Novel acidic porous clay heterostructure with highly ordered organic-inorganic hybrid structure: one-pot synthesis of mesoporous organosilica in the galleries of clay

A new class of organic-inorganic hybrid porous clay heterostructures (HPCHs) have been prepared through the surfactant-directed assembly of organosilica in the galleries of montmorillonite. The reaction involved hydrolysis and condensation of phenyltriethoxysilane and tetraethoxysilane in the presence of intragallery surfactant templates (dodecylame and cetyltrimethylammonium ion). The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), N-2 adsorption, solid-state Si-29 and C-13 NMR, and FTIR. XRD patterns indicated a regular interstratification of the clay layers for HPCHs. Depending on loading of phenyl groups, HPCHs had BET surface areas of 390-771 m(2) g(-1), pore volumes of 0.3-0.59 cm(3) g(-1), and the framework pore sizes in the supermicropore to small mesopore range (1.2-2.6 nm). HPCHs were hydrophobic and acidic.

Synthesis and characterization of polyethylene/clay-silica nanocomposites: A montmorillonite/silica-hybrid-supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT-Si) supported catalyst, was developed. MT-Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT-Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay-silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system.

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.