熔体插层制备尼龙6/蒙脱土纳米复合材料的性能表征

通过熔体插层成功地制备了尼龙６／蒙脱土纳米复合材料，测试了力学性能、耐热性能和耐溶剂性．通过ＴＥＭ、ＷＡＸＤ、ＤＳＣ等手段，研究了结构与结晶行为，并与插层聚合的尼龙６／蒙脱土纳米复合材料进行了对比．实验表明通过熔体插层可使尼龙６基体插层于蒙脱土中，所得到的复合物的性能较尼龙６有很大提高，且与插层聚合的尼龙６／蒙脱土纳米复合材料的性能相当．     

熔体黏度对黏土在聚丙烯/聚苯乙烯共混物中优先插层行为的影响

通过熔融共混法在160℃加工条件下制备了聚丙烯/聚苯乙烯/黏土(PP/PS/clay)复合材料.X射线衍射分析(XRD)和透射电镜分析(TEM)的结果表明,黏土在共混物中存在着优先插层现象.黏土优先被PS分子链所插层,且不受PS组分含量和加料方式的影响.基于复合材料中PP和PS组分的熔体黏度对温度敏感性的差别,通过改变加工温度的方法,研究组分的黏度差别对黏土优先插层行为的影响.随共混加工温度的升高,黏土在共混物中的分布位置逐渐从PS相向PP相迁移.TEM和动态黏弹行为测试(ARES)的结果表明,组分间黏度的差别能控制黏土的优先插层行为.组分黏度越高,加工过程中所能传递的剪切应力就越大,插层能力也就越强.     

尼龙6/蒙脱土纳米复合材料的等温结晶动力学研究

用ＤＳＣ法研究了熔体插层制备的尼龙６／蒙脱土纳米复合材料的等温结晶行为．结果表明,加入少量的蒙脱土可明显提高尼龙６的结晶速率,降低球晶径向生长的单位面积表面自由能．从Ａｖｒａｍｉ方程和Ｈｏｆｍａｎ理论出发,得出蒙脱土纳米粒子的存在可明显改变尼龙６的结晶行为     

GMMT复合材料的制备及吸附性能研究

采用直接插层法对钠基膨润土进行改性,制备了明胶/膨润土(简称GMMT)复合材料;研究了明胶插层复合改性膨润土的工艺条件;通过测定明胶插层复合前后膨润土的比表面积等的变化,探讨了GMMT复合材料的吸附性能.     

直接置换插层法0.85 nm水合高岭石的制备

以高岭石/尿素插层复合物作为中间相,利用简单的直接置换插层法制备了d001=0.85 nm的水合高岭石。利用X射线衍射、红外光谱、扫描电镜表征处理前后高岭石结构与形貌的变化。结果表明:尿素插层后的高岭石层间距从d001=0.72 nm增大到d001=1.08 nm,经不同温度酸洗或水洗后,插层复合物转变成层间有水分子的水合高岭石(d001=0.85 nm),且高岭石晶粒厚度明显从约25 nm减小到约10 nm。在高温条件下形成的水合高岭石含量最高,90℃水洗时d001=0.85 nm水合高岭石的转化率接近70%,这种水合高岭石具有进一步的置换插层能力,是一种制备其他高岭石插层复合物很好的前驱体。与乙二醇形成d001=1.10nm乙二醇/高岭石插层复合物,其置换率达到100%。     

过渡金属氧化物插层化学及其电催化应用的新进展（英文）

插层化学是指客体插入到主体形成插层化合物的过程.近年来,插层化学作为一种有效的材料结构修饰方法,已广泛应用于电化学储能和转换领域.过渡金属氧化物由于其结构和成分的可调性,在插层性能和应用方面取得了很大进展,但仍存在插层机理及性质变化原因不明确等问题.本文首先对过渡金属氧化物的插层机理进行了综合评述,分析归纳了常见的插层制备方法，然后总结了插层过渡金属氧化物在电催化中研究的最新进展,最后对该领域未来面临的机遇和挑战进行了展望.     

4—CH3SC6H4NH2对α—磷酸锆的插层特性

制备了４－ＣＨ３ＳＣ６Ｈ４ＮＨ２（ＭＭＡ）插层的α－Ｚｒ９ＨＰＯ４）２．Ｈ２Ｏ，研究了不同实验条件下ＭＭＡ的插层特性，发现插层反应与ＭＭＡ和α－ＺｒＰ摩尔比Ｒ有关；（１）当Ｒ〉２时，有插层产物相产生，但是即使在ＭＭＡ大大过量的条件下，仍然有部分α－ＺｒＰ颗粒大小等有关；插层产物的层间距约为２．３６ｎｍ，，层间距的大小不随反应物浓度，温度等条件变化。     

插层聚合聚丙烯-蒙脱土纳米复合材料的微观结构形态

使用偏光显微镜，扫描电镜，透射电镜和广角X射线衍射法研究了插层聚合法制备的聚丙烯－蒙脱土（PP－MMT）纳米复合材料的微观结构和形态发展。结果表明，随着插层聚合反应的进行，较大的初级MMT粒子逐渐剥离成较小的次级粒子。次级粒子由2－20片的单个MMT片层组成，其层间充满了PP分子链。提出了插层聚合过程中PP－MMT复合材料的形态发展模型。另外，MMT的加入对PP的球晶形态也有重要影响，PP完整的球晶随MMT的加入逐渐变小和趋于扭曲甚至破坏。     

铵离子插层mos2的制备与表征

以剥层重堆法制备了NH 4/MoS2插层复合物,该复合物可以作为长期储存的单层MoS2,同时也可作为先驱体以便插入其它客体分子制成新的插层复合物.通过XRD、热重分析和元素分析等测试技术对该插层复合物进行了表征.结果表明,MoS2经NH 4插层后,其层间距由0.615nm增加到0.954nm,由元素分析和热重分析得出插层复合物的组成分别为(NH 4)3.1 MoS2 和(NH 4 )2.9 MoS2 . 插层复合物在空气中放置30 d后,其XRD和热重分析的结果表明该插层复合物的储存稳定性良好. 此外,插层复合物的插层程度受氯化铵溶液浓度、反应温度、反应时间等反应条件的影响,质量分数为1.0%的氯化铵溶液, 反应温度30 ℃和反应时间12 h,所得到的NH 4 /MoS2插层复合物层间距最大.     

超声化学法制备高岭土/二甲亚砜插层复合物的研究

采用与传统方法不同的超声化学法,用二甲亚砜(DMSO)对高岭土进行插层,大大缩短了处理时间,而且达到了较理想的插层效果。采用X -衍射研究插层间距,发现硅酸盐片层间距从0.714 nm增加至1.123 nm左右,插层率为90.9%,并对不同超声条件对插层率的影响进行了探讨。同时用FT-IR和TG/DTA等方法对插层机理进行了分析和研究。     

高分子-无机夹层化合物的合成、结构和性能

由高分子和插入无机层状固体层间形成的夹层化合物是近年发展起来的一类具有诱人前景的新型功能材料,在许多领域具有广的前景。本文对这夹层化合的合成、结构、性能及应用前景等方面的研究进展进行了评述。     

Reversible de-intercalation and intercalation induced by polymer crystallization and melting in a poly(ethylene oxide)/organoclay nanocomposite

Semicrystalline polymer/layered silicate nanocomposites were prepared by solution blending of a low molecular weight poly(ethylene oxide) (PEO) with an organically modified montmorillonite, Cloisite 10A (C10A). The intercalation morphology was studied by temperature-dependent synchrotron wide-angle X-ray diffraction (WAXD). Unlike PEO homopolymers, significant secondary crystallization was observed in the PEO/C10A nanocomposites. Reversible de-intercalation and intercalation processes were detected during secondary crystallization and subsequent melting of secondary crystals. On the basis of two-dimensional WAXD results on oriented samples, an interphase layer between the silicate primary particles and PEO lamellar crystals was proposed. Secondary PEO crystallization in the interphase regions was inferred to be the primary driving force for polymer chains to diffuse out of the silicate gallery. This study provided a useful method to investigate polymer diffusion in nanoconfined spaces, which can be controlled by PEO secondary crystallization and melting outside the silicate gallery.     

A molecular model for epsilon-caprolactam-based intercalated polymer clay nanocomposite: Integrating modeling and experiments

In studying the morphology, molecular interactions, and physical properties of organically modified montmorillonite (OMMT) and polymer clay nanocomposites (PCNs) through molecular dynamics (MD), the construction of the molecular model of OMMT and PCN is important. Better understanding of interaction between various constituents of PCN will improve the design of polymer clay nanocomposite systems. MD is an excellent tool to study interactions, which require accurate modeling of PCN under consideration. Previously, the PCN models were constructed by different researchers on the basis of specific criteria such as minimum energy configuration, density of the polymer clay nanocomposite, and so forth. However, in this article we describe the development of models combining experimental and conventional molecular modeling to develop models, which are more representative of true intercalated PCN systems. The models were used for studying the morphological interactions and physical properties. These studies gave useful information regarding orientation of organic modifiers, area of coverage of organic modifiers over the interlayer clay surface, interaction of organic modifiers with clay in OMMT, interaction among different constituents of PCN, conformational and density change, and actual proportion of mixing of polymer with clay in PCN. We have X-ray diffraction and photoacoustic Fourier transform infrared spectroscopy to verify the model.     

Electrical characterization of poly(ethylene oxide)–clay nanocomposites prepared by microwave irradiation

Poly(ethylene oxide) (PEO)–clay (montmorillonite, hectorite, and laponite) nanocomposites were prepared by a melting intercalation procedure induced by microwave irradiation. The influence of parameters such as the time of irradiation, power, amount and relative ratio of the reagents, and relative humidity was investigated. X-ray diffraction, differential scanning calorimetry, elemental microanalysis, Fourier transform infrared, and scanning electron microscopy techniques were applied to characterize the resulting nanocomposites. Techniques involving impedance spectroscopy, thermoelectric power, and electrical polarization in the solid state were used to characterize the electrical properties of the nanocomposites. The electrical behavior of these PEO–silicate nanocomposites, including those containing an excess of alkaline metal salts in comparison with that of similar systems prepared by alternative procedures such as direct intercalation from polymer solutions or melting intercalation, was also examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3249–3263, 2003     

Altered phase model for polymer clay nanocomposites

This paper describes a multiscale approach used to model polymer clay nanocomposites (PCNs) based on a new altered phase concept. Constant-force steered molecular dynamics (SMD) is used to evaluate nanomechanical properties of the constituents of intercalated clay units in PCNs, which were used in the finite element model. Atomic force microscopy and nanoindentation techniques provided additional input to the finite element method (FEM) model. FEM is used to construct a representative PCN model that simulates the composite response of intercalated clay units and the surrounding polymer matrix. From our simulations we conclude that, in order to accurately predict mechanical response of PCNs, it is necessary to take into account the molecular-level interactions between constituents of PCN, which are responsible for the enhanced nanomechanical properties of PCNs. This conclusion is supported by our previous finding that there is a change in crystallinity of polymeric phase due to the influence of intercalated clay units. The extent of altered polymeric phase is obtained from observations of a zone of the altered polymeric phase surrounding intercalated clay units in the "phase image" of PCN surface, obtained using an atomic force microscope (AFM). An accurate FEM model of PCN is constructed that incorporates the zone of the altered polymer. This model is used to estimate elastic modulus of the altered polymer. The estimated elastic modulus for the altered polymer is 4 to 5 times greater than that of pure polymer. This study indicates that it is necessary to take into account molecular interactions between constituents in nanocomposites due to the presence of altered phases, and furthermore provides us with a new direction for the modeling and design of nanocomposites.     

Comparison of solution-blending and melt-intercalation for the preparation of poly(ethylene-co-acrylic acid)/organoclay nanocomposites

Ethylene-acrylic acid copolymers (EAAs) and commercial montmorillonite clays organically modified with dimethyldihydrogenatedtallowammonium ions (Cloisite^® 15A and 20A) were used for the synthesis of nanocomposites by melt-compounding, static melting of polymer/clay mixtures and solution-intercalation in order to compare the effectiveness of these procedures and to shed light on the thermodynamics and the kinetics of the intercalation process. The preparation from solution was made by the use of several solvents, such as toluene, xylene, chloroform, etc., which were then removed from the hybrids by precipitation in different non-solvents or by evaporation. Particular attention was paid to the effect of the thermal treatments which are often used when processing the composites prepared from solution. X-ray diffraction (XRD) of the solution-blended composites showed that no intercalation of the EAAs inside the clay galleries can be achieved if solvent removal is made by precipitation in non-solvents or by room-temperature evaporation. On the contrary, intercalation was found to occur very rapidly (in less than 1 min) when both the hybrids prepared from solution and the mechanical blends of powdered components were melted in the absence of shear. Polymer intercalation was also found to occur, though with a lower rate, upon annealing the powder mixtures at temperatures lower than the EAA melting point. Microscopic observations made by polarized optical microscopy, scanning electron microscopy and transmission electron microscopy showed that the clay particles dispersion is appreciably lower for the composites prepared from solution, compared to those produced in the melt under shear flow conditions. The hybrids obtained by static melting of powder mixtures, on the other side, were expectedly found to comprise micron sized clay agglomerates, although intercalation was demonstrated also for these materials by XRD. The structure of the intercalated silicate layers stacks, characterized by an interlayer spacing of 4.0 nm, was shown to be independent of the preparation procedure and to correspond to thermodynamic equilibrium.     

Poly(vinylidene fluoride)/clay nanocomposites prepared by melt intercalation: Crystallization and dynamic mechanical behavior studies

The preparation and properties of poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported for the first time. PVDF/clay nanocomposites were prepared by melt intercalation with organophilic clay. The composites were characterized with X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical analysis. X‐ray diffraction results indicated intercalation of the polymer into the interlayer spacing. PVDF in the nanocomposites crystallized in the β form. Differential scanning calorimetry nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity, as evidenced by the melting and crystallization peaks. Isothermal crystallization studies showed an enhanced rate of crystallization with the addition of clay, as evidenced by a reduction in the crystallization time. Dynamic mechanical analysis indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. The tan δ peak signifying the glass‐transition temperature of PVDF shifted to higher temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1682–1689, 2002     

聚合物-锂改性蒙脱石复合材料离子迁移

以聚合物（ＰＥＯ,ＰＥＯ－ＰＭＭＡ）和锂改性蒙脱石作为主要原料,采用聚合物粉末直接熔融嵌入的方法,制备聚合物－蒙脱石复合材料．利用ＮＭＲ、ＡＣ阻抗等分析方法探讨了复合材料中聚合物链对 Ｌｉ＋离子迁移的影响．结果表明,聚合物（ＰＥＯ）嵌入蒙脱石层间,层间聚合物链的无序度增大,有利于Ｌｉ＋离子迁移．ＰＭＭＡ引入对ＰＥＯ链的改性,进一步加大聚合物链的无序度,更易于层间Ｌｉ＋离子迁移;复合材料的常温离子电导率接近１０－２Ｓ·ｃｍ－１,且具有良好的温度稳定性．     

Ionothermal Synthesis of Triazine–Heptazine‐Based Copolymers with Apparent Quantum Yields of 60 % at 420 nm for Solar Hydrogen Production from “Sea Water”

Polymeric carbon nitride (PCN), in either triazine or heptazine form, has been regarded as a promising metal‐free, environmentally benign, and sustainable photocatalyst for solar hydrogen production. However, PCN in most cases only exhibits moderate activity owing to its inherent properties, such as rapid charge carrier recombination. Herein we present a triazine–heptazine copolymer synthesized by simple post‐calcination of PCN in eutectic salts, that is, NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of an internal triazine–heptazine donor–acceptor (D‐A) heterostructure was affirmed to significantly accelerate interface charge transfer (CT) and thus boost the photocatalytic activity (AQY=60 % at 420 nm). This study highlights the construction of intermolecular D‐A copolymers in NaCl/KCl molten salts with higher melting points but in the absence of lithium to modulate the chemical structure and properties of PCN.     

Morphology, crystalline structure and thermal properties of PEO/MEEP blends

Poly(ethylene oxide) and poly[bis[2-(2′-methoxyethoxy) ethoxy] phosphazene], PEO/MEEP, polymer blends were investigated by thermal analysis, X-ray diffraction, and atomic force microscopy. MEEP is an amorphous polymer and its semicrystalline blends with PEO showed two distinct glass transitions, whose composition dependence was analysed by the Lodge and McLeish self-concentration model. It appears that an amorphous miscible phase is present in these blends. Excess melting enthalpy was observed for blends with high MEEP concentration. PEO lamellar characteristics exhibited changes as a function of MEEP content, both in X-ray patterns and AFM images that indicated the intercalation of MEEP side chains in the lamellar crystalline structure.