含季鏻阳离子的抗菌改性蒙脱土的制备及表征

采用离子交换法将十六烷基三苯基插入到钠基蒙脱土的层间得到4种不同季鏻阳离子含量的改性蒙脱土,通过热重分析（TGA）、X射线衍射法（XRD）和扫描电镜（SEM）表征了结构,并测试了其Zeta电位和抗菌活性. 发现4种改性蒙脱土中季鏻阳离子的热分解起始温度都高于230℃,具有较好的热稳定性. 并且随着改性蒙脱土中季鏻阳离子含量的增加,其层间距变大、Zeta电位升高、抗菌活性增强. 钠基蒙脱土为片状结构,粒子之间相互缠绕在一起,而改性蒙脱土显示不规则形状. 对季鏻阳离子含量为23.55wt%的QPC/MMT 3样品,其对大肠杆菌（E.coli）和金黄色葡萄球菌（S.aureus）的最低抑菌浓度（MICs）分别为1.2和0.1g/L;与细菌接触24h后,1.0g/L的样品可杀死99.9%以上的E.coli,0.1g/L的样品可杀死所有的S.aureus. QPC/MMT 3还具有较好的耐水性能.     

Mechanism of p-nitrophenol adsorption from aqueous solution by HDTMA+-pillared montmorillonite--implications for water purification

HDTMA+-pillared montmorillonites were obtained by pillaring different amounts of the surfactant hexadecyltrimethylammonium bromide (HDTMAB) into sodium montmorillonite (Na-Mt) in an aqueous solution. The optimum conditions and batch kinetics of sorption of p-nitrophenol from aqueous solutions are reported. The solution pH had a very important effect on the sorption of p-nitrophenol. The maximum p-nitrophenol absorption/adsorption occurs when solution pH (7.15-7.35) is approximately equal to the pKa (7.16) of the p-nitrophenol ion deprotonation reaction. X-ray diffraction analysis showed that surfactant cations had been pillared into the interlayer and the p-nitrophenol affected the arrangement of surfactant. With the increased concentration of surfactant cations, the arrangement of HDTMA+ within the clay interlayer changes and the sorption of p-nitrophenol increases. HDTMA+-pillared montmorillonites are more effective than Na-Mt for the adsorption of p-nitrophenol from aqueous solutions. The Langmuir, Freundlich and dual-mode sorption were tested to fit the sorption isotherms.     

Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(II) and Co(II)

Anionic surfactant modified Fe-pillared montmorillonites were prepared by Fe-hydrate solution and sodium dodecyl sulfate (SDS) solution. These organo–inorgano complex montmorillonites were divided into three types (CM1, CM2 and CM3) depending on different intercalation processes. X-ray diffraction spectra, the Fourier transform infrared (FTIR) spectra were used to analyze the structure of the raw and modified montmorillonites. X-ray photoelectron spectra of the simples have been studied to determine spectral characteristics to allow the identification of Fe(III) hydroxide. The specific surface area of the host montmorillonite (M0) is 73.2 m²/g, while for the modified montmorillonites it is 114.0 m²/g, 117.2 m²/g, and 115.8 m²/g, respectively. The mesopore volumes of the montmorillonites decrease after modification. Ions of copper and cobalt were selected as adsorbates to evaluate the adsorption performance of each montmorillonite. The adsorption data was analyzed by both Freundlich and Langmuir isotherm models and the data was well fit by the Langmuir isotherm model. The adsorption was efficient and significantly influenced by metal speciation, metal concentration, contact time, and pH. Higher adsorption capacity of the modified montmorillonites were obtained at pH 5–6. The results of desorption indicated that the metal ions were covalently bound to the modified montmorillonites.     

THERMAL ANALYSIS OF ION-EXCHANGED MONTMORILLONITE

As part of its program in mineral waste management, the Bureau of Mines has investigated the effect of ion exchange on the dewatering potential of clay minerals. Clays of the smectite group possess exchangeable cations to compensate for the overall net negative charge of the clay lattice. The ratio of the valence of the exchange cation to its ionic radius, referred to as the ionic potential, is indicative of the electrostatic influence that a given cation can exert on adjacent molecules. Differential scanning calorimetry (DSC) and thermogravimetric analyses (TG) were performed on eight ion-exchanged montmorillonices (Li⁺, Na⁺, K⁺, NH₄⁺, Ca²⁺, Ba²⁺, Mg²⁺, and ^Sr2+). Results of these analyses indicate that the energy required to dehydrate the ion-exchanged montmorillonites and the associated dehydration water loss are directly related to the ionic potential of the exchange cation. Furthermore, the ordering influence of the exchange ion is responsible for different hydration states within the interlayer water.     

蒙脱土有机改性对丁基橡胶复合材料微观结构与性能的影响

采用季铵盐有机改性蒙脱土(OMMT)与丁基橡胶(IIR)机械共混和硫化制备成复合材料。研究了蒙脱土有机改性前后对复合材料的微观结构、力学和芥子气防护性能的影响。透射电镜(TEM)和X射线衍射(XRD)显示IIR/OMMT复合材料为插层型纳米复合材料,而IIR/MMT为未插层的微米复合材料。复合材料的微观结构和填料的界面活性对其力学性能影响重大,IIR/OMMT复合材料的力学性能明显优于IIR/MMT复合材料的力学性能。添加有机或无机蒙脱土都可使芥子气在丁基橡胶中的扩散系数显著降低。而芥子气在IIR/OMMT中的扩散系数更低,这显示出IIR/OMMT复合材料的芥子气防护性能更加优异。     

有机化试剂结构对粘弹性大分子插层蒙脱土的影响

以Gemini季铵盐、十六烷基二甲基甜菜碱和十二烷基三甲基溴化铵为有机化试剂对蒙脱土进行有机化处理和粘弹性大分子插层反应,通过XRD分析测试手段,研究了有机化试剂空间结构大小及可反应基团获得的有机化蒙脱土结构差异,以及粘弹性大分子对不同有机化结构蒙脱土的插层行为,结果表明Gemini季铵盐对蒙脱土进行有机化处理效果最好,粘弹性大分子插层Gemini季铵盐有机化蒙脱土的插层量大于含可反应基团的十六烷基二甲基甜菜碱有机化蒙脱土以及十二烷基三甲基溴化铵有机化蒙脱土的插层量。     

Geochemical aspects of environmentally safe conservation of liquid radioactive waste

Physicochemical features of the sorption of Sr, Cs, and U radionuclides on natural mineral sorbents (montmorillonites of Na and Ca type, kaolinites, illites) were studied. The main processes responsible for binding and retention of radionuclides are ion exchange and formation of complexes on the mineral surface. The influence of pH, salt composition of the solution, specific surface area of the sorbent, and its pore size on the radionuclide immobilization efficiency was examined.     

Effect of the presence of excess ammonium ions on the clay surface on permeation properties of epoxy nanocomposites

Epoxy nanocomposites with commercially and self-modified montmorillonites of different cation exchange capacities carrying ammonium modifications of various chemical architectures were synthesized using solution casting approach. The commercially treated montmorillonites were observed to contain a large excess of unbound ammonium ions on the surface, which had a negative impact on the permeation properties of the composites owing to the suspected interactions of these unbound ammonium ions with the epoxy polymer. The permeation behavior was significantly improved when self-modified clays free of any excess ammonium modification were used. The microstructure development was unaffected by the physical state of the clay surface indicating that the potential changes in the polymer properties at the interface as well as interfacial interactions in the composites carrying the commercially modified clays may have led to increase in the free volume. Optimal preparation of the clay surface holds the key to achieve enhancement in the composite performance.     

X-ray photoelectron spectroscopy and Auger electron spectroscopy of the influence of cations and anions of organometallic adhesion promoters on the interface between steel cord and rubber skim compounds

The influence of cations and anions of the adhesion promoters on the interface between brass-coated steel cord and natural rubber skim compounds has been studied by employing Auger electron spectroscopy and X-ray photoelectron spectroscopy at three different etching times. Cobalt stearate, cobalt boroacylate and nickel boroacylate have been used as organometallic adhesion promoters. The atomic concentrations of sulfur and carbon decreased, while those of copper and zinc increased significantly with etching times. Cobalt/nickel was only found at higher etching times. Cobalt boroacylate increased the atomic concentration of copper, zinc and sulfur with the formation of Cu_xS and ZnS on the top two layers more than the nickel boroacylate. The sulfidation reaction was, however, only partial in the presence of cobalt stearate, and ZnO was observed in the top layer. The atomic concentrations of copper and zinc were also much lower than those of the system containing cobalt boroacylate. A model, based on the results, is proposed to show the difference in activity of the cations and anions.     

阴-非离子型有机蒙脱石粉体的制备和表征

用阴离子表面活性剂硬脂酸钠、十二烷基苯磺酸钠和十二烷基磺酸钠分别与非离子表面活性剂曲拉通100组合,制备阴-非离子型有机蒙脱石粉体。通过X射线粉晶衍射分析,研究阴-非离子型有机蒙脱石粉体的制备、阴离子表面活性剂种类和蒙脱石类型对蒙脱石改性效果的影响。结果表明,3种阴离子表面活性剂均能进入蒙脱石层间,得到层间距分别为5.65、4.29、3.73 nm的阴-非离子型有机蒙脱石。用阴-非离子表面活性剂改性不同类型蒙脱石的研究结果表明,蒙脱石的膨胀容明显影响阴-非离子型改性剂改性蒙脱石的效果,并呈规律性变化,蒙脱石的膨胀容值越大,改性效果越好。