Effect of aging on swelling and swell-shrink behavior of a compacted expansive soil

Effect of aging on swelling and swell-shrink behavior of a compacted expansive soil is investigated in this paper. An expansive soil having a liquid limit of 100% is used for this purpose. Compacted specimens were prepared and aged for a predetermined number of days (7, 15, 30, and 90 days) to study their swelling and swell-shrink behavior. It has been shown that aging improves the resistance to compression of compacted specimens. The swelling potentials of specimens also decreased with aging. The dominant factors that influence the aging effects are the water content and degree of saturation at the beginning of the aging process. The changed behavior of aged specimens is attributed to particle rearrangements and formation of bonds, which affect the surface area absorbing water during swelling. The cyclic swell-shrink tests on aged specimens indicated that the differences in vertical displacement during the first swelling were eliminated in the subsequent cycles when specimens were shrunk more, but the aging effect was found to persist with cycles for specimens subjected to lower shrinkage magnitudes.

Efficient visible light induced nuclease activity of a ternary mono-1,10-phenanthroline copper(II) complex containing 2-(methylthio)ethylsalicylaidimine

Ternary Schiff base copper(II) complex [CuL(phen)](ClO4), where HL is 2-(methylthio)ethylsalicylaldimine and phen is 1,10-phenanthroline, has been prepared and structurally characterized by X-ray crystallography. The complex shows a CuN3OS coordination in a square-pyramidal (4 + 1) geometry with the sulfur as an equatorial ligand. The complex is an avid binder to double-stranded DNA in the minor groove and exhibits both photonuclease and chemical nuclease activity. When exposed to UV light of 312 nm (96 W) or visible light of 532 nm (125 W) under aerobic conditions, the complex causes significant cleavage of supercoiled pUC19 DNA in the absence of any externally added reducing agent or H2O2.

Role of soil structure and matric suction in collapse of a compacted clay soil

This paper examines the role of microstructure and matric suction in the collapse behavior of a compacted clay soil from Bangalore District in Karnataka State, India. The microstructure of the compacted specimens was examined by mercury intrusion porosimetry (MIP), and the ASTM Filter Paper Method was used to determine their matric suction. The microstructure and matric suction of the compacted specimens were changed by varying their compaction water content, dry density, and clay content (< 2 mum fraction). Experimental results showed that relative abundance of coarse (60 to 6 mum) pores was mainly affected by increasing the dry density of the specimens from 1.49 to 1.77 g/cm(3). The relative abundance of coarse and fine (0.01 to 0.002 mum) pores was affected by increasing the compaction water content from 10.6 to 26.4%. Variations in dry density, compaction water content, and clay contents notably affected the matric suction of the compacted specimens. The collapse behavior of the compacted specimens is explained from analysis of the MIP and matric suction results.

Synthesis and photoluminescent properties of ZnS nanocrystals doped with copper and halogen

A novel wet-chemical precipitation method is optimized for the synthesis of ZnS nanocrystals doped with Cu+ and halogen. The nanoparticles were stabilized by capping with polyvinyl pyrrolidone (PVP). XRD studies show the phase singularity of ZnS particles having zinc-blende (cubic) structure. TEM as well as XRD line broadening indicate that the average crystallite size of undoped samples is similar to2 nm. The effects of change in stoichiometry and doping with Cu+ and halogen on the photoluminescence properties of ZnS nanophosphors have been investigated. Sulfur vacancy (Vs) related emission with peak maximum at 434 nm has been dominant in undoped ZnS nanoparticles. Unlike in the case of microcrystalline ZnS phosphor, incorporation of halogens in nanoparticles did not result V-Zn related self-activated emission. However, emission characteristics of nanophosphors have been changed with Cu+ activation due to energy transfer from vacancy centers to dopant centers. The use of halogen as co-activator helps to increase the solubility of Cu+ ions in ZnS lattice and also enhances the donor-acceptor type emission efficiency. With increase in Cu+ doping, Cu-Blue centers (CuZn-Cui+), which were dominant at low Cu+ concentrations, has been transformed into Cu-Green (Cu-Zn(-)) centers and the later is found to be situated near the surface regions of nanoparticles. From these studies we have shown that, by controlling the defect chemistry and suitable doping, photoluminescence emission tunability over a wide wavelength range, i.e., from 434 to 514 nm, can be achieved in ZnS nanophosphors. (C) 2003 Elsevier B.V. All rights reserved.

Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

The influence of grain size on deformation of copper

It is well know that grain boundaries enhance strength at low temperatures by acting as obstacles to dislocation motion, and they retard strength at higher temperatures by processes involving grain boundary sliding. The available data on the influence of grain boundaries on deformation in copper is summarized. Equi-channel angular extrusion offers a convenient means for imposing severe plastic deformation to refine the grain size in bulk materials. Experimental data on fine grained copper produced by equi-channel angular extrusion will be described, and the implications of the data for diffusion creep and superplasticity will be discussed.

Reliability-based load and resistance factors for soil-nail walls

Existing soil nailing design methodologies are essentially based on limit equilibrium principles that together with a lumped factor of safety or a set of partial factors on the material parameters and loads account for uncertainties in design input parameter values. Recent trends in the development of design procedures for earth retaining structures are towards load and resistance factor design (LRFD). In the present study, a methodology for the use of LRFD in the context of soil-nail walls is proposed and a procedure to determine reliability-based load and resistance factors is illustrated for important strength limit states with reference to a 10 m high soil-nail wall. The need for separate partial factors for each limit state is highlighted, and the proposed factors are compared with those existing in the literature.

Analytical solutions for protective filters based on soil-retention and permeability criteria with respect to the phenomenon of soil boiling

For the successful performance of a granular filter medium, existing design guidelines, which are based on the particle size distribution (PSD) characteristics of the base soil and filter medium, require two contradictory conditions to be satisfied, viz., soil retention and permeability. In spite of the wider applicability of these guidelines, it is well recognized that (i) they are applicable to a particular range of soils tested in the laboratory, (ii) the design procedures do not include performance-based selection criteria, and (iii) there are no means to establish the sensitivity of the important variables influencing performance. In the present work, analytical solutions are developed to obtain a factor of safety with respect to soil-retention and permeability criteria for a base soil - filter medium system subjected to a soil boiling condition. The proposed analytical solutions take into consideration relevant geotechnical properties such as void ratio, permeability, dry unit weight, effective friction angle, shape and size of soil particles, seepage discharge, and existing hydraulic gradient. The solution is validated through example applications and experimental results, and it is established that it can be used successfully in the selection as well as design of granular filters and can be applied to all types of base soils.

Volume Change Behaviour of Soil Influenced with Sulfuric Acid

The paper brings out the role of calcium carbonate (CaCO3) on the volume change behaviour of natural black cotton soil with 1N sulfuric acid (H2SO4) as pore fluid. Natural black cotton soil contained predominantly montmorillonite [Ca0.2(Al,Mg)2Si4 O10 (OH)2 .4H2O] along with other minerals such as amesite [(Mg Fe)2 Al (Si Al)2 O5 (OH)4], kalsilite [KAlSiO4] and quartz [SiO2]. The calcitic soil, reacted with H2SO4 during consolidation testing, showed the presence of the new mineral yavapaiite [K Fe(SO4)2]. Consequently, the carbonate soil treated with 1N H2SO4 led to higher swell at seating load and more compression upon loading than the soil with no carbonate. The swelling increased with increase in the amount of carbonate present in the soil.

Numerical modeling of the contaminant Transport through stratified soil

The transport processes of the dissolved chemicals in stratified or layered soils have been studied for several decades. In case of the solute transport through stratified layers, interface condition plays an important role in determining appropriate transport parameters. First‐ type and third‐ type interface conditions are generally used in the literature. A first‐type interface condition will result in a continuous concentration profile across the interface at the expense of solute mass balance. On the other hand, a discontinuity in concentration develops when a third‐ type interface condition is used. To overcome this problem, a combined first‐ and third‐ type condition at the interface has been widely employed which yields second‐ type condition. This results in a similar break‐through curve irrespective of the layering order, which is non‐physical. In this work, an interface condition is proposed which satisfies the mass balance implicitly and brings the distinction between the breakthrough curves for different layering sequence corroborating with the experimental observations. This is in disagreement with the earlier work by H. M. Selim and co‐workers but, well agreement with the hypothetical result by Bosma and van der Zee; and Van der Zee.

Volume Change behaviour in Calcitic Soil influenced with Sulphuric Acid using Artificial Neural Networks

This paper elucidates the methodology of applying artificial neural network model (ANNM) to predict the percent swell of calcitic soil in sulphuric acid solutions, a complex phenomenon involving many parameters. Swell data required for modelling is experimentally obtained using conventional oedometer tests under nominal surcharge. The phases in ANN include optimal design of architecture, operation and training of architecture. The designed optimal neural model (3-5-1) is a fully connected three layer feed forward network with symmetric sigmoid activation function and trained by the back propagation algorithm to minimize a quadratic error criterion.The used model requires parameters such as duration of interaction, calcite mineral content and acid concentration for prediction of swell. The observed strong correlation coefficient (R2 = 0.9979) between the values determined by the experiment and predicted using the developed model demonstrates that the network can provide answers to complex problems in geotechnical engineering.

Ferrocene-Conjugated L-Tryptophan Copper(II) Complexes of Phenanthroline Bases Showing DNA Photocleavage Activity and Cytotoxicity

Ferrocene-conjugated L-tryptophan (L-Trp) reduced Schiff base (Fc-TrpH) copper(II) complexes [Cu(Fc-Trp)(L)](ClO(4)) of phenanthroline bases (L), viz. 2,2'-bipyridine (bpy in 1), 1,10-phenanthroline (phen in 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 4), were prepared and characterized and their photocytotoxicity studied. Cationic reduced Schiff base (Ph-TrpH) complexes [Cu(Ph-Trp)(L)(H(2)O)] (ClO(4)) (L = phen in 5; dppz in 6) having the ferrocenyl moiety replaced by a phenyl group and the Zn(II) analogue (7) of complex 4 were prepared and used as control species. The crystal structures of 1 and 5 with respective square-planar CuN(3)O and square-pyramidal CuN(3)O(2) coordination geometry show significantly different core structures. Complexes 1-4 exhibit a Cu(II)-Cu(I) redox couple near -0.1 V and the Fc(+)-Fc couple at similar to 0.5 V vs SCE in DMF-0.1 M [Bu(4)(n)N] (ClO(4)) (Fc = ferrocenyl moiety). The complexes display a copper(II)-based d-d band near 600 nm and a Fc-centered band at similar to 450 nm in DMF-Tris-HCl buffer. The complexes are efficient binders to calf thymus DNA. They are synthetic chemical nucleases in the presence of thiol or H(2)O(2), forming hydroxyl radicals. The photoactive complexes are cleavers of pUC19 DNA in visible light, forming hydroxyl radicals. Complexes 2-6 show photocytotoxicity in HeLa cancer cells, giving IC(50) values of 4.7, 10.2, 1.3, 4.8, and 4.3 mu M, respectively, in visible light with the appearance of apoptotic bodies. The complexes also show photocytotoxicity in MCF-7 cancer cells. Nuclear chromatin cleavage has been observed with acridine orange/ethidium bromide (AO/EB) dual staining with complex 4 in visible light. The complexes induce caspase-independent apoptosis in the HeLa cells.

Modeling wrap faced reinforced soil retaining walls subjected to dynamic excitation

This paper describes some of the physical and numerical model tests of reinforced soil retaining walls subjected to dynamic excitation through uni-axial shaking tests. Models of retaining walls are constructed in a perspex box with geotextile reinforcement using the wrap around technique with dry sand backfill and instrumented with displacement sensors, accelerometers and soil pressure sensors. Numerical modelling of these shaking table tests is carried using FLAC. Numerical model is validated by comparing physical model results. Responses of wrap faced walls with different number of reinforcement layers are discussed from both the physical and numerical model tests. Results showed that the displacements are decreasing with the increase in number of reinforcement layers while acceleration amplifications are not affected significantly.