Strength mobilization in clays and silts

A large database of 115 triaxial, direct simple shear, and cyclic tests on 19 clays and silts is presented and analysed to develop an empirical framework for the prediction of the mobilization of the undrained shear strength, cu, of natural clays tested from an initially isotropic state of stress. The strain at half the peak undrained strength (γM=2) is used to normalize the shear strain data between mobilized strengths of 0.2cu and 0.8cu. A power law with an exponent of 0.6 is found to describe all the normalized data within a strain factor of 1.75 when a representative sample provides a value for γM=2. Multi-linear regression analysis shows that γM=2 is a function of cu, plasticity index Ip, and initial mean effective stress p′0. Of the 97 stress-strain curves for which cu, Ip, and p′0 were available, the observed values of γM=2 fell within a factor of three of the regression; this additional uncertainty should be acknowledged if a designer wished to limit immediate foundation settlements on the basis of an undrained strength profile and the plasticity index of the clay. The influence of stress history is also discussed. The application of these stress-strain relations to serviceability design calculations is portrayed through a worked example. The implications for geotechnical decision-making and codes of practice are considered.

Structural tuning of Montmorillonite clays by pillaring: Designing of shape selective solid acid catalysts and PANI - Montmorillonite nanocomposites

Green chemistry boots eco-friendly,natural clays as catalysts in the chemical as well as in the pharmaceutical industry.Industry demands thermal stability,mechanical strength etc for the catalyst and there the modification methods becomes important.Pillaring tunes clays as efficient catalytic templates for shape selective organic synthesis.Here pillared clays are used as promising alternatives for the environmentally hazardous homogeneous catalysts in some industrially important Friedel-Crafts alkylation reactions of arenes with lower alchohols and higher olefins.The layer structure is enhanced upon pillaring and allows the nanocomposite formation with polyaniline to develop today’s nanoscale diameter devices.Present work gives an entry of pillared clays to the world of conducting composite nanofibers.

Estudo comparativo entre a pirólise do polietileno de baixa densidade, utilizando vermiculita modificada e SBA-15

Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials

Argilas modificadas: remoção de antraceno e ácido 9-antróico como modelo para aromáticos (hpa) presentes em águas

Pós-graduação em Química - IBILCE

Synthesis and characterization of structurally well-defined polymer-layered silicate nanocomposites

Zusammenfassung Nanokomposite aus Polymeren und Schichtsilikaten werden zumeist auf der Basis natürlicher Tone wie Montmorillonit hergestellt. Für NMR- und EPR-Untersuchungen der Tensidschicht, die das Silikat mit dem Polymer kompatibilisiert, ist der Eisengehalt natürlicher Tone jedoch abträglich, weil er zu einer Verkürzung der Relaxationszeiten und zu einer Linienverbreiterung in den Spektren führt. Dieses Problem konnte überwunden werden, indem als Silikatkomponente eisenfreies, strukturell wohldefiniertes Magadiit hydrothermal synthetisiert und für die Kompositbildung eingesetzt wurde. Die Morphologie des Magadiits wurde durch Rasterelektronenmikroskopie charakterisiert und der Interkalationsgrad von schmelzinterkalierten Polymer-Nanokompositen wurde durch Weitwinkelröntgenstreuung bestimmt. Polymere mit Carbonylgruppen scheinen leichter zu interkalieren als solche ohne Carbonylgruppen. Polycaprolacton interkalierte sowohl in Oragnomagadiite auf der Basis von Ammoniumtensiden als auch in solche auf der Basis von Phosphoniumtensiden. Die Dynamik auf einer Nanosekundenzeitskala und die Struktur der Tensidschicht wurden mittels ortsspezifisch spinmarkierter Tensidsonden unter Nutzung von Dauerstrich- (CW) und Puls-Methoden der elektronenparamagnetischen Resonanzspektroskopie (EPR) untersucht. Zusätzlich wurde die statische 2H-Kernmagnetresonanz (NMR) an spezifisch deuterierten Tensiden angewendet, um die Tensiddynamik auf einer komplementären Zeitskala zwischen Mikrosekunden und Millisekunden zu erfassen. Sowohl die CW-EPR- als auch die 2H-NMR-Ergebnisse zeigen eine Beschleunigung der Tensiddynamik durch Interkalation von Polycaprolacton auf, während sich in den nichtinterkalierten Mikrokompositen mit Polystyrol die Tensiddynamik verlangsamt. Die Rotationskorrelationszeiten und Aktivierungsenergien offenbaren verschiedene Regime der Tensiddynamik. In Polystyrol-Mikrokompositen entspricht die Übergangstemperatur zwischen den Regimen der Glasübergangstemperatur von Polystyrol, während sie in Polycaprolacton-Nanokompositen bei der Schmelztemperatur von Polycaprolacton liegt. Durch die erhebliche Verlängerung der Elektronenspin-Relaxationszeiten bei Verwendung von eisenfreiem Magadiit können Messdaten hoher Qualität mit Puls-EPR-Experimenten erhalten werden. Insebsondere wurden die Vier-Puls-Elektron-Elektron-Doppelresonanz (DEER), die Elektronenspinechoenveloppenmodulation (ESEEM) und die Elektronen-Kern-Doppelresonanz (ENDOR) an spinmarkierten sowie spezifisch deuterierten Tensiden angewandt. Die ENDOR-Ergebnisse legen ein Model der Tensidschicht nahe, in dem zusätzlich zu den Oberflächenlagen auf dem Silikat eine wohldefinierte mittlere Lage existiert. Dieses Modell erklärt auch Verdünnungseffekte durch das Polymer in Kompositen mit Polycaprolacton und Polystyrol. Die umfangreiche Information aus den Magnetresonanztechniken ergänzt die Information aus konventionellen Charakterisierungstechniken wie Röntgendiffraktion und Transmissionselektronenmikroskopie und führt so zu einem detaillierteren Bild der Struktur und Dynamik der Tensidschicht in Nanokompositen aus Polymeren und Schichtsilikaten.

Clay-supported graphene materials: application to hydrogen storage

The present work refers to clay–graphene nanomaterials prepared by a green way using caramel from sucrose and two types of natural clays (montmorillonite and sepiolite) as precursors, with the aim of evaluating their potential use in hydrogen storage. The impregnation of the clay substrates by caramel in aqueous media, followed by a thermal treatment in the absence of oxygen of these clay–caramel intermediates gives rise to graphene-like materials, which remain strongly bound to the silicate support. The nature of the resulting materials was characterized by different techniques such as XRD, Raman spectroscopy and TEM, as well as by adsorption isotherms of N2, CO2 and H2O. These carbon–clay nanocomposites can act as adsorbents for hydrogen storage, achieving, at 298 K and 20 MPa, over 0.1 wt% of hydrogen adsorption excess related to the total mass of the system, and a maximum value close to 0.4 wt% of hydrogen specifically related to the carbon mass. The very high isosteric heat for hydrogen sorption determined from adsorption isotherms at different temperatures (14.5 kJ mol−1) fits well with the theoretical values available for hydrogen storage on materials that show a strong stabilization of the H2 molecule upon adsorption.

Obtenção de organovermiculitas utilizando tensoativos e microemulsões e suas aplicações na separação de isômeros do Xileno

Surfactants are versatile organic compounds that have, in a single molecule, double chemical affinity. The surfactant molecule is composed by a hy drophobic tail group, a hydrocarbon chain (linear, branched, or mixed), and by a hydrophilic head group, which contains polar groups that makes it able to be applied in the organophilization process of natural clays. Microemulsions are microheterogeneous b lends composed by: a surfactant, an oily phase (non - polar solvent), an aqueous phase, and, sometimes, a co - surfactant (short - chain alcohol). They are systems with thermodynamic stability, transparent, and have high solubility power. Vermiculite is a clay m ineral with an expandable crystalline structure that has high cation exchange capacity. In this work vermiculite was used to obtain organoclays. The ionic surfactants dodecyl ammonium chlori de (DDAC) and cetyltrimethylammonium bromide (C 16 TAB) were used in the organophilization process. They were used as surfactant aqueous solutions and, for DDAC, as a microemulsion system. The organoclays were used to promote the separation of binary mixtures of xylene isomers (ortho - and meta - xylene). Dif ferent analytical techniques were used to characterize microemulsion systems and also the nanoclays. It was produced a water - rich microemulsion system with 0.92 nm droplet average diameter. The vermiculite used in this work has a cationic exchange capacity of 172 meq/100g and magnesium as main cation (24.25%). The basal spacing of natural vermiculite and organo - vermiculites were obtained by X - ray Diffraction technique. The basal spacing was 1.48nm for natural vermiculite, 4.01nm for CTAB - vermiculite (CTAB 4 ) , and 3.03nm for DDAC - vermiculite (DDAC M1A), that proves the intercalation process. Separation tests were carried out in glass columns using three binary mixtures of xylene (ortho - xylene and meta - xylene). The results showed that the organovermiculite pre sented an enhanced chemical affinity by the mixture of hydrocarbons, when compared with the natural vermiculite, and also its preference by ortho - xylene. A factorial experimental design 2 2 with triplicate at the central point was used to optimize the xylen e separation process. The experimental design revealed that the initial concentration of isomers in the mixture and the mass of organovermiculite were the significant factors for an improved separation of isomers. In the experiments carried out using a bin ary mixture of ortho - xylene and meta - xylene (2:1), after its percolating through the organovermiculite bed (DDAC M1), it was observed the preference of the organoclay by the ortho - xylene isomer, which was retained in greater quantity than the meta - xylene o ne. At the end of the treatment, it was obtained a final concentration in meta - xylene of 47.52%.

Características estruturais e fotocatalíticas do compósito oxihidróxido de nióbio/vermiculita

The preparation of nanostructured materials using natural clays as support, has been studied in literature under the same are found in nature and consequently, have a low price. Generally, clays serve as supports for metal oxides by increasing the number of active sites present on the surface and can be applied for various purposes such as adsorption, catalysis and photocatalysis. Some of the materials that are currently highlighted are niobium compounds, in particular, its oxides, by its characteristics such as high acidity, rigidity, water insolubility, oxidative and photocatalytic properties. In this scenario, the study aimed preparing a composite material oxyhydroxide niobium (NbO2OH) / sodium vermiculite clay and evaluate its effectiveness with respect to the natural clay (V0) and NbO2OH. The composite was prepared by precipitation-deposition method and then characterized by X-ray diffraction, infrared spectroscopy (XRD), energy dispersive X-ray (EDS), thermal analysis (TG/DTG), scanning electron microscopy (SEM), N2 adsorption-desorption and investigation of distribution of load. The application of the material NbO2OH/V0 was divided in two steps: first through oxidation and adsorption methods, and second through photocatalytic activity using solar irradiation. Studies of adsorption, oxidation and photocatalytic oxidation monitored the percentage of color removal from the dye methylene blue (MB) by UV-Vis spectroscopy. The XRD showed a decrease in reflection d (001) clay after modification; the FTIR indicated the presence of both the clay when the oxyhydroxide niobium to present bands in 1003 cm-1 related to Si-O stretching bands and 800 cm-1 to the Nb-O stretching. The presence of niobium was also confirmed by EDS indicated that 17 % by mass amount of the metal. Thermal analysis showed thermal stability of the composite at 217 °C and micrographs showed that there was a decrease in particle size. The investigation of the surface charge of NbO2OH/V0 found that the material exhibits a heterogeneous surface with average low and high negative charges. Adsorption tests showed that the composite NbO2OH/V0 higher adsorption capacity to remove 56 % of AM, while the material removed from V0 only 13 % showed no NbO2OH and adsorptive capacity due to the formation of H-aggregates. The percent removal of dye color for the oxidation tests showed little difference from the adsorption, being 18 and 66 % removal of dye color for V0 and NbO2OH/V0 respectively. The NbO2OH/V0 material shows excellent photocatalytic activity managing to remove just 95,5 % in 180 minutes of the color of MB compared to 41,4 % and 82,2 % of V0 the NbO2OH, proving the formation of a new composite with distinct properties of its precursors.

Fresh water and acid sensitivity of authigenic clays in sandstone reservoirs

Authigenic illite-smectite and chlorite in reservoir sandstones from several Pacific rim sedimentary basins in Australia and New Zealand have been examined using an Electroscan Environmental Scanning Electron Microscope (ESEM) before, during, and after treatment with fresh water and HCl, respectively. These dynamic experiments are possible in the ESEM because, unlike conventional SEMs that require a high vacuum in the sample chamber (10-6 torr), the ESEM will operate at high pressures up to 20 torr. This means that materials and processes can be examined at high magnifications in their natural states, wet or dry, and over a range of temperatures (-20 to 1000 degrees C) and pressures. Sandstones containing the illite-smectite (60-70% illite interlayers) were flushed with fresh water for periods of up to 12 hours. Close examination of the same illite-smectite lines or filled pores, both before and after freshwater treatments, showed that the morphology of the illite-smectite was not changed by prolonged freshwater treatment. Chlorite-bearing sandstones (Fe-rich chlorite) were reacted with 1M to 10M HCl at temperatures of up to 80 degrees C and for periods of up to 48 hours. Before treatment the chlorites showed typically platy morphologies. After HCl treatment the chlorite grains were coated with an amorphous gel composed of Ca, Cl, and possibly amorphous Si, as determined by EDS analyses on the freshly treated rock surface. Brief washing in water removed this surface coating and revealed apparently unchanged chlorite showing no signs of dissolution or acid attack. However, although the chlorite showed no morphological changes, elemental analysis only detected silicon and oxygen.

Near infrared spectroscopy of selected natural magnesium carbonates: implications for geosequestration

The approach to remove greenhouse gases by pumping liquid CO2 several kilometres below the ground implies that many carbonate containing minerals will be formed. Among these minerals, the formation of hydromagnesite, dypingite and nesquehonite are possible, thus necessitating a study of such minerals. These minerals with a hydrotalcite-related formulae have been characterised by a combination of infrared and near infrared spectroscopy. Layered double hydroxides (also known as anionic clays or hydrotalcites) are a group of layered clay minerals described by the general formula: [M1–x2+Mx3+(OH)2]x+[An–]x/n∙mH2O. The infrared spectra of the minerals are characterised by OH and water stretching vibrations. Both the first and second fundamental overtones of these bands are observed in the NIR spectra in the 7030–7235 cm–1 and 10,490–10,570 cm–1 spectral ranges. Intense (CO3)2– symmetrical and anti-symmetrical stretching vibrations confirm the distortion of the carbonate anion. The position of the water bending vibration indicates water is strongly hydrogen-bonded to the carbonate anion in the mineral structure. NIR spectroscopy offers a method for quickly analysing such materials.

Yielding of sensitive clays: micromechanical considerations

Test results reported on several natural sensitive soils show significant anisotropy of the yield curves, which are generally oriented along the coefficient of earth pressure at rest (K-0) axis. An attempt is made in this paper to explain the anisotropy in yielding from microstructural considerations. An elliptic pore, with particle domains aligned along the periphery of the pore, and with the major axis of the pore being oriented along the direction of the in situ major principal stress, is chosen as the unit of microstructure. An analysis of forces at the interdomain contacts around the ellipse is carried out with reference to experimentally determined yield stress conditions of one soil, and a yield criteria is defined. The analysis, with the proposed yield criteria, enables one to define the complete yield curve for any other soil from the results of only two tests (one constant eta compression test with eta close to eta(K?0), where eta is the stress ratio (= q/p) and eta(K?0) is the stress ratio corresponding to anisotropic K-0 compression, and another undrained shear test). Predicted yield curves are compared with experimental yield curves of several soils reported in the literature.

A study of geotechnical properties of Cochin Marine Clays

Most of the Greater Cochin area, which is undergoing rapid industrialisation, consists of extremely soft marine clay calling for expensive deep foundations. This paper presents a study on the physical properties and engeering characteristics of Cochin marine clays. These marine clays are characterised by high Atterberg limits and natural water contents. They are moderately sensitive with liquidity indices ranging over 0.46 to 0.87.The grain size distribution shows almost equal fractions of clay and silt size with sand content varying around 20%. Use of a dispersing agent in carrying out grain size distribution test plays an important role. The fabric of these clays had been identified as flocculant. The pore water has low salinity which results in marginal changes in properties on washing.Consolidation test results showed a preconsolidation pressure of up to about 0.5 kg/cm2 with high compression indices. Compression index vs liquid limit yielded a correlation comparable to that of published data. The undisturbed samples have a much larger coefficient of secondary consolidation as a result of flocculant fabric. These clays have very low undrained shear strength.

Engineering behavior of uplifted Smectite-rich Cochin and Mangalore marine clays

The present study aims to assess whether the smectite-rich Cochin and Mangalore clays, which were deposited in a marine medium and subsequently uplifted, exhibit consistency limits response typical of expanding lattice or nonexpanding (fixed) lattice-type clays on artificially changing the chemical environment. The chemical and engineering behaviors of Cochin and Mangalore marine clays are also compared with those of the smectite-rich Ariake Bay marine clay from Japan. Although Cochin, Mangalore, and Ariake clays contain comparable amounts of smectite (32-45%), Ariake clay exhibits lower consistency limits and much higher ranges of liquidity indices than the Indian marine clays. The lower consistency limits of the Ariake clay are attributed to the absence of well-developed, long-range, interparticle forces associated with the clay. Also, Ariake clay exhibits a significantly large (48-714 times) decrease in undrained strength on remolding in comparison to Cochin and Mangalore clays (sensitivity ranges between 1 and 4). A preponderance of long-range, interparticle forces reflected in the high consistency limits of Cochin and Mangalore clays (wL range from 75 to 180%) combined with low natural water contents yield low liquidity indices (typically <1) and high, remolded, undrained strengths and are considered to be responsible for the low sensitivity of the Indian marine clays.