Preparation and Properties of Iodine-Doped Radiopaque Natural Rubber

Polymers exhibit low electron density and they are radiolucent. Polymers can be made radiopaque by different techniques. We report a method for the preparation of radiopaque material from natural rubber (NR). NR in its latex form was iodinated. Iodinated natural rubber (INR) was characterized by using UV, thermo gravimetric analysis (TGA), and X-ray images. INR was compounded at high and low temperatures and its physical properties were measured. The low temperature cured samples show good radiopacity and conductivity. The optical density of low temperature cured samples was measured.

Electro-Optical Properties of Metal Phthalocyanines and Naphthalocyanines

The thesis deals with the preparation of chemical, optical, thermal and electrical characterization of five compounds, namely metal free naphthalocyanine, vanadyl napthalocyanine, zinc naphlocyanine, europium dinaphthalocyanine, and europium diphthalocyanine in the pristine and iodine-doped forms. Two important technological properties of these compounds have been investigated. The electrical properties are important in applications sensors and semiconductor lasers. Opto-thermal properties assume significance for optical imaging and data recording. The electrical properties were investigated by dc and ac techniques. This work has revealed some novel information on the conduction mechanism in five macrocyclic compounds and their iodine-doped forms. Also useful data on the thermal diffusivity of the target compounds have been obtained by optical techniques.

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

Changes in Protein, Carbohydrate and lipid content of cashew kernels during storage under two humidity conditions

The changes occuring to cashew kernels during storage at two humidity levels - 80% to 20% with respect to organoleptic characteristics, protein content, carbohydrate content, oil content, iodine and peroxide values were studied. From the present study it is concluded that organoleptic characteristics of cashew kernels deteriorates with increase in humidity. Decrease in protein and carbohydrate content of stored cashew kernel is dependent on humidity. Humidity increased oxidative rancidification.

Determination of the nature of the diperiodatocuprate(III) species in aqueous alkaline medium through a kinetic and mechanistic study on the oxidation of iodide ion

The nature of the diperiodatocuprate(III) (DPC) species present in aqueous alkaline medium has been investigated by a kinetic and mechanistic study on the oxidation of iodide by DPC. The reaction kinetics were studied over the 1.0 ´ 10)3±0.1 mol dm)3 alkali range. The reaction order with respect to DPC, as well as iodide, was found to be unity when [DPC] [I)]. In the 1.0 ´ 10)3±1.0 ´ 10)2 mol dm)3 alkali region, the rate decreased with increase in the alkali concentration and a plot of the pseudo-®rst order rate constant, k versus 1/[OH)] was linear. Above 5.0 ´ 10)2 mol dm)3, a plot of k versus [OH)] was also linear with a non-zero intercept. An increase in ionic strength of the reaction mixtures showed no e ect on k at low alkali concentrations, whereas at high concentrations an increase in ionic strength leads to an increase in k. A plot of 1/k versus [periodate] was linear with an intercept in both alkali ranges. Iodine was found to accelerate the reaction at the three di erent alkali concentrations employed. The observed results indicated the following equilibria for DPC.

Evaluation of electrical conductivity and thermal diffusivity of vanadyl naphthalocyanine

The electrical conductivity and thermal diffusivity of pristine and iodine doped vanadyl naphthalocyanine (VONc) were studied. In the pristine sample, the temperature dependence was very weak below 300 K. The increase in conductivity at higher temperature must be due to an enhancement in carrier density with increase in thermal energy. The electrical conductivity of VONc increased when doped with iodine. The behavior of VONcI indicated that considerable changes have occurred in the electronic environment of the molecule as a result of doping. Iodine doping enhanced the thermal diffusivity of VONc. The increase in thermal diffusivity of the iodine doped sample may be due to the disorder of iodine atoms occupying the channels in one dimensional lattices.

Studies on Heat Diffusion in Selected Conducting Polymers using Probe Beam Deflection and Photoacoustic Techniques

In the present study, radio frequency plasma polymerization technique is used to prepare thin films of polyaniline, polypyrrole, poly N-methyl pyrrole and polythiophene. The thermal characterization of these films is carried out using transverse probe beam deflection method. Electrical conductivity and band gaps are also determined. The effect of iodine doping on electrical conductivity and the rate of heat diffusion is explored.Bulk samples of poyaniline and polypyrrole in powder form are synthesized by chemical route. Open photoacoustic cell configuration is employed for the thermal characterization of these samples. The effect of acid doping on heat diffusion in these bulk samples of polyaniline is also investigated. The variation of electrical conductivity of doped polyaniline and polypyrrole with temperature is also studied for drawing conclusion on the nature of conduction in these samples. In order to improve the processability of polyaniline and polypyrrole, these polymers are incorporated into a host matrix of poly vinyl chloride. Measurements of thermal diffusivity and electrical conductivity of these samples are carried out to investigate the variation of these quantities as a function of the content of polyvinyl chloride.

Electrochemical studies on Metal phthalocyanines

The primary aim of these investigations was to probe the elecnuchemical and material science aspects of some selected metal phthalocyanines(MPcs).Metal phthalocyanines are characterised by a unique planar molecular structure. As a single class of compounds they have been the subject of ever increasing number of physicochemical and technological investigations. During the last two decades the literature on these compounds was flooded by an outpour of original publications and patents. Almost every branch of materials science has benefited by their application-swface coating, printing, electrophotography, photoelectrochemistry, electronics and medicine to name a few.The present study was confined to the electrical and electrochemical properties of cobalt, nickel, zinc. iron and copper phthalocyanines. The use of soluble Pes as corrosion inhibitor for aluminium was also investigated.In the introductory section of the thesis, the work done so far on MPcs is reviewed. In this review emphasis is given to their general methods of synthesis and the physicochemical properties.In phthalocyanine chemistry one of the formidable tasks is the isolation of singular species. In the second chapter the methods of synthesis and purification are presented with necessary experimental details.The studies on plasma modified films of CoPe, FePc, ZnPc. NiPc and CuPc are also presented.Modification of electron transfer process by such films for reversible redox systems is taken as the criterion to establish enhanced electrocatalytic activity.Metal phthalocyanines are p- type semiconductors and the conductivity is enhanced by doping with iodine. The effect of doping on the activation energy of the conduction process is evaluated by measuring the temperature dependent variation of conductivity. Effect of thennal treatment on iodine doped CoPc is investigated by DSC,magnetic susceptibility, IR, ESR and electronic spectra. The elecnucatalytic activity of such doped materials was probed by cyclic voltammetry.The electron transfer mediation characteristics of MPc films depend on the film thickness. The influence of reducing the effective thickness of the MPc film by dispersing it into a conductive polymeric matrix was investigated. Tetrasulphonated cobalt phthalocyanine (CoTSP) was electrostatically immobilised into polyaniline and poly(o-toluidine) under varied conditions.The studies on corrosion inhibition of aluminium by CoTSP and CuTSP and By virtue of their anionic character they are soluble in water and are strongly adsorbed on aluminium. Hence they can act as corrosion inhibitors. CoTSP is also known to catalyze the reduction of dioxygen.This reaction can accelerate the anodic dissolution of metal as a complementary reaction. The influence of these conflicting properties of CoTSP on the corrosion of aluminium was studied and compared with those of CuTSP.In the course of these investigations a number of gadgets like cell for measuring the electrical conductivity of solids under non-isothermal conditions, low power rf oscillator and a rotating disc electrode were fabricated.

Studies on new processing aids and other compounding ingredients in special purpose rubbers

In the first part of the study we probed the effectiveness of rice bran oil as a multipurpose compounding ingredient for nitrile (NBR) and chloroprene (CR) rubbers. This oil has already been successfully employed in the compounding of NR and SBR in this laboratory.In this context we thought it worthwhile to try this oil in the polar rubbers viz, NBR and CR also. The principle of like dissolves like as applicable to solvents is equally applicable while selecting a plasticiser, elastomer combination. Because of the compatibility considerations polar plasticisers are preferred for polar rubbers like NBR and CR. Although plasticisation is a physical phenomenon and no chemical reaction is involved, the chemical structure of plasticisers determines how much physical attraction there is between the rubber and the plasticiser. In this context it is interesting to note that the various fatty acids present in rice bran oil have a long paraffinic chain, characteristic of waxes, with an acid group at the end of the molecule. The paraffinic end of the molecule contributes lubricating effects and limits compatibility whereas the acid end group contributes some polarity and is also chemically reactive. Because of absorption of acid group on the surface of pigments, these acids will have active pigment wetting characteristics also. These factors justifies the role of rice bran oil as a co-activator and lubricating agent for NBR and CR. In fact in our study we successfully replaced stearic acid as co-activator and aromatic oillDOP as processing aid for CR and NBR with rice bran oil.This part of the study has got special significance in the fact that rubber industry now heavily depends on petroleum industry for process oils. The conventional process oils like aromatic, naphthenic and paraffinic oils are increasingly becoming costlier, as its resources in nature are fast depleting. Moreover aromatic process oils are reported to be carcinogenic because of the presence of higher levels of polycyclic aromatic compounds in these oils.As a result of these factors, a great amount research is going on world over for newer processing aids which are cost effective, nontoxic and performanance wise at par with the conventional ones used in the rubber industry. Trials with vegetable oils in this direction is worth trying.Antioxidants are usually added to the rubber compound to minimise ageing effects from heat, light, oxygen etc. As rice bran oil contains significant amount of tocopherols and oryzanol which are natural antioxidants, we replaced a phenolic antioxidant like styrenated phenol (SP) from the compound recipe of both the rubbers with RBO and ascertained whether this oil could function in the role of antioxidant as well.Preparation and use of epoxidised rice bran oil as plasticiser has already been reported.The crude rice bran oil having an iodine value of 92 was epoxidised in this laboratory using peracetic acid in presence of sulphuric acid as catalyst. The epoxy content of the epoxidised oil was determined volumetrically by treating a known weight of the oil with excess HCI and back titrating the residual HCI with standard alkali solution. The epoxidised oil having an epoxy content of 3.4% was tried in the compounding of NBR and CR as processing aids. And results of these investigations are also included in this chapter. In the second part of the study we tried how RBO/ERBO could perform when used as a processing aid in place of aromatic oil in the compounding of black filled NRCR blends. Elastomers cannot have all the properties required for a particular applications, so it is common practice in rubber industry to blend two elastomers to have desired property for the resulting blend.In this RBO/ERBO was tried as a processing aid for plasticisation, dispersion of fillers, and vulcanisation of black filled NR-CR blends.Aromatic oil was used as a control. The results of our study indicate that these oils could function as a processing aid and when added together with carbon black function as a cure accelerator also.PVC is compatible with nitrile rubber in all proportions, provided NBR has an acrylonitrile content of 25 to 40%. Lower or higher ACN content in NBR makes it incompatible with PVC.PVC is usually blended with NBR at high temperatures. In order to reduce torque during mixing, additional amounts of plasticisers like DOP are added. The plasticiser should be compatible both with PVC and NBR so as to get a homogeneous blend. Epoxidised soyaben oil is reported to have been used in the compounding of PVC as it can perfonn both as an efficient plasticiser and heat stabilizer.At present DOP constitute the largest consumed plasticiser in the PVC compounding. The migration of this plasticiser from food packaging materials made of PVC poses great health hazards as this is harmful to human body. In such a scenario we also thought it worthwhile to see whether DOP could be replaced by rice bran oil in the compounding of NBR-PVC blends Different blends of NBR-PVC were prepared with RBO and were vulcanized using sulphur and conventional accelerators. The various physical and mechanical properties of the vulcanisates were evaluated and compared with those prepared with DOP as the control plasticiser. Epoxidised rice bran oil was also tried as plasticiser for the preparation of NBR-PVC blends. A comparison of the processability and cure characteristics of the different blends prepared with DOP and ERBO showed that ERBO based blends have better processability and lower cure time values. However the elastographic maximum torque values are higher for the DOP based blends. Almost all of the physical properties evaluated are found to be slightly better for the DOP based blends over the ERBO based ones. However a notable feature of the ERBO based blends is the better percentage retention of elongation at break values after ageing over the DOP based blends. The results of these studies using rice bran oil and its epoxidised variety indicated that they could be used as efficient plasticisers in place of DOP and justifies their role as novel, nontoxic, and cheap plasticisers for NBR-PVC blends.

Investigations on the mechanism of carrier transport in plasma polymerized pyrrole thin films

Plasma polymerization is found to be an excellent technique for the preparation of good quality, pinhole-free, polymer thin films from different monomer precursors. The present work describes the preparation and characterization of polypyrrole (PPy) thin films by ac plasma polymerization technique in their pristine and in situ iodine doped forms. The electrical conductivity studies of the aluminiumpolymeraluminium (AlpolymerAl) structures have been carried out and a space charge limited conduction (SCLC) mechanism is identified as the most probable mechanism of carrier transport in these polymer films. The electrical conductivity shows an enhanced value in the iodine doped sample. The reduction of optical band gap by iodine doping is correlated with the observed conductivity results.

On the optical and electrical properties of rf and a.c. plasma polymerized aniline thin films

Polyaniline is a widely studied conducting polymer and is a useful material in its bulk and thin film form for many applications, because of its excellent optical and electrical properties. Pristine and iodine doped polyaniline thin films were prepared by a.c. and rf plasma polymerization techniques separately for the comparison of their optical and electrical properties. Doping of iodine was effected in situ. The structural properties of these films were evaluated by FTIR spectroscopy and the optical band gap was estimated from UV-vis-NIR measurements. Comparative studies on the structural, optical and electrical properties of a.c. and rf polymerization are presented here. It has been found that the optical band gap of the polyaniline thin films prepared by rf and a.c. plasma polymerization techniques differ considerably and the band gap is further reduced by in situ doping of iodine. The electrical conductivity measurements on these films show a higher value of electrical conductivity in the case of rf plasma polymerized thin films when compared to the a.c. plasma polymerized films. Also, it is found that the iodine doping enhanced conductivity of the polymer thin films considerably. The results are compared and correlated and have been explained with respect to the different structures adopted under these two preparation techniques

Fabrication of a quantum well heterostructure based on plasma polymerized aniline and its characterization using STM/STS

Two-dimensional electronic systems play a crucial role in modern electronics and offer a multitude of opportunities to study the fundamental phenomena at low dimensional physics. A quantum well heterostructure based on polyaniline (P) and iodine doped polyaniline (I) thin films were fabricated using radio frequency plasma polymerization on indium tin oxide coated glass plate. Scanning probe microscopy and scanning electron microscopy studies were employed to study the morphology and roughness of the polymer thin films. Local electronic density of states (LDOS) of the P–I–P heterostructures is probed using scanning tunnelling spectroscopy (STS). A step like LDOS is observed in the P–I–P heterostructure and is attributed to the quantum well confinement of electrons in the polymer heterostructure.