Relationship between the continually expanded interlayer distance of layered silicates and excess intercalation of cationic surfactants

Excess intercalation of cationic surfactants into Na-montmorillonites (MMTs) was investigated in organically modified silicates (OMSs), synthesized with MMTs and octadecylammonium chloride (OAC) by systematically varying the surfactant loading level from 0.625 to 1, 1.25, 1.56, 2, and 2.5 with respect to the cation exchange capacity (CEC) of MMTs. Wide-angle X-ray diffraction and thermogravimetric analysis results indicated that the continuous increase of interlayer distances came from the entering of surfactants into the interlayer of MMTs. Excess surfactants were extracted with a Soxhlet apparatus, which showed two kinds of intercalation states of surfactants in the interlayer when the surfactant loading level was beyond the CEC. Fourier transform infrared spectroscopy and differential scanning calorimetry were used to explore the microstructures of OMSs. It was found that the surfactants arranged more orderly as the loading level increased and the excess surfactants piled up in the interlayer together with counterions, forming a sandwiched surfactant layer. On the basis of the results, the layer structures of OMSs and the mechanism by which the surfactants entered the interlayer were expounded: surfactant cations entered the interlayer through cation exchange reactions and were tightly attracted to the silicate platelet surfaces when the surfactant loading level was below the CEC;

Layered silicates in Chondritic Porous Aggregate W7029*A : a case of primary growth

An important subset of extraterrestrial particles that reach the Earth's stratosphere include the so-called Chondritic Porous Aggregates (CPA's) [1-3]. In general, CPA's have a fluffy morphology and consist of numerous (>104)subparticles that are often <100A in size [4]. Mineral species in CPA's include Mg-rich pyroxene and olivine, Fe- and (Fe,Ni)-sulphides, taenite, Fe,Ni-carbides, magnetite, Ti-metal, a Bi-phase (metal or oxide), and variable amounts of carbonaceous material [1, 5-7]. Hydrated silicates are rare in CPA's and are limited to aggregates that have not been severely altered (thermo-metamorphosed) during atmospheric entry [8]. The presence of hydrated silicates in one cosmic dust particle was established by X-ray diffraction [2] and has been inferred in others by infra-red spectroscopy [8]. If CPA's are cometary, their mineralogy and morphology suggest that at least two episodes of aggregation occurred and that variations in porosity may be related to local differences in ice-to-dust ratio [3].

The trapping and decomposition of toxic gases such as hydrogen cyanide using modified mesoporous silicates

Selected silicas were modified with the covalently bound ligand 2,6-bis(benzoxazoyl)pyridine (BBOP), equilibrated with copper(II) nitrate, then challenged with toxic vapour containing HCN (8000 mg m(-3) at 80% relative humidity). The modified SBA-15 material (Cu-BBOP-SBA-15) had an improved breakthrough time for HCN (36 min at a flow rate of 30 cm(3) min(-1)) when compared to the other siliceous materials prepared in this study, equating to a hydrogen cyanide capacity of 58 mg g(-1), which is close to a reference activated carbon adsorbent (24 min at 50 cm(3) min(-1)) that can trap 64 mg g(-1). The enhanced performance observed with Cu-BBOP-SBA-15 has been related to the greater accessibility of the functional groups, arising from the ordered nature of the interconnected porous network and large mesopores of 5.5 nm within the material modified with the Cu(II)-BBOP complex. Modified MCM-41 and MCM-48 materials (Cu-BBOP-MCM-41 and Cu-BBOP-MCM-48) were found to have lower hydrogen cyanide capacities (38 and 32 mg g(-1) respectively) than the Cu-BBOP-SBA-15 material owing to the restricted size of the pores (2.2 and <2 nm respectively). The materials with poor nano-structured ordering were found to have low hydrogen cyanide capacities, between 11 and 19 mg g(-1), most likely owing to limited accessibility of the functional groups. (C) 2004 Elsevier Inc. All rights reserved.

(Table 1) Chemical composition of Fe-rich layered silicates from the East Korean Rise, Japan Sea

Mineral and chemical compositions of highly ferruginous layered silicates (HLS) of glauconite sands occurred on the East Korean Rise outside volcanic structures and on an unnamed volcano and the Chentsov Volcano have been studied. The use of cluster and discriminant analyses has resulted to more objectively distinguished groups among HLS, and the use of factor analysis - to illustrate correlations between chemical elements in different groups. It has been found that green mineral assemblages of the East Korean Rise are heterogeneous in terms of morphology, composition and origin, and their formation is a complex multistage process including both neoformation and degradation.

Processing and Characterization of Nano-biocomposites Based on Mater-Bi® with Layered Silicates

The development of new nano-biocomposites has been one of the main research areas of interest in polymer science in recent years, since they can combine the intrinsic biodegradable nature of matrices with the ability to modify their properties by the addition of selected nano-reinforcements. In this work, the addition of mineral nanoclays (montmorillonites and sepiolites) to a commercial starch-based matrix is proposed. A complete study on their processing by melt-intercalation techniques and further evaluation of the main properties of nano-biocomposites has been carried out. The results reported show an important influence of the nano-biocomposites morphology on their final properties. In particular, the rheological and viscoelastic characteristics of these systems are very sensitive to the dispersion level of the nanofiller, but it is possible to assess that the material processing behaviour is not compromised by the presence of these nano-reinforcements. In general, both nanofillers had a positive influence in the materials final properties. Mechanical performance shows improvements in terms of elastic modulus, without important limitations in terms of ductility. Thermal properties are improved in terms of residual mass after degradation and low improvements are also observed in terms of oxygen barrier properties.

Morphology and properties of thermoplastic polyurethane nancomposites incorporating hydrophilic layered silicates

Hydrophilic layered silicate/polyurethane nanocomposites were prepared via twin screw extrusion and solvent casting. Good dispersion and delamination was achieved-regardless of processing route, illustrating that the need for optimised processing conditions diminishes when there is a strong driving for de for intercalation between the polymer and organosilicate. Evidence for altered polyurethane microphase morphology in the nanocomposites was provided by DMTA and DSC. WAXD results suggested that the appearance of an additional high temperature melting endotherm in some melt-compounded nanocomposites was not due to the formation of a second crystal polymorph, but rather due to more well-ordered hard microdomains. Solvent casting was found to be the preferred processing route due to the avoidance of polyurethane and surfactant degradation associated with melt processing. While tensile strength and elongation were not improved on organosilicate addition, large increases in stiffness were observed. At a 7 wt% organosilicate loading, a 3.2-fold increase in Young's modulus was achieved by solvent casting. The nanocomposites also displayed higher hysteresis and permanent set. (C) 2004 Elsevier Ltd. All rights reserved.

An investigation on the dispersion of montmorillonite (MMT) primary particles in PP matrix

A novel path of preparing PP/o-MMT nanocomposites, which pay attention to the breaking up of MMT original agglomerates and dispersing of its primary particles, rather than the intercalation or exfoliation degree of o-MMT, was reported. The method of predispersing the o-MMT particles into a polar poly(vinyl alcohol) (PVA) matrix and then melt blending the pre-treated PVA/o-MMT hybrids with PP was studied. 3-isopropenyl-alpha,alpha-dimethylbenzene-isocyanate (TMI) was used as a modifier of PVA to improve the compatibility between PVA and PP matrix. Pre-disperse o-MMT with TMI modified PVA was proved to be an effective way to get a composite with fine o-MMT particles dispersion. But the method, which is pre-dispersing o-MMT with non modified PVA and then using TMI to modify such PVA/o-MMT hybrid, would largely reduce the reaction degree between TMI and PVA because of the relatively lower reaction temperature. Although the latter method also can obtain finer dispersion composites than that with using PP-g-MAH as compatibilizer, the relatively higher degradation degree of PP matrix in this method will limit the use of this nanocomposite.

Effects of surfactant loadings on the dispersion of clays in maleated polypropylene

A series of organically modified clays (OMCs) with a surfactant loading range from 0.625 to 2.5 times the cation exchange capacity (CEC) were melt-mixed with maleated polypropylene (PPMA). Wide-angle X-ray diffraction and transmission electron microscopy results of these narrocomposites show that dispersion of clays becomes unfavorable in the PPMA matrix during melt intercalation as the surfactant loading increases in the process of modifying clays, though larger interlayer distances are obtained in their corresponding OMCs. It is even important that clays uniformly disperse at the nanoscale level in the PPMA matrix when the surfactant loadings are below the CEC, which implies that incomplete exchange of inorganic cations in the process of modifying clay benefits the dispersion of clays in the PPMA matrix.

Segmented polyurethane nanocomposites: Impact of controlled particle size nanofillers on the morphological response to uniaxial deformation

A series of TPU nanocomposites were prepared by incorporating organically modified layered silicates with controlled particle size. To our knowledge, this is the first study into the effects of layered silicate diameter in polymer nanocomposites utilizing the same mineral for each size fraction. The tensile properties of these materials were found to be highly dependent upon the size of the layered silicates. A decrease in disk diameter was associated with a sharp upturn in the stress-strain curve and a pronounced increase in tensile strength. Results from SAXS/SANS experiments showed that the layered silicates did not affect the bulk TPU microphase structure and the morphological response of the host TPU to deformation or promote/hinder strain-induced soft segment crystallization. The improved tensile properties of the nanocomposites containing the smaller nanofillers resulted from the layered silicates aligning in the direction of strain and interacting with the TPU sequences via secondary bonding. This phenomenon contributes predominantly above 400% strain once the microdomain architecture has largely been disassembled. Large tactoids that are unable to align in the strain direction lead to concentrated tensile stresses between the polymer and filler, instead of desirable shear stresses, resulting in void formation and reduced tensile properties. In severe cases, such as that observed for the composite containing the largest silicate, these voids manifest visually as stress whitening.

Effect of the average soft-segment length on the morphology and properties of segmented polyurethane nanocomposites

Two organically modified layered silicates (with small and large diameters) were incorporated into three segmented polyurethanes with various degrees of microphase separation. Microphase separation increased with the molecular weight of the poly(hexamethylene oxide) soft segment. The molecular weight of the soft segment did not influence the amount of polyurethane intercalating the interlayer spacing. Small-angle neutron scattering and differential scanning calorimetry data indicated that the layered silicates did not affect the microphase morphology of any host polymer, regardless of the particle diameter. The stiffness enhancement on filler addition increased as the microphase separation of the polyurethane decreased, presumably because a greater number of urethane linkages were available to interact with the filler. For comparison, the small nanofiller was introduced into a polyurethane with a poly(tetramethylene oxide) soft segment, and a significant increase in the tensile strength and a sharper upturn in the stress-strain curve resulted. No such improvement occurred in the host polymers with poly(hexamethylene oxide) soft segments. It is proposed that the nanocomposite containing the more hydrophilic and mobile poly(tetramethylene oxide) soft segment is capable of greater secondary bonding between the polyurethane chains and the organosilicate surface, resulting in improved stress transfer to the filler and reduced molecular slippage. (c) 2006 Wiley Periodicals, Inc.