Silane Grafting of Polyethylenes

Reactive extrusion is an attractive means of polymer processing since the shaping and reaction take place in a single operation. In this paper we report the silane grafting of polyethylenes in a single screw extruder. The optimum conditions for silane grafting, viz. temperature, shear rate, silane and DCP concentrations, were determined on a torque rheometer and then actual extrusion was performed using these conditions. The study shows that an optimum low level of grafting/ crosslinking can be introduced into polyethylene during its extrusion for better mechanical behavior and=or thermal stability without affecting the processability.

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.

Effect of Silane Coupling Agent on Cure Characteristics and Mechanical Properties of Nitrile Rubber/Reclaimed Rubber Blend

Blends of nitrile rubber and reclaimed rubber containing different levels of a coupling agent, Si 69 (bis(3- triethoxysilyl propyl)(tetrasulphide) were prepared and the cure characteristic's and mechanical properties were studied. Optimum loading of Si-69 was found to be a function of blend ratio. 3 phi- of Si 69 in a 70:30. Blend was found to be the optimum combination with respect to the mechanical properties. The rate and state of cure were also affected bv the conp/ing agent. Tensile strength, tear strength and abrasion resistance were improved in the presence of coupling agent. While the state of cure improved, the cure rate and scorch time decreased with increasing silane content. Ageing studies showed that the blends containing the coupling agent were inferior to the unmodified blends.

Effect of Silane Coupling Agent on Cure Characteristics and Mechanical Properties of Chloroprene Rubber/Reclaimed Rubber Blend

Chloroprene rubber was blended with whole tire reclaimed rubber (WTR) in presence of different levels of a coupling agent Si69 [bis- (3-(triethoxysilyl)propy1)tetrasuIfide] and the cure characteristics and mechanical properties were studied. The rate and state of cure were also affected by the coupling agent. While the cure time was increased, the cure rate and scorch time were decreased with increasing silane content. Tensile strength, tear strength, and abrasion resistance were improved in the presence of coupling agent. Compression set and resilience were adversely affected in presence of silane-coupling agent.Aging studies showed that the blends containing the coupling agent were inferior to the unmodified blends.

Studies on the Utilisation of Rubber Reclaim in Elastomers

The thesis describes utilisation of reclaimed rubber, Whole Tyre Reclaim (WTR) produced from bio non- degradable solid pollutant scrap and used tyres. In this study an attempt has made to optimize the substitution of virgin rubber with WTR in both natural and synthetic rubber compounds without seriously compromising the important mechanical properties. The WTR is used as potent source of rubber hydrocarbon and carbon black filler. Apart from natural rubber (NR), Butadiene rubber (BR), Styrene butadiene rubber (SBR), Acrylonitrile butadiene rubber (NBR) and Chloroprene rubber (CR) were selected for study, being the most widely used general purpose and specialty rubbers. The compatibility problem was addressed by functionalisation of WTR with maleic anhydride and by using a coupling agent Si69.The blends were systematically evaluated with respect to various mechanical properties. The thermogravimetric analyses were also carried out to evaluate the thermal stability of the blends.Mechanical properties of the blends were property and matrix dependant. Presence of reinforcing carbon black filler and curatives in the reclaimed rubber improved the mechanical properties with the exception of some of the elastic properties like heat build up, resilience, compression set. When WTR was blended with natural rubber and synthetic rubbers, as the concentration of the low molecular weight, depolymerised WfR was increased above 46-weight percent, the properties deteriorates.When WTR was blended with crystallizing rubbers such as natural rubber and chloroprene rubber, properties like tensile strength, ultimate elongation were decreased in presence of WTR. Where as in the case of blends of WTR with non-crystallizing rubbers reinforcement effect was more prominent.The effect of functionalisation and coupling agent was studied in three matrices having different levels of polarity(NBR, CR and SBR).The grafting of maleic anhydride on to WTR definitely improved the properties of its blends with NBR, CR and SBR, the effect being prominent in Chloroprene rubber.Improvement in properties of these blends could also achieved by using a coupling agent Si69. With this there is apparent plasticizing effect at higher loading of the coupling agent. The optimum concentration of Si69 was 1 phr for improved properties, though the improvements are not as significant as in the case of maleic anhydride grafting.Thermal stability of the blend was increased by using silane-coupling agent.

Studies on Natural Rubber/Clay Nanocomposites: Effect of Maleic Anhydride Grafting of Rubber

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

Chemical Modification of Blends of Poly (Vinyl Chloride) With Linear Low Density Polyethylene

The effects of modifying blends of poly(vinyl chloride) (PVC) with linear low density polyethylene (LLDPE) by means of acrylic acid, maleic anhydride, phenolic resins and p-phenylene diamine were investigated. Modification by acrylic acid and maleic anhydride in the presence of dicumyl peroxide was found to be the most useful procedure for improving the mechanical behaviour and adhesion properties of the blend. The improvement was found to be due mainly to the grafting of the carboxylic acid to the polymer chains; grafting was found to be more effective in LLDPE/PVC blends than in pure LLDPE.

Cure Characteristics and Mechanical Properties of Maleic Anhydride Grafted Reclaimed Rubber/ Styrene Butadiene Rubber Blends

Blends of styrene butadiene rubber (SBR) with maleic anhydride grafted whole tire reclaim (MA-g-WTR) have been prepared and the cure and mechanical properties have been studied with respect to the reclaim content. The grafting was carried out in the presence of dicumylperoxide (DCP) in a Brabender Plasticorder at 150'C. The presence of anhydride group on the WTR was confirmed by infrared spectrometry (IR) study. The properties were compared with those of the blends containing unmodified WTR. Though the cure time was marginally higher, the mechanical properties of the blends containing grafted WTR were better than that of the unmodified blends.

Studies - on Maleic Anhydride Grafted Reclaimed Rubber/Acrylonitrile Butadiene Rubber Blends

Blends of Acrylonitrile rubber with Maleic anhydride grafted Whole Tyre Reclaim WTR (MA-g-WTR) have been prepared and the cure and mechanical properties have been studied with respect to reclaim content. Control compounds containing unmodified WTR were also prepared for comparison. Grafting was confirmed by IR studies. Blends containing grafted WTR showed higher minimum torque and (max-min) torque. They also showed longer cure time, scorch time and lower cure rate. Grafting of the WTR with maleic anhydride also resulted in the improved tensile strength, abrasion resistance, compression set and resilience. However, the heat build up under dynamic loading was marginally higher for the blends containing grafted reclaimed rubber.

Recyclable Short Fibre Reinforced Plastics PP/Nylon and HDPE/Nylon composites

The study shows that standard plastics like polypropylene and high density polyethylene can be reinforced by adding nylon short fibres. Compared to the conventional glass reinforced thermoplastics this novel class of reinforced thermoplastics has the major advantage of recyclability. Hence such composites represent a new spectrum of recyclable polymer composites. The fibre length and fibre diameter used for reinforcement are critical parameters While there is a critical fibre length below which no effective reinforcement takes place, the reinforcement improves when the fibre diameter decreases due to increased surface area.While the fibres alone give moderate reinforcement, chemical modification of the matrix can further improve the strength and modulus of the composites. Maleic anhydride grafting in presence of styrene was found to be the most efficient chemical modification. While the fibre addition enhances the viscosity of the melt at lower shear rates, the enhancement at higher shear rate is only marginal. This shows that processing of the composite can be done in a similar way to that of the matrix polymer in high shear operations such as injection moulding. Another significant observation is the decrease in melt viscosity of the composite upon grafting. Thus chemical modification of matrix makes processing of the composite easier in addition to improving the mechanical load bearing capacity.For the development of a useful short fibre composite, selection of proper materials, optimum design with regard to the particular product and choosing proper processing parameters are most essential. Since there is a co-influence of many parameters, analytical solutions are difficult. Hence for selecting proper processing parameters 'rnold flow' software was utilized. The orientation of the fibres, mechanical properties, temperature profile, shrinkage, fill time etc. were determined using the software.Another interesting feature of the nylon fibre/PP and nylon fibre/HDPE composites is their thermal behaviour. Both nylon and PP degrade at the same temperature in single steps and hence the thermal degradation behaviour of the composites is also being predictable. It is observed that the thermal behaviour of the matrix or reinforcement does not affect each other. Almost similar behaviour is observed in the case of nylon fibre/HDPE composites. Another equally significant factor is the nucleating effect of nylon fibre when the composite melt cools down. In the presence of the fibre the onset of crystallization occurs at slightly higher temperature.When the matrix is modified by grafting, the onset of crystallization occurs at still higher temperature. Hence it may be calculated that one reason for the improvement in mechanical behaviour of the composite is the difference in crystallization behaviour of the matrix in presence of the fibre.As mentioned earlier, a major advantage of these composites is their recyclability. Two basic approaches may be employed for recycling namely, low temperature recycling and high temperature recycling. In the low temperature recycling, the recycling is done at a temperature above the melting point of the matrix, but below that of the fibres while in the high temperature route. the recycling is done at a temperature above the melting points of both matrix and fibre. The former is particularly interesting in that the recycled material has equal or even better mechanical properties compared to the initial product. This is possible because the orientation of the fibre can improve with successive recycling. Hence such recycled composites can be used for the same applications for which the original composite was developed. In high temperature recycling, the composite is converted into a blend and hence the properties will be inferior to that of the original composite, but will be higher than that of the matrix material alone.

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.

Physicochemical and Biochemical Characterization of Enzymes Immobilized on lnorganic Matrices

Biotechnology is currently considered as a useful altemative to conventional process technology in industrial and catalytic fields. The increasing awareness of the need to create green and sustainable production processes in all fields of chemistry has stimulated materials scientists to search for innovative catalysts supports. lmmobilization of enzymes in inorganic matrices is very useful in practical applications due to the preserved stability and catalytic activity of the immobilized enzymes under extreme conditions. Nanostructured inorganic, organic or hybrid organic-inorganic nanocomposites present paramount advantages to facilitate integration and miniaturization of the devices (nanotechnologies), thus affording a direct connection between the inorganic, organic and biological worlds. These properties, combined with good chemical stability, make them competent candidates for designed biocatalysts, protein-separation devices, drug delivery systems, and biosensors Aluininosilicate clays and layered double hydroxides, displaying, respectively, cation and anion exchange properties, were found to be attractive materials for immobilization because of their hydrophilic, swelling and porosity properties, as well as their mechanical and thermal stability.The aim of this study is the replacement of inorganic catalysts by immobilized lipases to obtain purer and healthier products.Mesocellular silica foams were synthesized by oil-in-water microemulsion templating route and were functionalized with silane and glutaraldehyde. " The experimental results from IR spectroscopy and elemental analysis demonstrated the presence of immobilized lipase and also functionalisation with silane and glutaraldehyde on the supports.The present work is a comprehensive study on enzymatic synthesis of butyl isobutyrate through esterification reaction using lipase immobilized onto mesocellular siliceous foams and montmorillonite K-10 via adsorption and covalent binding. Moreover, the irnrnobil-ization does not modify the nature of the kinetic mechanism proposed which is of the Bi-Bi Ping—Pong type with inhibition by n-butanol. The immobilized biocatalyst can be commercially exploited for the synthesis of other short chain flavor esters. Mesocellular silica foams (MCF) were synthesized by microemusion templating method via two different routes (hydrothermal and room temperature). and were functionalized with silane and glutaraldehyde. Candida rugosa lipase was adsorbed onto MCF silica and clay using heptane as the coupling medium for reactions in non-aqueous media. I From XRD results, a slight broadening and lowering of d spacing values after immobilization and modification was observed in the case of MCF 160 and MCF35 but there was no change in the d-spacing in the case of K-10 which showed that the enzymes are adsorbed only on the external surface. This was further confirmed from the nitrogen adsorption measurements

Spray Pyrolysed Tin Chalcogenide Thin Films: Optimization of optoelectronic properties of SnS for possible photovoltaic application as an absorber layer

In the early 19th century, industrial revolution was fuelled mainly by the development of machine based manufacturing and the increased use of coal. Later on, the focal point shifted to oil, thanks to the mass-production technology, ease of transport/storage and also the (less) environmental issues in comparison with the coal!! By the dawn of 21st century, due to the depletion of oil reserves and pollution resulting from heavy usage of oil the demand for clean energy was on the rising edge. This ever growing demand has propelled research on photovoltaics which has emerged successful and is currently being looked up to as the only solace for meeting our present day energy requirements. The proven PV technology on commercial scale is based on silicon but the recent boom in the demand for photovoltaic modules has in turn created a shortage in supply of silicon. Also the technology is still not accessible to common man. This has onset the research and development work on moderately efficient, eco-friendly and low cost photovoltaic devices (solar cells). Thin film photovoltaic modules have made a breakthrough entry in the PV market on these grounds. Thin films have the potential to revolutionize the present cost structure of solar cells by eliminating the use of the expensive silicon wafers that alone accounts for above 50% of total module manufacturing cost.Well developed thin film photovoltaic technologies are based on amorphous silicon, CdTe and CuInSe2. However the cell fabrication process using amorphous silicon requires handling of very toxic gases (like phosphene, silane and borane) and costly technologies for cell fabrication. In the case of other materials too, there are difficulties like maintaining stoichiometry (especially in large area films), alleged environmental hazards and high cost of indium. Hence there is an urgent need for the development of materials that are easy to prepare, eco-friendly and available in abundance. The work presented in this thesis is an attempt towards the development of a cost-effective, eco-friendly material for thin film solar cells using simple economically viable technique. Sn-based window and absorber layers deposited using Chemical Spray Pyrolysis (CSP) technique have been chosen for the purpose

Covulcanization of elastomer blends with special reference to NR/EPDM blends

Attempts have been made to attain satisfactory network structures in each of the phases of a rubber blend by minimising the cure rate imbalance by employing methods such as grafting of accelerators to the slow curing rubber, chemically bonding the crosslinking agents to the rubber in which it has lower solubility, functionalisation of the slow curing rubber, masterbatching of the curing agents to the slow curing rubber etc. Functionalisation of the slow curing constituents of NR/IIR and NR/EIPDM blends is tried using novel reagents as the first part of this study. However, the crux of the present study is a more direct approach to attaining a covulcanized state in NR/IIR and NR/EPDM blends: Precuring the slow curing rubber (IIR or EPDM) to a low level when it can still blend with NR and then to ck) the final curing after blending with NR. TNM3 precuring is also likely to minimise the viscosity mismatch. Since a low level of resmmal crosslink density is likely to be present lJ1 reclaimed rubbers, blending heat resistant reclaimed rubber such as butyl reclaim with NR may also have the same effect of precuring IIR, and then blending with NR. Hence use of IIR reclaim for developing blends with NR is also proposed to be investigated in this study

Utilization of waste expanded polystyrene: Blends with silica-filled natural rubber

Expanded polystyrene (EPS) constitutes a considerable part of thermoplastic waste in the environment in terms of volume. In this study, this waste material has been utilized for blending with silica-reinforced natural rubber (NR). The NR/EPS (35/5) blends were prepared by melt mixing in a Brabender Plasticorder. Since NR and EPS are incompatible and immiscible a method has been devised to improve compatibility. For this, EPS and NR were initially grafted with maleic anhydride (MA) using dicumyl peroxide (DCP) to give a graft copolymer. Grafting was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy. This grafted blend was subsequently blended with more of NR during mill compounding. Morphological studies using Scanning Electron Microscopy (SEM) showed better dispersion of EPS in the compatibilized blend compared to the noncompatibilized blend. By this technique, the tensile strength, elongation at break, modulus, tear strength, compression set and hardness of the blend were found to be either at par with or better than that of virgin silica filled NR compound. It is also noted that the thermal properties of the blends are equivalent with that of virgin NR. The study establishes the potential of this method for utilising waste EPS