Studies on the Development and Control of Desiccation cracks in compacted clay liner soils

The present study aimed at critically looking at the current practice of the installation of compacted clay liner using bentonite enhanced sand (BES). The application of bentonite is currently the most accepted practice for lining purposes. The ideal bentonite sand combination, which satisfies the liner requirements is 20% bentonite and 80% sand, was selected as one of the liner materials for the investigation of development of desiccation cracks. Locally available sundried marine clay and its combination with bentonite were also included in the study. The desiccation tests on liner materials were conducted for wet/dry cycles to simulate the seasonal variations. Digital image processing techniques were used to measure the crack intensity factor (CIF), a useful and effective parameter for quantification of desiccation cracking. The repeatability of the tests could be well established, as the variation in CIF values of identical samples had a very narrow range of 0 to 2%. The studies on the development of desiccation cracks showed that the CIF of bentonite enhanced sand mixture (BES) was 18.09%, 39.75% and 21.22% for the first, second and third cycles respectively, while it was only 9.83%, 7.52% and 4.58% respectively for sun dried marine clay (SMC). Thus the locally available, alternate liner material suggested, viz SMC, is far superior to BES, when subjected to alternate wet/dry cycles. Further, the improvement of these liner materials when amended with randomly distributed fibre reinforcements was also investigated. Three types of fibres ,namely nylon fibre, polypropylene monofilament and polypropylene fibre mesh were used for the study of fibre amended BES and SMC.The influence of these amendments on the properties of the above liner materials is also studied. The results showed that there is definite improvement in the properties of the liner materials when it is reinforced with discrete random fibres. The study also proved that the desiccation cracks could be controlled with the help of fibre reinforcement.

Laser induced surface damage, thermal transport and microhardness studies on certain organic and semiorganic nonlinear optical crystals

N-alkyl-2,6-dimethyl-4(1H)-pyridinones, salts of 4-dimethylaminopyridine and 2-amino-5-nitropyridine are considered to be potential candidates for nonlinear optical (NLO) applications, in particular for the generation of blue-green laser radiation. Single crystals were grown following the slow evaporation technique at constant temperature. Single-shot laserinduced surface damage thresholds in the range 3–10 GW/cm2 were measured using a 18 ns Q-switched Nd:YAG laser. The surface morphologies of the damaged crystals were examined under an optical microscope and the nature of damage identified. The Vicker’s microhardness was determined at a load of 98.07 mN. The thermal transport properties, thermal diffusivity (α), thermal effusivity (e), thermal conductivity (K) and heat capacity (Cp), of the grown crystals were measured by an improved photopyroelectric technique at room temperature. All the results are presented and discussed.

Studies on the Synthesis and Transformations of a few Bicyclic and Dispiro Compounds

In this thesis, we report our endeavours in the synthesis of a few polycyclic compounds. We were interested in the synthesis of a few bicyclic compounds designed to undergo interesting photochemical transformations including tripletmediated di-π-methane rearrangement and/or competing singlet-mediated electrocyclic reactions. Our target molecules have "inbuilt" structural features which will potentially alter the photochemistry of the substrate under consideration.The present investigation was undertaken to test our hypothesis on selective intramolecular quenching of singlet or triplet excited states of molecules.We adopted Dies-Alder reaction for the synthesis of several of the bicyclic compounds we were interested in. Some of the precursor dienes synthesised by us are capable of undergoing intramolecular cycloaddition reactions as well. So, it was important to delineate the conditions and structural features that will enable a particular molecule to undergo intermolecular and intramolecular Dies-Alder reaction when treated with a suitable dienophile.Though, the main focus of this thesis is on the synthesis of bicyclic and tricyclic systems capable of undergoing di-π-methane rearrangement, in the last chapter of this thesis, we describe our findings on the synthesis of a few dispirocompounds. These systems were encountered as unexpected products in the attempted synthesis of novel dibenzoylalkene-type systems. Consequently, a brief survey on the synthesis and transformations of dibenzoylalkenes is also included as an integral part of this thesis.

STUDIES ON THE PHYSIOLOGICAL AND BIOCHEMICAL ASPECTS OF OSMOREGULATION IN TWO INTERTIDAL BIVALVE MOLLUSCS

Division of Marine Biology, Microbiology and Biochemistry, School of Marine Sciences, Cochin University of Science and Technology

Studies on Metallocene Polyolefin and Polyvinyl Chloride for Blood and Blood Component Storage Applications

Plasticized poly(vinyl chloride) (pPVC), although a major player in the medical field, is at present facing lot of criticism due to some of its limitations like the leaching out of the toxic plasticizer, di ethylhexyl phthalate (DEHP) to the medium and the emission of an environmental pollutant,dioxin gas,at the time of the post use disposal of PVC Products by incineration. Due to these reasons, efforts are on to reduce the use of pPVC considerably in the medical field and to find viable alternative materials. The present study has been undertaken in this context to find a suitable material for the manufacture of medical aids in place of pPVC. The main focus of this study has been to find out a non-DEHP material as plasticizer for pPVC and another suitable material for the complete repalcement of pPVC for blood/ blood component storage applications.Two approaches have been undertaken for this purpose-(1)the controversial plasticizer, DEHP has been partially replaced by polymeric plasticizers(2) an alternative material, namely, metallocene polyolefin (mPO) has been used and suitably modified to match the properties of flexible PVC used for blood and blood component storage applications.

Studies on Conducting Polymers and Conductive Elastomer Composites

The primary aim of this work has been to develop conductive silicone and nitrile rubbers, which are extensively used for making conductive pads in telephone sets, calculators and other applications. Another objective of the work has been to synthesise and characterize novel conducting polymers based on glyoxal and paraphenylenediamine- poly(p-phenylenediazomethine. Conducting polymer matrices were developed from polymer blends such as poly(pphenylenediazomethine), polyethylene, PVC and silica and their properties were studied.

Studies on the dynamics and rheology of dilute suspensions of Brownian particles in simple shear flow under the action of an external force

We present a novel approach to computing the orientation moments and rheological properties of a dilute suspension of spheroids in a simple shear flow at arbitrary Peclct number based on a generalised Langevin equation method. This method differs from the diffusion equation method which is commonly used to model similar systems in that the actual equations of motion for the orientations of the individual particles are used in the computations, instead of a solution of the diffusion equation of the system. It also differs from the method of 'Brownian dynamics simulations' in that the equations used for the simulations are deterministic differential equations even in the presence of noise, and not stochastic differential equations as in Brownian dynamics simulations. One advantage of the present approach over the Fokker-Planck equation formalism is that it employs a common strategy that can be applied across a wide range of shear and diffusion parameters. Also, since deterministic differential equations are easier to simulate than stochastic differential equations, the Langevin equation method presented in this work is more efficient and less computationally intensive than Brownian dynamics simulations.We derive the Langevin equations governing the orientations of the particles in the suspension and evolve a procedure for obtaining the equation of motion for any orientation moment. A computational technique is described for simulating the orientation moments dynamically from a set of time-averaged Langevin equations, which can be used to obtain the moments when the governing equations are harder to solve analytically. The results obtained using this method are in good agreement with those available in the literature.The above computational method is also used to investigate the effect of rotational Brownian motion on the rheology of the suspension under the action of an external force field. The force field is assumed to be either constant or periodic. In the case of con- I stant external fields earlier results in the literature are reproduced, while for the case of periodic forcing certain parametric regimes corresponding to weak Brownian diffusion are identified where the rheological parameters evolve chaotically and settle onto a low dimensional attractor. The response of the system to variations in the magnitude and orientation of the force field and strength of diffusion is also analyzed through numerical experiments. It is also demonstrated that the aperiodic behaviour exhibited by the system could not have been picked up by the diffusion equation approach as presently used in the literature.The main contributions of this work include the preparation of the basic framework for applying the Langevin method to standard flow problems, quantification of rotary Brownian effects by using the new method, the paired-moment scheme for computing the moments and its use in solving an otherwise intractable problem especially in the limit of small Brownian motion where the problem becomes singular, and a demonstration of how systems governed by a Fokker-Planck equation can be explored for possible chaotic behaviour.

Studies on grain refinement and alloying additions on the microstructure and mechanical properties of Mg-8Zn-4Al alloy

MAGNESIUM ALLOYS have strong potential for weight reduction in a wide range of technical applications because of their low density compared to other structural metallic materials. Therefore, an extensive growth of magnesium alloys usage in the automobile sector is expected in the coming years to enhance the fuel efficiency through mass reduction. The drawback associated with the use of commercially cheaper Mg-Al based alloys, such as AZ91, AM60 and AM50 are their inferior creep properties above 100ºC due to the presence of discontinuous Mg17A112 phases at the grain boundaries. Although rare earth-based magnesium alloys show better mechanical properties, it is not economically viable to use these alloys in auto industries. Recently, many new Mg-Al based alloy systems have been developed for high temperature applications, which do not contain the Mg17Al12 phase. It has been proved that the addition of a high percentage of zinc (which depends upon the percentage of Al) to binary Mg-Al alloys also ensures the complete removal of the Mg17Al12 phase and hence exhibits superior high temperature properties.ZA84 alloy is one such system, which has 8%Zn in it (Mg-8Zn-4Al-0.2Mn, all are in wt %) and shows superior creep resistance compared to AZ and AM series alloys. These alloys are mostly used in die casting industries. However, there are certain large and heavy components, made up of this alloy by sand castings that show lower mechanical properties because of their coarse microstructure. Moreover, further improvement in their high temperature behaviour through microstructural modification is also an essential task to make this alloy suitable for the replacement of high strength aluminium alloys used in automobile industry. Grain refinement is an effective way to improve the tensile behaviour of engineering alloys. In fact, grain refinement of Mg-Al based alloys is well documented in literature. However, there is no grain refiner commercially available in the market for Mg-Al alloys. It is also reported in the literature that the microstructure of AZ91 alloy is modified through the minor elemental additions such as Sb, Si, Sr, Ca, etc., which enhance its high temperature properties because of the formation of new stable intermetallics. The same strategy can be used with the ZA84 alloy system to improve its high temperature properties further without sacrificing the other properties. The primary objective of the present research work, “Studies on grain refinement and alloying additions on the microstructure and mechanical properties of Mg-8Zn-4Al alloy” is twofold: 1. To investigate the role of individual and combined additions of Sb and Ca on the microstructure and mechanical properties of ZA84 alloy. 2. To synthesis a novel Mg-1wt%Al4C3 master alloy for grain refinement of ZA84 alloy and investigate its effects on mechanical properties.

Studies of nonlinear absorption and aggregation in aqueous solutions of rhodamine 6G using a transient thermal lens technique

Dual-beam transient thermal lens studies were carried out in aqueous solutions of rhodamine 6G using 532 nm pulses from a frequency-doubled Nd:YAG laser. The analysis of the observed data showed that the thermal lens method can effectively be utilized to study the nonlinear absorption and aggregation which are taking place in a dye medium.

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Optical absorption studies of free (H2Pc) and rare earth (RePc) phthalocyanine doped borate glasses

Optical absorption studies of free base and rare earth incorporated phthalocyanine doped borate glass matrix are reported for the first lime. The absorption spectra recorded in the UV- VIS region show two well defined absorption bands of phthalocyanine (Pc) molecule, namely the Soret band (B) and the Q band. The Q band always shows its characteristic splitting in all the doped glass matrices and the intensities of these components are found to vary from one Pc to another. Some of the important optical parameters, namely optical absorption coefficient (a), molar extinction coefficient (ε), absorption cross section (σa), oscillator strength (f), electric dipole strength (q2), absorption half bandwidth (Δλ) of the principal optical transitions have also been evaluated. Moreover, the spectral dependence of refractive index (n) and thereby the optical dielectric constant (ε) on wavelength yielded values of carrier concentration to effective mass ratio (N/m*) of the phthalocyanine molecule in the present glassy systems. Optical band gap (Eg) and width of the band tail (Et) are computed and their variations among the prepared samples are also discussed.