In situ preparation of hetero-polymers/clay nanocomposites by CUAAC click chemistry

A series of polymer/clay nanocomposites containing mechanistically two different polymers, poly(ethylene glycol) (PEG) and poly(epsilon caprolactone) (PCL), were prepared by simultaneous copper(I)-catalyzed alkyne-azide cycloaddition click reactions. Both clickable polymers, PEG-Alkyne and PCL-Alkyne, were simultaneously clicked on to azide-functional montmorillonite (MMT-N₃) nanoclay to get corresponding PEG-PCL/MMT nanocomposites. The chemical structures of the resulting nanocomposites were verified by following azide and silicone-oxygen bands using FT-IR and characteristic bands of PEG and PCL segments using ¹H-NMR spectroscopy. The combined XRD and TEM analysis confirmed that all PEG-PCL/MMT nanocomposites had partially exfoliated/intercalated morphologies. In addition, the increase of MMT-N₃ loading not only improved the onset and maximum degradation temperatures of the nanocomposites but also their char yields. Furthermore, the incorporation of MMT-N₃ in the polymer matrix did not significantly influence the crystallization behavior of both PEG and PCL segments.     

Removal of Cd(II), Cu(II), and Pb(II) by adsorption onto natural clay: a kinetic and thermodynamic study

In this work, we study the elimination of three bivalent metal ions (Cd²⁺, Cu²⁺, and Pb²⁺) by adsorption onto natural illitic clay (AM) collected from Marrakech region in Morocco. The characterization of the adsorbent was carried out by X-ray fluorescence, Fourier transform infrared spectroscopy and X-ray diffraction. The influence of physicochemical parameters on the clay adsorption capacity for ions Cd²⁺, Cu²⁺, and Pb²⁺, namely the adsorbent dose, the contact time, the initial pH imposed on the aqueous solution, the initial concentration of the metal solution and the temperature, was studied. The adsorption process is evaluated by different kinetic models such as the pseudo-first-order, pseudo-second-order, and Elovich. The adsorption mechanism was determined by the use of adsorption isotherms such as Langmuir, Freundlich, and Temkin models. Experiments have shown that heavy metals adsorption kinetics onto clay follows the same order, the pseudo-second order. The isotherms of adsorption of metal cations by AM clay are satisfactorily described by the Langmuir model and the maximum adsorption capacities obtained from the natural clay, using the Langmuir isotherm model equation, are 5.25, 13.41, and 15.90 mg/g, respectively for Cd(II), Cu(II), and Pb(II) ions. Adsorption of heavy metals on clay is a spontaneous and endothermic process characterized by a disorder of the medium. The values of ΔH are greater than 40 kJ/mol, which means that the interactions between clay and heavy metals are chemical in nature.     

Poly(vinyl alcohol)/GO-MMT nanocomposites: Preparation,structure and properties

A facile, efficient and environment friendly method is established to prepare poly(vinyl alcohol)(PVA) based graphene oxide-montmorillonite(GO-MMT) nanocomposites in aqueous media. GO-MMT nanohybrid is obtained by the combination of GO and MMT in water without any reducing or stabilizing agents. The formation of GO-MMT nanohybrid is due to the hydrogen bonding and crosslinking effects. The sodium ions within MMT sheets act as crosslinkers between GO sheets and MMT platelets. The resultant nanocomposites are characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and mechanical testing. Compared to that of pure PVA, PVA nanocomposites show enhanced thermal stabilities and mechanical properties, which results from strong interfacial adhesion of the nanoadditives in PVA matrix. The further increase in the tensile strength and modulus results from strong interaction between PVA chains and layered GO-MMT as well as good mechanical properties of GO-MMT hybrid, compared to PVA/GO and PVA/MMT nanocompsoites.     

The reference shrinkage curve of clay soil

The objective of this work is to develop and validate a model that predicts the reference soil shrinkage curve, that is one without crack volume contribution, as a necessary preliminary step in future estimation of soil crack volume from soil shrinkage data. Current soil shrinkage models are based on the approximation of soil shrinkage data by some a priori taken mathematical expressions and justified by the fitting of their parameters to the data. However, the crack volume entering the data is not single valued and depends on shrinkage conditions. Unlike that the reference shrinkage curve is single valued. For soils with sufficiently high clay content when there are no large pores (lacunar pores) inside the intra-aggregate clay, the reference shrinkage curve is derived from the assumption of the rigid superficial (interface) layer of aggregates with changed pore-size range and distribution compared with the intra-aggregate matrix. This consideration is based on accounting for contributions of the interface aggregate layer and intra-aggregate matrix to the soil volume and water content during shrinkage. The reference shrinkage curve is predicted by eight fundamental physical immediately measured parameters of (i) the intra-aggregate matrix (including clay content); (ii) the aggregate structure; and (iii) the mean silt-sand grain size or mean interface layer thickness. The model was validated using the data for eight soils. In addition to the major potential application for estimating a soil crack volume, the model explains differences between the observed shrinkage curves of soil and pure clay, and it can have other numerous applications.     

陕北晋西砂黄土的胶结物与胶结作用研究

在野外调查的基础上,采用SEM、XRD、土壤物理和土壤化学等方法,对陕北晋西12个县市的48个马兰黄土样品进 行了全分散法粒度组成测定、聚集体分析以及黄土胶结物组成的测试分析。结果表明,砂黄土中的粘土矿物和超细碳酸盐、 游离氧化物和有机质等胶结物质主要是以聚集体包膜的形式存在于碎屑颗粒表面,并构成砂黄土骨架间的结构联结,具有弱 胶结特性。砂黄土中粘土矿物和有机质为非水稳性胶结物质,仅在干燥状态具有较弱的胶结作用;黄土中的CaCO3呈粗颗粒 骨架和细分散超细碳酸钙两种形式存在,并分别起着骨架作用和胶结作用,超细碳酸钙为不可逆的胶结材料,在聚集体形成、 保存以及聚集体与碎屑颗粒之间的联结方面发挥着重要作用;非晶质游离氧化物(SiO2、Fe2O3、Al2O3)含量虽低,但由于他们 是以薄膜形式分布在颗粒表面,在黄土胶结作用中也是不可忽视的,并与上述各种胶结物共同起作用。通过统计分析认为, 凝聚系数可以较好地反映黄土的胶结程度,成为联系黄土胶结特性与黄土物理力学性质之间的桥梁。黄土胶结物组成及其 胶结机理的研究不仅有助于深化砂黄土工程特性的认识,而且对揭示黄土高原表生地球化学环境具有重要意义。     

粘土担载的钼基催化剂的制备、结构及CO加氢合成醇性能

采用溶胶凝胶法与等体积浸渍相结合制备了一系列以粘土为载体的K-Co-Mo催化剂. 采用XRD、N₂等温吸脱附、H_{26+的还原,但对Mo⁴⁺和Co²⁺的还原没有明显的影响. 催化剂经还原后,在其表面生成了一种更低价态的Mo^δ+(1<δ<4)物种,被认为是合成醇的活性中心. 与非负载催化剂相比,粘土担载的K-Co-Mo具有更高的合成醇性能. 负载型催化剂具有较高的活性物种分散度,并且其介孔结构在一定程度上延长了合成醇反应中间体的滞留时间,从而促进了低碳醇的生成. 经773 K还原的催化剂具有较高的活性,其原因可为催化剂表面具有较高含量的Mo^δ+物种.}     

Near Infrared Spectroscopy of the Cretaceous Red Beds in Inner Mongolia DongshengmiaoSCIEI北大核心CSCD

Take the cores and surface weathered soil from the Cretaceous red beds in the western of Dongshengmiao mine of Inner Mongolia and analysis with near-infrared spectroscopy. The result shows that near-infrared spectroscopy can identify mineral quickly through the characteristic absorption peaks of each group. The Cretaceous red beds in the western of Dongshengmiao mine is argillaceous cementation, it is mainly composed of quartz, feldspar, montmorillonite, illite, chlorite, muscovite etc, the mineral composition is mainly affected by the upstream source area. The clay mineral like montmorillonite water swelling and uneven drying shrinkage expands the original crack and creates new cracks, reduces its strength, which is the mainly reason of its disintegration. According to the composition of clay mineral, we speculate its weathering process is mainly physical weathering, the climate during the weathering is cold and dry. The results can not only improve the geological feature of the mining area, but also show that the near-infrared spectroscopy technology can analyze the mineral composition of soil and rock effectively on the basis of Mineral spectroscopy, which demonstrates the feasibility of the near-infrared spectroscopy can analyze minerals in soil and rock quickly, that shows the feasibility in geology study, provides new ideas for the future research of soil and rock.     

龙井水库大坝的渗流和稳定分析

本文以龙井水库大坝为例,运用有限单元法对粘土心墙坝的渗流进行分析计算,同时运用瑞典圆弧滑动法和简化Bishop法对粘土心墙坝的坝体稳定进行分析计算,在此基础上对水库大坝进行了渗流安全评价和稳定性安全评价。     

深部土高压卸载变形结构性量化参数确定及本构模型

用取自山东巨野矿区埋深300～600m的深部粘土样,在三轴伺服仪上进行原状和重塑土的高压三轴卸载试验,对比分析其变形特点;提出一种描述深部土高压卸载变形与强度连续变化的土结构性参数的方法,并根据三轴卸载试验结果,确定了巨野矿区深部土高压卸载变形结构性参数,建立了描述巨野矿区深部土高压卸载结构性本构模型。     

Oxidative homocoupling of terminal alkynes under palladium-, ligand- and base-free conditions using Cu(II)-clay as a heterogeneous catalyst

Homocoupling of terminal alkynes to 1,3-diynes has been investigated with Cu(II)-modified clay under mild and operationally simple conditions without the use of any ligand or a stabilizing agent. The catalyst is robust, ecofriendly, efficient, furnishes good to excellent yields of the desired products and can be reused several times with negligible loss in catalytic activity.