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.

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.

Modification of Phenol Formaldehyde Resin for Improved Mechanical Properties

Phenolic resins suffer from the presence of microvoids on curing. This often leads to less than satisfactory properties in the cured resin. This disadvantage has limited the use of phenolic resins to some extent. This study is an attempt to improve the mechanical properties of the phenolic resol resins by chemical modification aimed at reducing the microvoid population. With this end in view various themoset resins synthesised under predetennined conditions have been employed for modifying phenolic resols. Such resins include unsaturated polyester, epoxy and epoxy novolac prepolymers. The results establish the effectiveness of these resins for improving the mechanical properties of phenolics. Experimental and analytical techniques used include FTIR, DMA, TGA, SEM and mechanical property evaluation. While most of the modifier resins employed give positive results the effect of adding UP is found to be surprising as well as impressive.

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

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.

Novel Approaches to Biodegradable Polymers: Synthesis and Biodegradation Studies

Biodegradable polymers have opened an emerging area of great interest because they are the ultimate solution for the disposal problems of synthetic polymers used for short time applications in the environmental and biomedical field. The biodegradable polymers available until recently have a number of limitations in terms of strength and dimensional stability. Most of them have processing problems and are also very expensive. Recent developments in biodegradable polymers show that monomers and polymers obtained from renewable resources are important owing to their inherent biodegradability, biocompatibility and easy availability. The present study is, therefore, mostly concemed with the utilization of renewable resources by effecting chemical modification/copolymerization on existing synthetic polymers/natural polymers for introducing better biodegradability and material properties.The thesis describes multiple approaches in the design of new biodegradable polymers: (1) Chemical modification of an existing nonbiodegradable polymer, polyethylene, by anchoring monosaccharides after functionalization to introduce biodegradability. (2) Copolymerization of an existing biodegradable polymer, polylactide, with suitable monomers and/or polymers to tailor their properties to suit the emerging requirements such as (2a) graft copolymerization of lactide onto chitosan to get controlled solvation and biodegradability and (2b) copolymerization of polylactide with cycloaliphatic amide segments to improve upon the thermal properties and processability.

Current status and biodiversity modification in the coastal wetland ecosystems of India with objectives for its sustainable management

The South West (S.W.) coast of India is blessed with a series of wetland systems popularly referred to as backwaters covering a total area of 46128.94 ha. These backwaters are internationally renowned for their aesthetic and scientific values including being a repository for several species fish and shell fishes. This is more significant in that three wetlands (Vembanad, Sasthamcotta and Ashtamudi) have recently been designated as Ramsar sites of international importance. Thirty major backwaters forming the crux of the coastal wetlands form an abode for over 200 resident or migratory fish and shellfish species. The fishing activities in these water bodies provide the livelihood to about 200,000 fishers and also provide full-time employment to over 50,000 fishermen. This paper describes the changes on the environmental and biodiversity status of selected wetlands, during 1994-2005 period. The pH was generally near neutral to alkaline in range. The salinity values indicated mixohaline condition ranging from 5.20-32.38 ppt. in the 12 wetlands. The productivity values were generally low in most of the wetlands during the study, where the gross production varied from 0.22 gC/m3/day in Kadinamkulam to 1.10 gC/m3/day in the Kayamkulam. The diversity of plankton and benthos was more during the pre-monsoon compared to the monsoon and post-monsoon periods in most of the wetlands. The diversity of plankton and benthos was more during the pre-monsoon compared to the monsoon and post-monsoon periods in most of the wetlands. The average fish yield per ha. varied from 246 kg. in Valapattanam to 2747.3 kg. in Azhikode wetland. Retting of coconut husk in most of the wetlands led to acidic pH conditions with anoxia resulting in the production of high amounts of sulphide, coupled with high carbon dioxide values leading to drastic reduction in the incidence and abundance of plankton, benthic fauna and the fishery resources. The major fish species recorded from the investigation were Etroplus suratensis, E. maculatus, Channa marulius, Labeo dussumieri, Puntius sp. Lutianus argentimaculatus, Mystus sp., Tachysurus sp. and Hemiramphus sp. The majority of these backwaters are highly stressed, especially during the pre monsoon period when the retting activity is at its peak. The study has clearly reflected that a more restrained and cautious approach is needed to manage and preserve the unique backwater ecosystems of South-west India