Electrochemical and electrogenerated chemiluminescence of clay nanoparticles/Ru(bpy)(3)(2+) multilayer films on ITO electrodes

The electrochemical and electrogenerated chemiluminescence of Ru(bpy)(3)(2+) immobilized in {clay/Ru(bpy)(3)(2+)}(n) multilayer films by layer-by-layer assembly were investigated. The stable multilayer films of clay and Ru(bpy)(3)(2+) were assembled by alternate adsorption of negatively charged clay platelets and positively charged Ru(bpy)(3)(2+) from their aqueous dispersions. UV-vis spectroscopy, quartz crystal microbalance (QCM), cyclic voltammetry, and electrogenerated chemiluminescence (ECL) were used to monitor the immobilization of Ru( bpy)(3)(2+) and the regular growth of the {clay/Ru( bpy)(3)(2+)}(n) multilayer films. The multilayer films modified electrode was used for the ECL detection of tripropylamine ( TPA) and oxalate. The proposed novel immobilized method exhibited good stability, reproducibility and high sensitivity for the determination of TPA and oxalate, which mainly resulted from the contributing of clay nanoparticles with appreciable surface area, special structural features and unusual intercalation properties.

Morphology and melt rheology of nylon 11/clay nanocomposites

Nylon 11 (PA11)/clay nanocomposites have been prepared by melt-blending, followed by melt-extrusion through a capillary. Transmission electron n-Licroscopy shows that the exfoliated clay morphology is dominant for low nanofiller content, while the intercalated one is prevailing for high filler loading. Melt rheological properties of PA11 nanocomposites have been studied in both linear and nonlinear viscoelastic response regions. In the linear regime, the nanocomposites exhibit much higher storage modulus (G') and loss modulus (G") values than neat PAIL The values of G' and G" increase steadily with clay loading at low concentrations, while the G' and G" for the sample with 5 wt % clay show an inverse dependence and lie between the modulus values of the samples with 1 and 2 wt % of clay. This is attributed to the alignment/orientation of nanoclay platelets in the intercalated nanocomposite induced by capillary extrusion. In the nonlinear regime, the nanocomposites show increased shear viscosities when compared with the neat resin. The dependence of the shear viscosity on clay loading has analogous trend to that of G' and G".

Controlling dispersed state and exfoliation process of clay in polymer matrix

In the present review, the authors do not try to provide a comprehensive review of researches on polymer/clay nanocomposites (PCNs), but some examples to demonstrate different exfoliation processes of the clay in various polymer matrixes and the dispersed state of clay. Interaction between polymers and layered silicates plays an important role in adjusting the exfoliation process of layered silicates and the microstructure of polymer nanocomposites. Properties of polymer/layered silicate nanocomposites mainly depend on the dispersed state of layered silicates. The authors will also address the outline of the present research in the direction of PCNs including the discussion of technical problems and their possible solutions.

High-temperature X-ray diffraction studies on polyamide6/clay nanocomposites upon annealing

The influence of nanodispersed clay on the alpha crystalline structure of polyamide 6 (PA6) was examined in-situ with X-ray diffraction (XRD) between room temperature and melting. In pure PA6 upon annealing the alpha crystalline phase was substituted by an unstable pseudohexagonal phase at 150degreesC, then it transformed into a new stable crystalline structure - high temperature alpha' phase above the transition temperature. However, in PA6/clay nanocomposite (PA6CN), the alpha phase did not present crystalline phase transition on heating. The increase in the annealing temperature only led to continuous intensity variation. The different behaviors were caused by the confined spaces formed by silicate layers, which constrained the mobility of the polymer chains in-between.

REE and epsilon(Nd) of clay fractions in sediments from the eastern Pacific Ocean: Evidence for clay sources

Clay fractions in the non-calcareous surface sediments from the eastern Pacific were analyzed for clay minerals, REE and Nd-143/Nd-144. Montmorillonite/illite ratio (M/I ratio), total REE contents (Sigma REE), LREE/HREE ratio and cerium anomaly (delta Ce) may effectively indicate the genesis of clay minerals. Clay fractions with M/I ratio > 1, delta Ce < 0.85, Sigma REE > 400 mu g/g, LREE/HREE ratio approximate to 4, and REE patterns similar to those of pelagic sediments are terrigenous and autogenetic mixed clay fractions and contain more autogenetic montmorillonite. Clay fractions with M/I ratio < 1, delta Ce=0.86 to 1.5, Sigma REE=200 to 350 mu g/g, LREE/HREE ratio approximate to 6 and REE distribution patterns similar to that of China loess are identified as terrigenous clay fraction. The Nd-143/Nd-144 ratios or epsilon(Nd) values of clay fractions inherit the features of terrigenous sources of clay minerals. Clay fractions are divided into 4 types according to epsilon(Nd) values. Terrigenous clay minerals of type I with the eNd values of -8 to -6 originate mainly from North American fluvial deposits. Those of type 11 with the epsilon(Nd) Values of -9 to -7 are mainly from the East Asia and North American fluvial deposits. Those of type III with epsilon(Nd) values of -6 to -3 could come from the central and eastern Pacific volcanic islands. Those of type IV with epsilon(Nd) values of -13 to -12 may be from East Asia eolian. The terrigenous and autogenetic mixed clay fractions show patchy distributions, indicating that there are volcanic or hot-spot activities in the eastern Pacific plate, while the terrigenous clay fractions cover a large part of the study area, proving that the terrigenous clay minerals are dominant in the eastern Pacific.

Clay mineral distributions in the southern Yellow Sea and their significance

To better understand the characteristics of the clay minerals in the southern Yellow Sea, the X-ray quantitative determinations have been carried out for the surface samples obtained from the Yellow Sea. With newly compiled clay mineral synoptic maps, the depositional processes were described for four main clay minerals (illite, chlorite, kaolinite and smectite). The analysis shows that most clay minerals are of terrigenous source with the Huanghe River acting as the major sediment supplier. Besides, the source of muddy sediments in the Yellow Sea was also discussed. As for the central Yellow Sea mud (CYSM), the sediments in its northern part mainly come from the Huanghe River, and those in the rest are of multi-origin. Very similarly, a large amount of sediments in the northern part of the southeastern Yellow Sea Mud (SEYSM) derive from the Keum River and Yeong-san River, while those in the southern part are of multi-origin.

Evolution and variability of the East Asian summer monsoon during the Pliocene: Evidence from clay mineral records of the South China Sea

The Late Pliocene is thought to be characterized by the simultaneous intensification of both the East Asian winter monsoon (EAWM) and East Asian summer monsoon (EASM). However, the evolution of the EASM during the Pliocene remains still controversial and only little is known about the dynamics of the EASM during the Pliocene on orbital time scales. Here we use clay mineral assemblages in sediments from Ocean Drilling Program (ODP) Site 1143 in the southern South China Sea (SCS) to obtain proxy records of past changes in the EASM climate during the Pliocene. Provenance analysis suggests that illite, chlorite and kaolinite originated mainly from the Mekong River drainage area. Smectite was derived mainly from the Indonesian islands. The kaolinite/illite ratio and the chemical index of alteration (CIA) of siliciclastic sediments allowed us to reconstruct the history of chemical weathering and physical erosion of the Mekong River drainage area and thus, the evolution of,the EASM during the Pliocene. Our clay minerals proxy data suggests a stronger EASM during the Early Pliocene than during the Late Pliocene. We propose that the long-term evolution of the EASM has been driven by global cooling rather than the uplift of the Tibetan Plateau. Spectral analysis of kaolinite/ illite ratio displays a set of strong periodicities at 100 ka, 30 ka, 28 ka, 25 ka, and 22 ka. with no clear obliquityrelated signal. Our study suggests that the Pliocene EASM intensity on orbital time scales is not only controlled by the Northern Hemisphere summer insolation, but also strongly influenced by equatorial Pacific ENSO-like ocean atmosphere dynamics. (C) 2010 Elsevier B.V. All rights reserved.

Characteristics of clay minerals in the northern South China Sea and its implications for evolution of East Asian monsoon since Miocene

Clay mineral assemblages, crystallinity, chemistry, and micromorphology of clay particles in sediments from ODP Site 1146 in the northern South China Sea (SCS) were analyzed, and used to trace sediment sources and obtain proxy records of the past changes in the East Asian monsoon climate since the Miocene, based on a multi-approach, including X-ray diffraction (XRD) and scanning electron microscopy combined with energy dispersive X-ray spectrometry (SEM-EDS). Clay minerals consist mainly of illite and smectite, with associated chlorite and kaolinite. The illite at ODP Site 1146 has very well-to-well crystallinity, and smectite has moderate-to-poor crystallinity. In SEM the smectite particles at ODP Site 1146 often appear cauliflower-like, a typical micromorphology of volcanic smecites. The smectite at ODP Site 1146 is relatively rich in Si element, but poor in Fe, very similar to the smectite from the West Philippine Sea. In contrast, the chemical composition of illite at ODP Site 1146 has no obvious differences from those of the Loess plateau, Yellow River, Yangtze River, and Pearl River. A further study on sediment source indicates that smectite originates mainly from Luzon, kaolinite from the Pearl River, and illite and chlorite from the Pearl River, Taiwan and/or the Yangtze River. The clay mineral assemblages at ODP Site 1146 were not only controlled by continental eathering regimes surrounding the SCS, but also by the changing strength of the transport processes. The ratios of (illite+chlorite)/smectite at ODP Site 1146 were adopted as proxies for the East Asian monsoon evolution. Relatively higher ratios reflect strongly intensified winter monsoon relative to summer monsoon, in contrast, lower ratios indicate a strengthened summer monsoon relative to winter monsoon. The consistent variation of this clay proxy from those of Loess plateau, eolian deposition in the North Pacific, planktonic, benthic foraminifera, and black carbon in the SCS since 20 Ma shows that three profound shifts of the East Asian winter monsoon intensity, and aridity in the Asian inland and the intensity of winter monsoon relative to summer monsoon, occurred at about 15 Ma, 8 Ma, and the younger at about 3 Ma. The phased uplift of the Himalaya-Tibetan plateau may have played a significant role in strengthening the Asian monsoon at 15 Ma, 8 Ma, and 3 Ma.

Recovery and fate of three species of marine dinoflagellates after yellow clay flocculation

The recovery and fate of three species of dinoflagellates, Alexandrium tamarense, Cochlodinium polykrikoides and Scrippsiella trochoidea, after having been sedimented by yellow clay, were investigated in the laboratory. The effect of burying period in yellow clay pellet and mixing on the recovery of settled algal cells were studied. The morphological changes of algal cells in yellow clay pellet were also tracked. Results showed that there was almost no recovery for A. tamarense and C. polykrikoides, and the cells decomposed after 2-3 days after visible changes in morphology and chloroplasts. There was some recovery for S. trochoidea. Moreover, S. trochoidea cysts were formed in clay pellet during the period of about 14 days, with the highest abundance of 87 000 cysts g(-1) clay and the incidence of cyst formation of 6.5%, which was considered as a potential threat for the further occurrence of algal blooms. S. trochoidea cysts were isolated from yellow clay and incubated to test their viability, and a germination ratio of more than 30% was obtained after incubation for 1 month. These results showed the species specificity of the mitigation effect of yellow clay. It is suggested that cautions be taken for some harmful species and thorough risk assessments be conducted before using this mitigation strategy in the field.

Clay surface modification and its coagulation of red tide organisms

Surface modification of montmorillonite by means of Mg2+ insertion reaction has been studied and a positively charged montmorillonite has been prepared. The effects of preparation temperature and Mg2+ concentration on the positive charge property of the clay and on the clay coagulating Heterosigma akashiwo have been studied. The results showed that the modified clay enhanced the coagulation and the used amount decreased to 1/5-1/10 of the original. The removal rates of Heterosigma akashiwo were correlated positively with positive charge on the clay in accordance with theoretical model.

膨胀土化学改性实验研究

Expansive soil is a kind of typical unsaturated soil with characteristics of high swelling-shrinking deformation, cracks and over consolidation. It is very harmful to civil engineering, As a new processing method deal with expansive soil, Chemistry treatment has widespread applied in developed countries such as Europe and America, and also gained remarkable result. Based on the embankment filling soil improving testing projects in Meng-Xin freeway, this paper proposed a new processing method to expansive soil embankment wrapped with PAS-treated soil, experimental study of expansive soil chemical improved by PAS is been carried out. The water content change is the external factor which causes expansive soil to have swelling-shrinkage deformation. this reflected that the soil body swelling-shrinkage characteristic mainly depends on its mineral ingredient and the soil-water mutual function. This paper takes expansive soil as one kind of ordinary high plastic clay from angle of clay-water mutual function explained the expansive soil swelling-shrinkage deformation mechanism on microscopic. And take this swelling-shrinkage mechanism as the master line, Cooperates with the China Academy of Chemistry, we developed the new method PAS treatment, trough ionic exchange, joint, package and flocculation, the stronger static electricity function weakened the level through adsorption and the stronger static electricity function, PAS can weakened the negative charge repulsion between levels, causes the electric potential to reduce, diffusion layer thickness to be thinner, and improves the water affinity performance of expansive soil effectively. Moreover the space network architecture compromised with PAS and soil enhanced the joint strength between the clay particles , enable the soil body to have comparatively high strength and the distortion rate. pointed proposed the PAS modified principle. Combine with the construction of experimented road, this paper sums up and presents the construction craft and technology requirement of PAS treatment to expansive soil embankment. Through many experimental studied the basic physical property, the intensity characteristic and water stability changes of expansive soil and PAS-treated soil. The results of study indicate that adding lime into the expansive soil can reduce the content of clay gain obviously, reduce the plasticity notably, increase the strength greatly, control the property of swelling and shrinking effectively, and can meliorate the stability of sucking water clearly. Simultaneity PAS don’t change the cultivate capacity of the soil, the modified slope of the embankment can adopt plant fixed slope method as ecology protection. Finally the processing effect of use different treatment has analyzed through numerical simulation, summarized the PAS chemical wrapping treatment process in the actual project application, and appraised its processing effect and the project efficiency. The research indicated that PAS chemical treatment is one effective method to improve expansive soil. Compare with long-distance replacement, especially in the high plastic expansive soil massive distribution area, PAS treatment has the very greatly economical superiority to be promoted. The study in the paper not only afforded technique method to Meng-Xin expressway construction but also important for improvement of the expressway construction theory in swelling soil areas. Key words: PAS; expansive soil; swelling-shrinkage deformation mechanism; wrapping embankment; chemical modified treatment.

中国东部上第三系硬粘土的工程地质特性及边坡开挖工程环境效应研究

The engineering geological properties of Neogene hard clays and related engineering problems are frontiers in the fields of Engineering Geology, Soil Mechanics and Rock Mechanics. Recently, it has been recognized that Neogene hard clay is the intermediate type of material between the soil and the rock. Many aspects of them, such as sampling, testing, calculating and engineering process, are special, which could not be researched by means of theories and methods of traditional Soil Mechanics of Rock Mechanics. In order to get real knowledge and instruct the engineering practice, intersect studying of multiple disciplines, including Engineering Geology, Soil Mechanics and Rock Mechanics, etc., is necessary. Neogene hard clay is one of the important study objects of regional problem rocks & soils in our country, which extensively distributed in China, especially in Eastern China. Taking the related areas along the middle line of the Project of Transferring Water from the South to the North (e.g. Nanyang basin, Fangcheng-Baofeng area and Handan-Yongnian area), South-west of Shandong, Xu-Huai area and Beijing area, etc. as main study areas, the paper divided Neogene hard clays into reduction environment dominated origin and oxidation environment dominated origin, which distributed on areas western and eastern to Mount Taihangshan respectively. Intermediate types are also existed in some areas, which mainly distribute near the edges of depositional basins; they are usually of transitions between diluvial and lacustrine deposits. As to Neogene hard clays from Eastern China, the clay particle content is high, and montmorillonite or illite/montmorillonite turbostratic mineral is the dominating clay mineral. The content of effective montmorillonite is very high in each area, which is the basis for the undesirable engineering properties of Neogene hard clays. For hard clays from the same area, the content of effective montmorillonite in gray-greenish hard clay is much higher than that in purple-brownish or brown-yellowish hard clay, which is the reason why the gray-greenish hard clay usually has outstanding expansive property. On the other hand, purple-brownish or brown-yellowish hard clay has relatively less montmorillonite, so its property is better. All of these prove that the composition (clay mineral) of Neogene hard clay is the control factor for the engineering properties. Neogene hard clays have obvious properties such as fissured, overconsolidated and expansive, which are the main reasons that many engineering problems and geological harzards usually occur in Neogene hard clays. The paper systematically elaborates the engineering properties of Neogene hard clays from Eastern China, analyses the relationships between engineering properties and basic indexes. The author introduces the ANN method into the prediction of engineering property indexes of hard clays, which provides a new way for quantitatively assessment and prediction of engineering property indexes. During investigation in the field, the author found that there exists obvious seam-sheared zone between different hard clays in Miocene Xiacaowan formation in Xu-Huai area. Similar phenomenon also exists near the borderline between Neogene hard clays and underlying coal measures in the Southwest of Shandong province, which could be observed in the cores. The discovery of seam-sheard zone has important theoretical and practical significance for engineering stability analysis and revealing the origin of fissures in Neogene hard clays. The macrostructure, medium structure and microstructure together control the engineering properties of hard clays. The author analyses and summarizes the structural effects on hard clays in detail. The complex of the strength property of hard clays is mostly related to the characteristics of fissures, which is one of the main factors that affect the choice of shear strength parameters. So structure-control theory must be inseparably combined with composition-control theory during the engineering geological and rock/soil mechanics research of hard clays. The engineering properties, such as fissured, overconsolidated and expansive, control the instability of engineering behaviors of Neogene hard clays under the condition of excavation, i.e. very sensitive to the change of existence environment. Based on test data analysis, the author elaborates the effects of engineering environment change on the engineering properties. Taking Nanyang basin as example, the author utilizes FEM to study the effects of various factors on stability of cutting canal slopes, than sets forth the characteristics, development laws and formation mechanism of the deformation and failure of hard clay canal slopes, summarizes the protection and reinforcement principles, as well as the protection and remedy steps. On the basis of comparison of engineering properties of domestic and foreign Neogene muddy deposits, in the view of whole globe and associated with the geological characteristics of China, the paper demonstrates that the intermediate type of the material between the soil and the rock, named "hard clay/soft rock", which can not be separated abruptly, really exists in China. The author has given a preliminary classification based on its geological origin and distribution law, which is very significant for promoting the mixture of Engineering Geology, Soil Mechanics and Rock Mechanics. In the course of large scales engineering construction in China, many engineering experiences and testing data are gained, summarizing these testing results and automatically managing them with computer technology are very necessary. The author develops a software named "Hard Clay-Soft Rock Engineering Geological Information Management and Analysis System (HRGIMS)", realizes the automatic and visual management of geo-engineering information, on the basis of information management, the functions of test data analysis and engineering property prediction are strengthened. This system has well merits for practice and popularization.