Characterization and FTIR spectral studies of human urinary stones from Southern India

Urinary stones resected from urinary bladders of patients hailing from Kollam district of Kerala State, India were analyzed by SEM, XRD and by thermal analysis techniques. The analytical results indicate that, stones have different composition, i.e., calcium phosphate, calcium phosphate hydroxide and sodium calcium carbonate. Infrared spectral studies also reveal the presence of phosphates or carbonates in these samples. Further, IR spectral investigations have revealed that amorphous carbonated species are occupied in PO4 sites in calcium phosphate type stone and OH sites in calcium phosphate hydroxide sample. Thermal studies of these samples also reveal that, carbon dioxide is released from carbonated samples upon heating which is related to amount of carbon content and bond strength. Crystals with defects and irregular morphology are grown inside the urinary bladder due to variation in crystal growth conditions

Raman and FTIR studies of the structural aspects of Nasicon-type crystals; AFeTi(PO4)3 [A ¼ Ca, Cd]

Raman and FTIR spectra of CaFeTi(PO4)3 and CdFeTi(PO4)3 are recorded and analyzed. The observed bands are assigned in terms of vibrations of TiO6 octahedra and PO4 tetrahedra. The symmetry of TiO6 octrahedra and PO4 tetrahedra is lowered from their free ion symmetry. The presence of Fe3+ ion disrupts the Ti–O–P–O–Ti chain and leads to the distortion of TiO6 octrahedra and PO4 tetrahedra. The PO4 3 tetrahedra in both crystals are linearly distorted. The covalency bonding factor of PO4 3 polyanion of both the crystals are calculated from the Raman spectra and compared to that of other Nasicon-type systems. The numerical values of covalency bonding factor indicates that there is a reduction in redox energy and cell voltage and is attributed to strong covalency of PO4 3 polyanionin

Analytical Characterization, Thermal And Ftir Studies Of Urinary Calculi

Urolithiasis is identified to be a major urological disorder affecting people all over the world irrespective of their age, sex and race. Urinary stone samples resected from the urinary bladders of two patients belonging to tropical region, Kollam District of Kerala State, India are investigated by using XRD,SEM, EDAX, TGA, DSC and FTIR to understand its chemical structure. Uric acid shows exothermic peak around 432°C is due to the decomposition with the evolution of CO and cracking of the remaining products. Results of analytical studies reveal that samples under investigation consist mainly in uric acid and hydrated uric acid. Hydrogen bonding exists in hydrated uric acid samples

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O are recorded and analyzed. The observed bands are assigned on the basis of BrO3 − and H2O vibrations. Additional bands obtained in the region of 3 and 1 modes in [Cu(H2O)6](BrO3)2 are due to the lifting of degeneracy of 3 modes, since the BrO3 − ion occupies a site of lower symmetry. The appearance 1 mode of BrO3 − anion at a lower wavenumber (771 cm−1) is attributed to the attachment of hydrogen to the BrO3 − anion. The presence of three inequivalent bromate groups in the [Al(H2O)6](BrO3)3 · 3H2O structure is confirmed. The lifting of degeneracy of 4 mode indicates that the symmetry of BrO3 − anion is lowered in the above crystal from C3v to C1. The appearance of additional bands in the stretching and bonding mode regions of water indicates the presence of hydrogen bonds of different strengths in both the crystals. Temperature dependent Raman spectra of single crystal [Cu(H2O)6](BrO3)2 are recorded in the range 77–523 K for various temperatures. A small structural rearrangement takes place in BrO3 − ion in the crystal at 391 K. Hydrogen bounds in the crystal are rearranging themselves leading to the loss of one water molecule at 485 K. This is preceded by the reorientation of BrO3 − ions causing a phase transition at 447 K. Changes in intensities and wavenumbers of the bands and the narrowing down of the bands at 77 K are attributed to the settling down of protons into ordered positions in the crystal

Studies On Supported Cobalt (Ii), Nickel (Ii) and Copper (Ii) Complexes Of O-Phenylenediamine and Schiff Bases Derived from 3-Hydroxyquinoxaline-2-Carboxaldehyde

The thesis deals with the synthesis, characterization and catalytic activity studies of supported cobalt(ii), nickel(II) and copper(II) complexes of O-phenylenediamine and Schiff bases derived from 3-hydroxyquinoxaline -2-carboxaldehyde. Zeolite encapsulation and polymer anchoring was employed for supporting the complexes. The characterization techniques proved that the encapsulation as well as polymer supporting has been successfully achieved. The catalytic activity studies revealed that the activities of the simple complexes are improved upon encapsulation. Various characterization techniques are used such as, chemical analysis, EPR, magnetic measurements, FTIR studies, thermal analysis, electronic spectra, XRD, SEM, surface area, and GC.The present study indicated that the that the mechanism of oxidation of catechol and DTBC by hydrogen peroxide is not altered by the change in the coordination sphere around the metal ion due to encapsulation. This fact suggests outer sphere mechanism for the reactions. The catalytic activity by zeolite encapsulated complex was found to be slower than that by the neat complex. The slowing down of the reaction in the zeolite case is probably due to the constraint imposed by the zeolite framework. The rate of DTBC ( 3,5-di-tert-butylchatechol)oxidation was found to be greater than the rate of catechol oxidation. This is obviously due to the presence of electron donating tertiary butyl groups.

Sol-Gel Nanocrystalline Catalytic Titania Powders and Functional Coatings

In the present work Titania bulk powders and coatings were prepared by subjecting titanium isopropoxide solution to a controlled hydrolysis-condensation process. The powders were characterized using techniques such as FTIR for their chemical interactions, TG-DTA for the thermal decomposition features, XRD for the phase assemblage, BET specific surface area analysis for the textural features. The study discusses the preparation methods and the characterization techniques employed and a detailed discussion on the physico-chemical characterization of the prepared systems. The influence of dopants and leaching on the physico-chemical properties as well as their influence on photo activity is also included. The structural/functional coatings of different Titania compositions includes in this study. Coatings on pre-treated glass surfaces with the best compositions prepared showed 90 % transmittance in the visible region.

Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Vacuum-ultraviolet photochemically initiated modification of polystyrene surfaces: morphological changes and mechanistic investigations

Vacuum-ultraviolet (VUV) irradiation (kexc: 172 ± 12 nm) of polystyrene films in the presence of oxygen produced not only oxidatively functionalized surfaces, but generated also morphological changes. Whereas OH- and C=O-functionalized surfaces might be used for e.g. secondary functionalization, enhanced aggregation or printing, processes leading to morphological changes open new possibilities of microstructurization. Series of experiments made under different experimental conditions brought evidence of two different reaction pathways: introduction of OH- and C=O-groups at the polystyrene pathways is mainly due to the reaction of reactive oxygen species (hydroxyl radicals, atomic oxygen, ozone) produced in the gas phase between the VUV-radiation source and the substrate. However, oxidative fragmentation leading to morphological changes, oxidation products of low molecular weight and eventually to mineralization of the organic substrate is initiated by electronic excitation of the polymer leading to C–C-bond homolysis and to a complex oxidation manifold after trapping of the C-centred radicals by molecular oxygen. The pathways of oxidative functionalization or fragmentation could be differentiated by FTIR-ATR analysis of irradiated polystyrene surfaces before and after washing with acetonitrile and microscopic fluorescence analysis of the surfaces secondarily functionalized with the N,N,N-tridodecyl-triaza-triangulenium (TATA) cation. Ozonization of the polystyrene leads to oxidative functionalization of the polymer surface but cannot initiate the fragmentation of the polymer backbone. Oxidative fragmentation is initiated by electronic excitation of the polymer (contact-mode AFM analysis), and evidence of the generation of intermediate C-centred radicals is given e.g. by experiments in the absence of oxygen leading to cross-linking (solubility effects, optical microscopy, friction-mode AFM) and disproportionation (fluorescence).

Studies on the Toughening of Epoxy Resins

This thesis aims to develop new toughened systems for epoxy resin via physical and chemical modifications. Initially the synthesis of DGEBA was carried out and the properties compared with that of the commercial sample. Subsequently the modifier resins to be employed were synthesized. The synthesized resin were characterized by spectroscopic method (FTIR and H NMR), epoxide equivalent and gel permeation chromatography. Chemical modification involves the incorporation of thermoset resins such a phenolics, epoxy novolacs, cardanol epoxides and unsaturated polyester into the epoxy resin by reactive belnding. The mechanical and thermal properties of the blends were studied. In the physical modification route, elastomers, maleated elastomers and functional elastomers were dispersed as micro-sized rubber phase into the continuous epoxy phase by a solution blending technique as against the conventional mechanical blending technique. The effect of matrix toughening on the properties of glass reinforced composites and the effect of fillers on the properties of commercial epoxy resin were also investigated. The blends were characterized by thermo gravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy and mechanical property measurements. Among the thermoset blends, substantial toughening was observed in the case of epoxy phenolic novolacs especially epoxy para cresol novolac (ECN). In the case of elastomer blending , the toughest blends were obtained in the case of maleic anhydride grafted NBR. Among functional elastomers the best results were obtained with CTBN. Studies on filled and glass reinforced composites employing modified epoxy as matrix revealed an overall improvement in mechanical properties

Studies on Some Simple and Zeolite-Y Encapsulated 3d-Transition Metal Complexes of Schiff Bases Derived From 2-Aminobenzothiazole

In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.

Zeolite-encapsulated Co(II), Ni(II) and Cu(II) complexes as catalysts for partial oxidation of benzyl alcohol and ethylbenzene

Co(II), Ni(II) and Cu(II) complexes of dimethylglyoxime and N,N-ethylenebis(7-methylsalicylideneamine) have been synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. The hybrid materials obtained have been characterized by elemental analysis, SEM, XRD, surface area, pore volume, magnetic moment, FTIR, UV-Vis and EPR techniques. Analysis of data indicates the formation of complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activities for hydrogen peroxide decomposition and oxidation of benzyl alcohol and ethylbenzene of zeolite complexes are reported. Zeolite Cu(II) complexes were found to be more active than the corresponding Co(II) and Ni(II) complexes for oxidation reactions. The catalytic properties of the complexes are influenced by their geometry and by the steric environment of the active sites. Zeolite complexes are stable enough to be reused and are suitable to be utilized as partial oxidation catalysts.

Copper(II) complexes of embelin and 2-aminobenzimidazole encapsulated in zeolite Y-potential as catalysts

Copper(II) complexes of two biologically important ligands, viz., embelin (2,5-dihydroxy-3-undecyl-2,5-cyclohexadien 1,4-dione) and 2-aminobenzimidazole were entrapped in the cages of zeolite Y by the flexible ligand method. The capability of these compounds in catalyzing the reduction of oxygen (industrially known as deoxo reaction) was explored and the results indicate an enhancement of the catalytic properties from that of the simple copper ion exchanged zeolite. These point to the ability of the ligands in enhancing the oxygen binding capability of the metal ion. Elemental analyses, Fourier transform infrared (FTIR), diffuse reflectance and EPR spectral studies, magnetic susceptibility measurements, TG, surface area analyses and powder X-ray diffraction studies were used in understanding the presence, composition and structure of the complexes inside the cages. The study also reveals the increased thermal and mechanical stability of the complexes as a result of encapsulation.

ANALYSIS, MODIFICATION, AND EVALUATION OF THE COLD FLOW PROPERTIES OF VEGETABLE OILS AS BASE OIL FOR INDUSTRIAL LUBRICANTS

Poor cold flow properties of vegetable oils are a major problem preventing the usage of many abundantly available vegetable oils as base stocks for industrial lubricants. The major objective of this research is to improve the cold flow properties of vegetable oils by various techniques like additive addition and different chemical modification processes. Conventional procedure for determining pour point is ASTM D97 method. ASTM D97 method is time consuming and reproducibility of pour point temperatures is poor between laboratories. Differential Scanning Calorimetry (DSC) is a fast, accurate and reproducible method to analyze the thermal activities during cooling/heating of oil. In this work coconut oil has been chosen as representative vegetable oil for the analysis and improvement cold flow properties since it is abundantly available in the tropics and has a very high pour point of 24 °C. DSC is used for the analysis of unmodified and modified vegetable oil. The modified oils (with acceptable pour points) were then subjected to different tests for the valuation of important lubricant properties such as viscometric, tribological (friction and wear properties), oxidative and corrosion properties.A commercial polymethacrylate based PPD was added in different percentages and the pour points were determined in each case. Styrenated phenol(SP) was added in different concentration to coconut oil and each solution was subjected to ASTM D97 test and analysis by DSC. Refined coconut oil and other oils like castor oil, sunflower oil and keranja oil were mixed in different proportions and interesterification procedure was carried out. Interesterification of coconut oil with other vegetable oils was not found to be effective in lowering the pour point of coconut oil as the reduction attained was only to the extent of 2 to 3 °C.Chemical modification by acid catalysed condensation reaction with coconut oil castor oil mixture resulted in significant reduction of pour point (from 24 ºC to -3 ºC). Instead of using triacylglycerols, when their fatty acid derivatives (lauric acid- the major fatty acid content of coconut oil and oleic acid- the major fatty acid constituents of monoand poly- unsaturated vegetable oils like olive oil, sunflower oil etc.) were used for the synthesis , the pour point could be brought down to -42 ºC. FTIR and NMR spectroscopy confirmed the ester structure of the product which is fundamental to the biodegradability of vegetable oils. The tribological performance of the synthesised product with a suitable AW/EP additive was comparable to the commercial SAE20W30 oil. The viscometric properties (viscosity and viscosity index) were also (with out additives) comparable to commercial lubricants. The TGA experiment confirmed the better oxidative performance of the product compared to vegetable oils. The sample passed corrosion test as per ASTM D130 method.

Polyaniline/Pillared Montmorillonite Clay Composite Nanofibers

In situ polymerization of aniline is done inside the pillared clay matrix. The nonswellable pillared clay confined matrix allows efficient polymerization that leads to nanofibrous morphology. As a result high polymer order and crystallinity is attained and is evident from XRD patterns. The strong interaction between the clay layers and polyaniline (PANI) is understood from FTIR and DRS spectra. Additionally these analytical results suggest that the prepared PANI is in the doped state. The PANI/pillared clay nanocomposite formation gives additional thermal stability to the polymer backbone and is clear from the DTG curves.

Thermal Properties of Dicalcium Lead Propionate Across the Prominent Transition Temperatures

The thermal transport properties, thermal diffusivity, thermal conductivity and specific heat capacity of Dicalcium Lead Propionate (DLP) crystal have been measured following a modified photopyroelectric thermal wave method. The measurements have been carried out with thermal waves propagating along the three principal symmetry directions, so as to bring out the anisotropy in these parameters. The variations of the above parameters through two prominent phase transition temperatures of this crystal have also been measured to understand the variation of these parameters as it undergoes ferroelectric phase transitions. In addition, complete thermal analysis and FTIR measurements have been done on the crystal to bring out the correlation of these results with the corresponding thermal transport properties. All these results are presented and discussed. The data presented in this paper form a comprehensive set of results on the thermal transport properties of this crystal.