结晶度下降, 球晶尺寸随蒙脱土含量明显减少. 蒙脱土引起的β相在 160℃退火表明是相当稳定的. 根据这些实验结果, 对由于蒙脱土的引入引起的聚偏氟乙烯结晶结构的变化提出了可能的解释.     

辐照法制备PVAc/蒙脱土纳米复合材料及其表征

蒙脱土有机化后 ,片层结构间距离增大 ,对有机物的亲和性有所增强 .采用VAc单体渗入有机化蒙脱土层间 .经γ 射线辐照引发原位插层聚合 ,使蒙脱土片层结构发生剥离 ,形成无机 有机纳米复合材料 .并用X衍射、红外光谱、扫描电镜以及透射电镜等现代测试手段对复合材料进行了表征     

蒙脱土/阳离子偶氮染料插层纳米复合物离子交换吸附

从有机阳离子与蒙脱土离子交换吸附原理出发，推导出吸附等温式和表面二维状态方程理论关系，给出了热失重确定吸附量的数据处理方法．选择具有光致变色功能、整个分子共轭的有机阳离子GTL作为插层剂，成功制备了一系列插层纳米复合物．GTL阳离子交换吸附实验数据符合推导出的吸附等温式，插层复合物界面压强π随其含水量增大而线性减小，在较低π下，层间GTL以平行于蒙脱土片层表面的单分子层形态排列；随着π增大，层间GTL以倾斜于蒙脱土片层表面的头尾交指型团聚体形态排列；在更大的π下，层间GTL倾向垂直于蒙脱土片层表面成双分子层排列，其尾端重叠自组装形成超分子共轭纳米结构，层间GTL热稳定性大幅度提高。     

聚N,N-二乙基丙烯酰胺蒙脱土纳米复合物的合成及溶胀性能

在制成钠基蒙脱土的基础上 ,对蒙脱土进行了改性 ,并把改性后的蒙脱土分散在N ,N 二乙基丙烯酰胺水溶液中进行聚合 .结果表明这种蒙脱土插层聚合的水凝胶的低温溶胀性能大大提高 ,其对水的释放曲线在特定的温度下也由S形转变为近一直线形 .由于蒙脱土的改性 ,在蒙脱土和聚合物之间的界面化学发生了改变 ,用X衍射分析表明此水凝胶是纳米复合材料 .而加入蒙脱土量达 10 %的水凝胶的溶胀比和温度响应性能也都发生很大改善 .     

Surface Modification of Montmorillonites by Chlorosilanes

Montmorillonite was modified by chlorosilane derivatives (trimethylchlorosilane and tert-butyldimethylchlorosilane)based on the reaction between OH group and chlorosilane,Fourier-transformed infrared spectra(FTIR)confirmed that chlorosilanes did react with the OH groups of montmorillonite.The effect of reaction time and dispersing agents on the intercalation was studied by wide angle X-ray diffraction(WAXD) method.Further experiments proved that there is no reactive OH group on the surface of layers in the interlayer galleries of montmorillonite.The cation exchange capacity(CEC) of montmorillonites was measured.showing that after modification by chlorosilane derivatives,CEC values drastically decreased.The dispersibility measurements of montmorillonites were conducted.which showed that the dispersibility of modified montmorillonites both in H2O and toluene wer improved due to the decrease of attractions of particles and layers.     

Preparation and Characterization of the Antibacterial Zn2+ or/and Ce3+ Loaded Montmorillonites

A series of modified montmorillonites including Zn²⁺ loaded montmorillonite (Zn/MMT), Ce³⁺ loaded montmorillonite (Ce/MMT) and Zn²⁺‐Ce³⁺ loaded montmorillonites (Zn‐Ce/MMT) were prepared by an ion‐exchange reaction, and characterized using X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), and scanning electron microscopy (SEM). The specific surface areas, zeta potentials and antibacterial activity of the modified montmorillonites were also investigated. Zinc and cerium were proved to be present as bivalent zinc state and trivalent cerium state in the modified montmorillonites. For the modified montmorillonites, the d₀₀₁ basal spacings increased and the particles were formed of irregular shapes. The antibacterial activity of the modified montmorillonites was enhanced with the increase of specific surface areas and zeta potentials, and Zn²⁺‐Ce³⁺ loaded montmorillonites displayed obvious synergistic antibacterial effect. When Zn/Ce atomic ratio was 1.24, the Zn‐Ce/MMT showed high antibacterial efficiency and broad‐spectrum antibacterial activity, possessing the MIC against Escherichia coli, Staphylococcus aureus, Candida albicans and Mucor of 1500, 1000, 2000 and 3000 mg·L^?1, respectively.     

Thermogravimetric study of <Emphasis Type="Italic">n</Emphasis>-alkylammonium-intercalated montmorillonites of different cation exchange capacity

Three n-alkylammonium salts of varying alkyl chain length were ion exchanged with montmorillonites (MMT) of different cation exchange capacity (CEC). The intercalated MMTs were characterized by thermogravimetry (TG), XRD, FTIR to acquire an insight into the intergallery structural arrangement of the organic alkylammonium cations (AAC). The increment in the intergallery spacing from XRD pattern was correlated with chain length and interlayer arrangement of AAC. Multiple organic mass-loss stages in thermogravimetric analysis indicate two types of anchorage of AAC in intercalated clay. CEC of MMT was found to influence the intergallery confinement and excess adsorption of AAC.     

Preparation and Characteration of UV-cured EA/MMT Nanocomposites Via In-Situ Polymerization

A long-chain surfactant, enzoylbenzyl-N,N-dimethyl-N-octadecylammonium bromide (BDOB) with a benzophenone group, was synthesized to modify the montmorillonites (MMT) for the preparation of nanocomposites via photo-induced polymerization. The BDOB-modified MMT was characterized by the fourier transform infrared spectrometer (FTIR), thermal gravimetric analyzer (TGA) and X-ray diffraction (XRD), and the results of XRD indicated that the intercalated structures of BDOB-modified MMT was obtained. The conversion of the bisphenol A epoxy diacrylate (EA) was quantified by the FTIR, and the results indicated that conversion increased with an increase in the amount of BDOB-modified MMT. The morphologies of the UV-cured EA/MMT nanocomposites prepared from this organically modified MMT were studied by means of XRD and TEM, and the results showed that all the samples contained an intercalated structure with partial exfoliated structure. The results of TGA and mechanical properties also indicated that the thermal and mechanical properties of UV-cured nanocomposites were significantly enhanced due to the presence of the long chain surfactant organically modified MMT.     

SYNTHESIS AND CHARACTERIZATION OF ORGANOMONTMORILLONITE AND POLYAMIDE 66/MONTMORILLONITE NANOCOMPOSITES

The montmorillonites (MMTs), layered, smectite-type silicates, were premodified by two different methods priorto the polymer melt intercalation. In one case MMTs were modified with cetyltrimethylammonium bromide (CTAB), andtermed as organomontmorillonites (OMMTs); in the other case MMTs were modified by nylon, and the products were calledmodified montmorillonites (MMMTs). The effects of CTAB and nylon on the MMTs were investigated by using TG andWAXD. The results show that interlayer spacings of CTAN and nylon modified MMTs are larger than that of sodium MMTs.Then, polyamide 66 (PA 66)/MMT nanocomposites were obtained through the method of melt intercalation of polymers. Thenanocomposites were characterized by WAXD, TEM and Molau experiments. The results indicate that the MMTs dispersehomogeneously in the PA 66 matrix. The mechanical properties of nanocomposites, such as tensile properties and flexuralproperties, were also measured and show a tendency to increase with increase of MMT content and reach the maximumvalues at 5phr MMT content. The heat distortion temperature (HDT) of the nanocomposites (7 phr) is about 32 K higher thanthat of pure PA 66.     

Preparation, characterization and application of polymeric diols with comb-branched structure and their nanocomposites containing montmorillonites

The polymeric diols with comb-branched structure (CPD) and their nanocomposites containing montmorillonites (MMT) were prepared through three-step reaction on basis of molecular design. The effect of experimental parameters, such as molar mass of oligomer polyols, catalysts and MMT on conversion of -NCO group during polymerization was investigated by utilizing FTIR to measure content of -NCO group varied as reaction time. In addition, the structure of comb-branched polymeric diols was characterized by FTIR and ¹H NMR. The results show that the comb-branched chains contain reactive CC double bonds in CPD. The nature of dispersion of montmorillonites in CPD was characterized by X-ray diffraction. The results show that Na⁺-MMT is exfoliated and organo-MMT is intercalated in CPD via in-situ polymerization. Finally, the properties of water-borne polyurethane modified with CPD or CPD/2T-MMT nanocomposite were compared with those of common water-borne polyurethane, and the comb-branched chains and 2T-MMT improve the properties of water-borne polyurethane.     

New insight into the crystallization behavior of poly(ethylene terephthalate)/clay nanocomposites

Crystallization behavior of poly(ethylene terephthalate) (PET)/clay nanocomposites has been investigated in terms of differential scanning calorimeter (DSC) analysis, polarizing optical microscopy (POM), and scanning electron microscopy (SEM) observation. The nanocomposites for investigation were prepared via in situ polycondensation. Crystalline morphologies were observed through POM and SEM. The nonisothermal and isothermal crystallization rates of different samples were determined for comparison based on DSC data. Secondary nucleation analysis was also performed based on bulk crystallization data derived from DSC analysis. The results revealed that nucleating abilities of montmorillonites (MMT) depended on the dispersion state of clay in matrix, the surface modification status, and the metallic derivatives released from MMT during in situ synthesis. The quantities of metallic elements released were measured by inductively coupled plasma (ICP) analysis. The results showed that the release of these metallic derivatives was also affected by surfactant molecules anchored on the surface of MMT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2380–2394, 2008     

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.     

Role of montmorillonite in flame retardancy of ethylene-vinyl acetate copolymer

The effects of non-treated (MMT), organophilic (OMM), and olefin/silicone polymer intercalated (IMM) montmorillonites on the thermal stability of ethylene-vinyl acetate copolymer (EVA) and on the flammability of magnesium hydroxide filled EVA were studied. The influence of various treatments on the delamination of montmorillonites in EVA was detected by rheological measurements and by Raman microscopy. The latter was a unique method for rapid detection of the dispersion also in highly filled EVA. Enhancement of thermo-oxidative stability of EVA and flame-retarded EVA could be observed by thermal analysis in the presence of variously treated montmorillonites. The flame-retardant efficiency of magnesium hydroxide was improved by simultaneous application of MMT and IMM. The increased performance of magnesium hydroxide was explained by the rheological effect of the IMM, catalytic effect of MMT and chemical interactions of montmorillonites with the metal hydroxide.