A study on the parameters affecting the compressibility characteristics of Cochin marine clays

There are numerous parameters affecting the compressibility characteristics of soft clays. A few of them such as load increment ratio, type of drainage and thickness of sample were taken up for detailed investigation. However, the main thrust in the present investigations was to develop an insight into the benefits of preloading technique, envolve procedures and establish design charts for preparation of a precompression programme which will substantially reduce the consolidation settlements of the extremely soft deposits of Cochin marine clays.

Thermal characterisation of dye-intercalated K-10 montmorillonite ceramics using photoacoustic technique

Thermal diffusivity (TD) measurements were performed on some industrially important dyes – auramine O (AO), malachite green and methylene blue (MB) – adsorbed K-10 montmorillonites using photoacoustic method. The TD value for the dye-adsorbed clay mineral was observed to change with a variation in dye concentration. The contribution of the dye towards TD was also determined. The repeatedly adsorbed samples with MB and AO exhibited a lower TD than the single-adsorbed samples. TD values of sintered MB samples were also obtained experimentally. These sintered samples exhibit a higher TD, although they show a trend similar to that of non-sintered pellets. A variation in dye concentration and sintering temperature can be used for tuning the TD value of the clay mineral to the desired level

Thermal characterization of methylene blue intercalated montmorillonites by photoacoustic technique

Thermal diffusivity (TD) measurement on commercial K-10 and KSF montmorillonites was carried out by photoacoustic technique. The TD of the montmorillonites after methylene blue adsorption changed with the dye concentration. The repeatedly adsorbed samples showed a lesser TD than the single adsorbed samples. After methylene blue adsorption the acid leached K-10 samples showed well defined changes in TD when compared to the ordered KSF samples

A study on mitigating the effect of sulphates in lime stabilised Cochin marine clays

Soft clays known for their high compressibility, low stiffness and low shear strength are always associated with large settlement. In place soil treatment using calcium-based stabilizers like lime and cement is a feasible solution to readdress strength deficiencies and problematic shrink/swell behaviour of unstable subgrade soils. Out of these, lime has been proved unambiguously as the most effective and economical stabilising agent for marine clays. Lime stabilisation creates long-term chemical changes in unstable clay soils to create strong, but flexible, permanent structural layers in foundations and other pavement systems. Even though calcium-based stabilizers can improve engineering properties of soft clays, problems can arise when they are used in soils rich in sulphates. It is possible for marine clays to be enriched with sulphates, either by nature or due to the discharge of nearby industrial wastes containing sulphates. The presence of sulphates is reported to adversely affect the cation exchange and pozzolanic reactions of cement and lime treated soil systems. The anions of sulphates may combine with the available calcium and alumina, and form insoluble ettringite in the soil system. Literature on sulphate attack in lime treated marine clays reports that formation of ettringite in lime-sodium sulphate-clay system is capable of adversely affecting the engineering behavior of marine clays. Only very few studies have been conducted on soft marine clays found along the coastal belt of Kerala and that too, is limited to Cochin marine clays. The studies conducted also have the limitation that the strength behaviour of lime stabilised clay was investigated only for one year. Practically no data pertaining to long term adverse effects likely to be brought about by sulphates on the strength and compressibility characteristics of Cochin marine clays is available. The overriding goal of this investigation was thus to examine the effectiveness of lime stabilisation in Cochin marine clays under varying sulphate contents. The study aims to reveal the changes brought about by varying sulphate contents on both physical and engineering properties of these clays stabilised by lime and the results for various curing periods up to two years is presented in this thesis. Quite often the load causing an unacceptable settlement may be less than the load required to cause shear failure and therefore attempt has been made in this research to highlight sulphate induced changes in both the compressibility and strength characteristics of lime treated Cochin marine clays. The study also aimed at comparing the available IS methods for sulphate quantification and has attempted to determine the threshold level of sulphate likely make these clays vulnerable by lime stabilisation. Clays used in this study were obtained from two different sites in Kochi and contained sulphate in two different concentrations viz., 0.5% and 0.1%. Two different lime percentages were tried out, 3% and 6%. Sulphate content was varied from 1% to 4% by addition of reagent grade sodium sulphate. The long term influence of naturally present sulphate is also investigated. X-ray diffraction studies and SEM studies have been undertaken to understand how the soil-lime reactions are affected in the presence of sodium sulphate. Natural sulphate content of 0.1% did not seem to have influenced normal soil lime reactions but 0.5% sulphate could induce significant changes adversely in both compressibility and strength behaviour of lime treated clays after long duration. Compressibility is seen to increase drastically with increasing sulphate content suggesting formation of ettringite on curing for longer periods. Increase in compression index and decrease in bond strength with curing period underlined the adverse effects induced in lime treated marine clays by the presence of sulphates. Presence of sulphate in concentrations ranging from 0.5 % to 4% is capable of adversely affecting the strength of lime treated marine clays. Considerable decrease is observed with increasing concentrations of sulphate. Ettringite formation due to domination of sodium ions in the system was confirmed in mineralogical studies made. Barium chloride and barium hydroxide is capable of bringing about beneficial changes both in compressibility and strength characteristics of lime treated Cochin marine clays in the presence of varying concentrations of sulphate and is strongly influenced by curing time. Clay containing sodium sulphate has increased strength values when either of barium compounds was used with lime ascompared with specimens treated with lime only. Barium hydroxide is observed to remarkably increase the strength as compared to barium chloride,when used in conjunction with lime to counteract the effect of sulphate.

Catalysis by Modified Pillared Clays and Porous Clay Heterostructures

In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are  Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method.  Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications.  The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process.  Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process.  Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays.  The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification.  The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers.  Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs.  In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260  Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions.  For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia.  Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction.  SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials  In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis.  In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR.  In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis.  In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS.  Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261  Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties.  Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol.  Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol.  DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method.  DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.

A preliminary investigation of the release of oil from contaminated clays and other fine-grained sediments during consolidation

Fine-grained sediments on land, or in a freshwater or marine environment, may become contaminated with a wide range of pollutants including hydrocarbons. This paper is concerned with preliminary studies of the mobilization and transportation of hydrocarbons, during the process of consolidation, to adjacent sediments or water bodies. A modified Rowe Cell was used to measure the consolidation properties of prepared kaolinite and bentonite clay-water slurries, with and without the addition of oil, along with hydrocarbon-bearing drill-cuttings samples taken from the sea-bed adjacent to two North Sea oil-well platforms. The consolidation properties of the kaolinite and bentonite clay slurries were little altered by the addition of oil, which was present at concentrations of between 8073 and 59 572 mg kg(-1). During each consolidation stage, samples of the expelled pore-fluids were collected and analysed for oil content. These values were very low in comparison with the original oil concentration in the samples and changed little between each consolidation stage. Analysis of the slurry samples both before and after consolidation confirms that, proportionally, little oil is removed as a result of consolidation. The implication of these results is that, for the range of samples tested, the very high hydraulic gradients and particle rearrangements that occur during the process of consolidation are capable of releasing only proportionally small amounts of oil bound to the fine-grained clay and silt particles.

A preliminary investigation of the release of oil from contaminated clays and other fine-grained sediments during consolidation

Fine-grained sediments on land, or in a freshwater or marine environment, may become contaminated with a wide range of pollutants including hydrocarbons. This paper is concerned with preliminary studies of the mobilization and transportation of hydrocarbons, during the process of consolidation, to adjacent sediments or water bodies. A modified Rowe Cell was used to measure the consolidation properties of prepared kaolinite and bentonite clay-water slurries, with and without the addition of oil, along with hydrocarbon-bearing drill-cuttings samples taken from the sea-bed adjacent to two North Sea oil-well platforms. The consolidation properties of the kaolinite and bentonite clay slurries were little altered by the addition of oil, which was present at concentrations of between 8073 and 59 572 mg kg(-1). During each consolidation stage, samples of the expelled pore-fluids were collected and analysed for oil content. These values were very low in comparison with the original oil concentration in the samples and changed little between each consolidation stage. Analysis of the slurry samples both before and after consolidation confirms that, proportionally, little oil is removed as a result of consolidation. The implication of these results is that, for the range of samples tested, the very high hydraulic gradients and particle rearrangements that occur during the process of consolidation are capable of releasing only proportionally small amounts of oil bound to the fine-grained clay and silt particles.

Immobilisation of eta(3)-allyidicarbonyl complexes of Mo-II with bidentate nitrogen ligands within aluminium-pillared clays

Molybdenum(II) complexes [MOX(CO)(2)(eta(3)-allyl)(CH3CN)(2)] (X = Cl or Br) were encapsulated in an aluminium-pillared natural clay or a porous clay heterostructure and allowed to react with bidentate diimine ligands. All the materials obtained were characterised by several solid-state techniques. Powder XRD, and Al-27 and Si-29 MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. C-13 CP MAS NMR, FTIR, elemental analyses and low-temperature nitrogen adsorption showed that the immobilisation of the precursor complexes was successful as well as the in situ ligand-substitution reaction. The new complex [MoBr(CO)(2)(eta(3)-allyl)(2-aminodipyridyl)] was characterised by single-crystal X-ray diffraction and spectroscopic techniques, and NMR studies were used to investigate its fluxional behaviour in solution. The prepared materials are active for the oxidation of cis-cyclooctene using tert-butyl hydroperoxide as oxidant, though the activity of the isolated complexes is higher. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Study of picosecond processes of an intercalated dipyridophenazine Cr(iii) complex bound to defined sequence DNAs using transient absorption and time-resolved infrared methods

Picosecond transient absorption (TA) and time-resolved infrared (TRIR) measurements of rac-[Cr(phen)2(dppz)]3+ (1) intercalated into double-stranded guanine-containing DNA reveal that the excited state is very rapidly quenched. As no evidence was found for the transient electron transfer products, it is proposed that the back electron transfer reaction must be even faster (<3 ps).

The impact of charge transfer and structural disorder on the thermoelectric properties of cobalt intercalated TiS2

A family of phases, CoxTiS2 (0 ≤ x ≤ 0.75) has been prepared and characterised by powder X-ray and neutron diffraction, electrical and thermal transport property measurements, thermal analysis and SQUID magnetometry. With increasing cobalt content, the structure evolves from a disordered arrangement of cobalt ions in octahedral sites located in the van der Waals’ gap (x ≤ 0.2), through three different ordered vacancy phases, to a second disordered phase at x ≥ 0.67. Powder neutron diffraction reveals that both octahedral and tetrahedral inter-layer sites are occupied in Co0.67TiS2. Charge transfer from the cobalt guest to the TiS2 host affords a systematic tuning of the electrical and thermal transport properties. At low levels of cobalt intercalation (x < 0.1), the charge transfer increases the electrical conductivity sufficiently to offset the concomitant reduction in |S|. This, together with a reduction in the overall thermal conductivity leads to thermoelectric figures of merit that are 25 % higher than that of TiS2, ZT reaching 0.30 at 573 K for CoxTiS2 with 0.04 ≤ x ≤ 0.08. Whilst the electrical conductivity is further increased at higher cobalt contents, the reduction in |S| is more marked due to the higher charge carrier concentration. Furthermore both the charge carrier and lattice contributions to the thermal conductivity are increased in the electrically conductive ordered-vacancy phases, with the result that the thermoelectric performance is significantly degraded. These results illustrate the competition between the effects of charge transfer from guest to host and the disorder generated when cobalt cations are incorporated in the inter-layer space.

Iron oxyhydroxide nanostructured in montmorillonite clays: Preparation and characterization

Akaganeite is a very rare iron oxyhydroxide in nature. It can be obtained by many synthetic routes, but thermohydrolysis is the most common method reported in the literature. In this work, akaganeite-like materials were prepared through the thermohydrolysis of FeCl(3)center dot 6H(2)O in water and suspensions containing clay minerals. X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) data show that the clays determine the crystal phase and size of the iron oxyhydroxide crystals. According to XRD and FTIR data, beta-FeO(OH) (akaganeite) is the main metal oxyhydroxide phase. Considering the small basal spacing (d(0 0 1)) displacement observed when comparing the XRD patterns of pristine clays with the composites containing beta-FeO(OH), the iron oxyhydroxide should be mostly located on the basal and edge surfaces of the clay minerals. UV-Vis electronic absorption spectra indicate that the preferred phase of the iron oxyhydroxide is determined by the nature of the clay minerals. (C) 2010 Elsevier Inc. All rights reserved.

Oxidation of anilinium ions intercalated in montmorillonite clay by electrochemical route

Resonance Raman, FTIR, X-ray diffraction, UV-vis-NIR, electron paramagnetic resonance, X-ray absorption at Si K-edge and electron microscopy were employed for characterizing the products formed through electrochemical oxidation of intercalated anilinium ions inside the cationic montmorillonite (MMT) clay. The layer silicate structure was not affected by the anilinium oxidation between the layers. The intercalated products present only an electronic absorption band at 400 nm, very low conductivity (ca. 10(-7) S cm(-1)) and their Raman spectrum displays bands, with high relative intensities, assigned to the benzidine dication, indicating that this product was formed in high amount. Nevertheless, bands that can be correlated to phenazine-like segments and 1,4-phenylenediamine repeat units (PANI like segments) are also observed. The very low EPR signal indicates that diamagnetic species are predominant. All results are compared to those obtained by anilinium-MMT chemically oxidized by persulfate and the differences are pointed out. (C) 2008 Elsevier B.V. All rights reserved.

Effect of sonication on the particle size of montmorillonite clays

This paper reports on the effect of sonication on SAz-1 and SWy-1 montmorillonite suspensions. Changes in the size of the particles of these materials and modifications of their properties have been investigated. The variation of the particle size has been analyzed by DLS (dynamic light scattering). In all cases the clay particles show a bimodal distribution. Sonication resulted in a decrease of the larger modal diameter, as well as a reduction of its volume percentage. Simultaneously, the proportion of the smallest particles increases. After 60 min of sonication, SAz-1 presented a very broad particle size distribution with a modal diameter of 283 nm. On the other hand, the SWy-1 sonicated for 60 min presents a bimodal distribution of particles at 140 and 454 nm. Changes in the properties of the clay suspensions due to sonication were evaluated spectroscopically from dye-clay interactions, using Methylene Blue. The acidic sites present in the interlamellar region, which are responsible for dye protonation, disappeared after sonication of the clay. The changes in the size of the scattering particles and the lack of acidic sites after sonication suggest that sonication induces delamination of the clay particles. (c) 2008 Elsevier Inc. All rights reserved.

Evolução diagenética e caracterização dos reservatórios da seção devoniana na Bacia do Rio do Peixe-Nordeste do Brasil

The Rio do Peixe Basin represents a main basin of northeastern Brazil and pioneering work positioned the rocks of this basin in the Early Cretaceous. However, a recent study, based on integrated pollen analysis from three wells, found an unprecedented siliciclastic sedimentary section, in the region, of early Devonian age. Therefore, the present study aims a detailed petrographic and petrological analysis of this devonian section, in the Rio do Peixe Basin and proposes a diagenetic evolution, to understand the characteristics of the porous system, identify the main reservoir petrofacies with the main factors impacting on the quality of these rocks as reservoirs and a quick study on the provenance of this section. The petrographic study was based on samples obtained from subsurface and surface. The diagenetic evolution of petrofacies and its identification were based only on subsurface samples and the study of provenance was based on surface samples. The thin sections were prepared from sandstones, pelites and sandstones intercalated with pelites. The original detrital composition for this section is arcosean and the main diagenetic processes that affected these rocks occur in various depths and different conditions, which resulted in extensive diagenetic variety. The following processes were identified: early fracture and healing of grains; albitization of K-feldspar and plagioclase; siderite; precipitation of silica and feldspar; mechanical infiltration of clay and its transformation to illite/esmectite and illite; autigenesis of analcime; dissolution; autigenesis of chlorite; dolomite/ferrous dolomite/anquerite; apatite; calcite; pyrite; titanium minerals and iron oxide-hidroxide. The occurrence of a recently discovered volcanism, in the Rio do Peixe Basin, may have influenced the diagenetic evolution of this section. Three diagenetic stages affected the Devonian section: eo, meso and telodiagenesis. This section is compositionally quite feldspathic, indicating provenance from continental blocks, between transitional continental and uplift of the basement. From this study, we observed a wide heterogeneity in the role of the studied sandstones as reservoirs. Seven petrofacies were identified, taking into account the main diagenetic constituent responsible for the reduction of porosity. It is possible that the loss of original porosity was influenced by intense diagenesis in these rocks, where the main constituent for the loss of porosity are clays minerals, oxides and carbonate cement (calcite and dolomite)

Recycling of glass cullet as aggregate for clays used to produce roof tiles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)