Optimization of Preparation Techniques and Dielectric Study of Polyanilines in the Microwave & High Frequency Field

The thesis deals with the preparation and dielectric characterization of Poly aniline and its analogues in ISM band frequency of 2-4 GHz that includes part of the microwave region (300 MHz to 300 GHz) of the electromagnetic spectrum and an initial dielectric study in the high frequency [O.05MHz-13 MHz]. PolyaniIine has been synthesized by an in situ doping reaction under different temperature and in the presence of inorganic dopants such as HCl H2S04, HN03, HCl04 and organic dopants such as camphorsulphonic acid [CSA], toluenesulphonic acid {TSA) and naphthalenesulphonic acid [NSA]. The variation in dielectric properties with change in reaction temperature, dopants and frequency has been studied. The effect of codopants and microemulsions on the dielectric properties has also been studied in the ISM band. The ISM band of frequencies (2-4 GHz) is of great utility in Industrial, Scientific and Medical (ISM) applications. Microwave heating is a very efficient method of heating dielectric materials and is extensively used in industrial as well as household heating applications.

Studies on the use of drying oils as ingredient in the vulcanization of elastomers

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology

Studies on Thermoplastic Elastomers Based on Polyethylene/Elastomer Blends

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology.

Studies on HDPE/LLDPE Blends

Dept. of Polymer Science and Rubber Technology, Cochin University of Science and Technology

Modification of Polyethylenes by Reactive Extrusion

The main aim of the study was to optimise the reactive extrusion conditions in the conventional modification processes of polyethylenes in a single screw extruder.The optimum conditions for peroxide crosslinking of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blend were determined in a torque rheometer. The actual reactive extrusion was performed in a laboratory single screw extruder using the optimum parameters. The influence of the coagent, triaUyl cyanurate (TAC), on the cross linking of low density polyethylene in the presence of peroxide was also investigated. The peroxide crosslinking was found to improve the mechanical properties and the thermal stability of the polyethylenes. The efficiency of crosslinking was found to be improved by the addition of coagent such as TAC.The optimum conditions for silane grafting viz temperature, shear rate, silane and DCP concentrations were determined on a torque rheometer in the case of LDPE, LLDPE and their blend. Silane grafting of LDPE in the presence of peroxide was performed with and without addition of water. Compounding of such mixtures in the melt at high temperatures caused decomposition of the peroxide and grafting of alkoxy silyl groups to the polyethylene chains.The optimum parameters for maleic anhydride modification of LDPE, LLDPE and their blend were determined. The grafting reaction was confinned by FTIR spectroscopy. Modification of polyethylenes with maleic anhydride in the presence of dicumyl peroxide was found to be useful in improving mechanical properties. The improvement was found to be mainly due to the grafting of carboxyl group and formation of crosslinks between the chains. The cross linking initiated improvements indicate extended property profiles and new application fields for polyethylenes.On the whole the study shows that the optimum conditions for modifying polyethylenes can be determined on a torque rheometer and actual modification can be performed in a single screw extruder by employing the optimum parameters for improved mechanical! thermal behaviour without seriously affecting their processing behaviour.

Modification of Short Fibre Reinforced pp and HDPE Using Nanosilica

The present study was undertaken to prepare nanosilica by a simple cost effective means and to use it as a potential nanomodifier in thermoplastic matrices and to develop useful composites. Nanosilica was prepared from sodium silicate and dilute hydrochloric acid by polymer induced crystallization technique under controlled conditions. The silica surface was modified by silane coupling agent to decrease the agglomeration and thus to increase the reinforcement with polymer. The pristine nanosilica and modified nanosilica were used to make nano-micro hybrid composites. Short glass fibres and nylon fibres were used as microfillers. The hybrid nanocomposites based on Polypropylene (PP) and High density poly ethylene (HOPE) are prepared. The mechanical, thermal, crystallization and dynamic mechanical properties of the composites are evaluated.

EPDM/CIIR Blends: Compatibility, Morphology and Physical Properties

A detailed study of the blends of ethylene-propylene-diene rubber (EPDM) and chlorobutyl rubber (CIIR) is proposed in this study. These blends may find application in the manufacture of curing diaphragms/curing envelopes for tire curing applications. EPDM possesses better physical properties such as high heat resistance, ozone resistance, cold and moisture resistance, high resistance to permanent defonnation, very good resistance to flex cracking and impact. Because of the low gas and moisture penneability, good weathering resistance and high thermal stability of CIIR, blends of EPDM with CIlR may be attractive, if sufficient mechanical strength can be developed. Although a lot of work has been done on elastomer blends, studies on the blends of EPDM and CIIR rubbers are meagre. Hence in this investigation it is proposed to make a systematic study on the characteristics of EPDM and CIIR rubber blends.The mechanical and physical properties of an elastomer blend depend mainly on the blend compatibility. So in the first part of the study, it is proposed to develop compatible blends of EPDM with CIIR. Various commercial grades of ethylenepropylene- diene rubber are proposed to be blended with a specific grade of chlorobutyl rubber at varying proportions. The extent of compatibility in these blends is proposed to be evaluated based on their mechanical properties such as tensile strength, tear strength and ageing resistance. In addition to the physical property measurements, blend compatibility is also proposed to be studied based on the glass transition behavlour of the blends in relation to the Tg's of the individual components using Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). The phase morphology of the blends is also proposed to be investigated by Scanning Electron Microscopy (SEM) studies of the tensile fracture surfaces. In the case of incompatible blends, the effect of addition of chlorosulfonated polyethylene as a compatibiliser is also proposed to be investigated.In the second part of the study, the effect of sulphur curing and resin curing on the curing behaviour and the vulcanizate properties of EPDM/CIIR blends are planned to be evaluated. Since the properties of rubber vulcanizates are determined by their network structures, it is proposed to determine the network structure of the vulcanizates by chemical probes so as to correlate it with the mechanical properties.In the third part of the work, the effect of partial precuring of one of the components prior to blending as a possible means of improving the properties of the blend is proposed to be investigated. This procedure may also help to bring down the viscosity mismatch between the constituent e1astomers and provide covulcanization of the blend.The rheological characteristics and processability of the blends are proposed to be investigated in the last part of the study. To explore their possible applications, the air permeability of the blend samples at varying temperatures is proposed to be measured. The thermal diffusivity behaviour of EPDM/CIlR blends is also proposed to be investigated using novel laser technique. The thermal diffusivity of the blends along with the thermal degradation resistance may help to determine whether the blends are suitable for high temperature applications such as in the manufacturing of curing envelope.

Novel adhesive systems based on neoprene-phenolic blends

The aim of the investigation is to develop new high performance adhesive systems based on neoprene-phenolic blends. Initially the effect of addition of all possible ingredients like fillers, adhesion promoters, curing agents and their optimum compositions to neoprene solution is investigated. The phenolic resin used is a copolymer of phenol-cardanolformaldehyde prepared in the laboratory. The optimum ratio between phenol and cardanol that gives the maximum bond strength in metal-metal, rubber-rubber and rubber-metal specimens has been identified. Further the ratio between total phenols and formaldehyde is also optimised. The above adhesive system is further modified by the addition of epoxidized phenolic novolacs. For this purpose, phenolic novolac resins are prepared in different stoichiometric ratios and are subsequently epoxidized. The effectiveness of the adhesive for bonding different metal and rubber substrates is another part of the study. To study the ageing behaviour, different bonded specimens are exposed to high temperature, hot water and salt water and adhesive properties have been evaluated. The synthesized resins have been characterized by FTIR , HNMR spectroscopy. The molecular weights of the resins have been obtained by GPC. Thermogravimetric analysis and differential scanning calorimetry are used to study the thermal properties. The fractured surface analysis is studied by scanning electron microscopy. The study has brought to light the influence of phenol/ formaldehyde stoichiometric ratio, addition of cardanol (a renewable resource), adhesion promoters and suitability of the adhesive for different substrates and the age resistance of adhesive joints among other things.

Modification of Polypropylene and Polystyrene Using Nanosilica

The present work focuses on the modification of the commonly used thermoplastics, polypropylene and polystyrene using nanosilica preparcd from a cheap source of sodium silicate. Melt compounding technique has been used for nanocomposite preparation as it is simple and suited to injection moulding. Nanosilica in a polymer matrix provide significant enhancement in strength, stiffness and impact strength. Incorporation of silica particles in a polymer also improves its thennal stability. To achieve better dispersion of fillers in polymer matrices the mixing was done at different shear rates. The enhancement in material properties indicates that at higher shear rates there is greater interaction between particles and the matrix and it depends on filler concentration and type of polymer used. N anosilica is a useful filler in thennoplastic polymers and has been applied in automotive applications, electronic appliances and consumer goods.This thesis is divided into six chapters. General introduction to the topic is described in chapter 1. Salient features of polymer nanocomposites, their synthesis, properties and applications are presented. A review of relevant literature and the scope and objectives are also mentioned in this chapter.The materials used and the vanous experimental method and techniques employed in the study are described in chapter 2. Preparation of nanocomposites by melt blending using Thenno Haake Rheocord, preparation of samples, evaluation of mechanical and thennal properties using UTM, Impact testing and characterization using DMA, TGA and DSC and morphology by SEM are described.The preparation of nanosilica from a laboratory scale to a pilot plant scale is described in chapter 3. Generation of surface modified silica, evaluation of kinetic parameters of the synthesis reaction, scale up of the reactor and modeling of the reactor are also dealt with in this chapter.The modification of the commodity thennoplastic, Polypropylene using nanosilica is described in chapter 4. Preparation of PP/silica nanocomposites, evaluation of mechanical properties, thermal and crystallization characteristics, water absorption and ageing resistance studies are also presented.The modification of Polystyrene using synthesized nanosilica IS described in chapter 5. The method of preparation of PS/silica nanocomposites, evaluation of mechanical properties (static and dynamic), thermal properties melt flow characteristics using Haake Rheocord, water absorption and ageing resistance of these nanocomposites are studied.

Development of thermoplastic conducting polymer composites based on polyaniline and polythiophenes for microwave and electrical applications

The microwave and electrical applications of some important conducting polymers are analyzed in this investigation.One of the major drawbacks of conducting polymers is their poor processability,and a solution to overcome this is sought in this investigation.Conducting polymer thermoplastic composites were prepared by the insitu polymerization method to improve the extent of miscibility probably to a semi IPN level.The attractive features of the conducting composite developed are excellent processability,good microwave and electrical conductivity,good microwave absorption,load sensitivity and satisfactory mechanical properties.The composite shows typical frequency selective microwave absorption and refelection behaviors.

NANO - ZINC OXIDE: A Novel Modifier for Thermoplastics

Various synthesis routes have been developed in recent years for the preparation of nanoparticles. One of those methods is polymer induced crystallization. The first objective of the present work was to prepare nano ZnO powder by polymer induced crystallization in chitosan solution and to characterize the material using different techniques like TEM, SEM, XRD, FTLR, UV spectroscopy, TGA, DSC etc.The second object of the study is to prepare composites using nano ZnO. It has been undertaken to explore the potential of nano ZnO as reinforcement in engineering as well as commodity thermoplastics to widen their application spectra. We selected three engineering thermoplastics like [poly ethylene terephthalate, polyamide 6, and polycarbonate] and three commodity plastics like [polypropylene, high density polyethylene, and polystyrene] for the study. To date one of the few disadvantages associated with nanoparticle incorporation has concerned toughness and impact performance. Modification of polymers could reduce impact performance. The present study also focused on whether nano ZnO can act as a modifier for thennoplastics, without sacrificing their impact strength.

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.

Optimisation of the Mechanical Properties of HDPE/PP Blends and Their Recyclable Composites

This study was undertaken in order to upgrade blends of HDPE and PP, two of the most widely used standard plastics so as to widen their application spectrum. Dicumyl peroxide was used as the modifier for the upgradation. Optimum concentration of dicumyl peroxide required for modification was detennined by measurement of mechanical, rheological, thermal and morphological properties. Selected blends were used to prepare recyclable composites with nylon clothes by compression moulding. The composites were characterized by measurement of mechanical and thermal properties. The composites were recycled and the mechanical propertics of the recycled material were determined.

Studies on PVC Blends with Special Reference to PVC/CR and PVC/LLDPE Blends

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology

Isora Fibre Reinforced Polyester and Epoxy Composites

The aim of this investigation is to study the effectiveness of isora fibre as reinforcement material in short and long forms, for unsaturated polyester and epoxy resins.Studies on the optimization of fibre length and fibre loading of randomly oriented isora-polyester composite are described.The salient features of the alkali treatment of short isora fibre on the properties of randomly oriented isora-polyester composite are outlined in this thesis.The effect of surface modification of the hydrophilic isora fibre by different chemical treatments on the properties of randomly oriented isora-polyester composite is outlined.The properties of oriented and randomly oriented isora fibre reinforced epoxy composites with special reference to the effect of fibre loading are reported and also the dynamic mechanical properties ofthe oriented and randomly oriented isora-polyester and isora-epoxy composites are presented and the water absorption kinetics of oriented and randomly oriented isora-polyester composites and oriented isoraepoxy composites are given. The effect of hot air oven aging on the tensile and flexural properties of oriented isora-polyester and isora-epoxy composites are also reported in this thesis.