Synthesis, characterization and properties of Conductive elastomeric composites based on Polypyrrole and short Nylon-6 fiber

The search for new materials especially those possessing special properties continues at a great pace because of ever growing demands of the modern life. The focus on the use of intrinsically conductive polymers in organic electronic devices has led to the development of a totally new class of smart materials. Polypyrrole (PPy) is one of the most stable known conducting polymers and also one of the easiest to synthesize. In addition, its high conductivity, good redox reversibility and excellent microwave absorbing characteristics have led to the existence of wide and diversified applications for PPy. However, as any conjugated conducting polymer, PPy lacks processability, flexibility and strength which are essential for industrial requirements. Among various approaches to making tractable materials based on PPy, incorporating PPy within an electrically insulating polymer appears to be a promising method, and this has triggered the development of blends or composites. Conductive elastomeric composites of polypyrrole are important in that they are composite materials suitable for devices where flexibility is an important parameter. Moreover these composites can be moulded into complex shapes. In this work an attempt has been made to prepare conducting elastomeric composites by the incorporation of PPy and PPy coated short Nylon-6 fiber with insulating elastomer matrices- natural rubber and acrylonitrile butadiene rubber. It is well established that mechanical properties of rubber composites can be greatly improved by adding short fibers. Generally short fiber reinforced rubber composites are popular in industrial fields because of their processing advantages, low cost, and their greatly improved technical properties such as strength, stiffness, modulus and damping. In the present work, PPy coated fiber is expected to improve the mechanical properties of the elastomer-PPy composites, at the same time increasing the conductivity. In addition to determination of DC conductivity and evaluation of mechanical properties, the work aims to study the thermal stability, dielectric properties and electromagnetic interference shielding effectiveness of the composites. The thesis consists of ten chapters.

New accelerator system for low temperature curing of elastomers with special reference to NR, NBR and NR/BR blends

The primary objective of this work is to develop an efficient accelerator system for low temperature vulcanization of rubbers. Although xanthates are known to act as accelerators for low temperature vulcanization, a systematic study on the mechanism of vulcanization, the mechanical properties of the vulcanizates at varying temperatures of vulcanization, cure characteristics etc are not reported. Further. xanthate based curing systems are not commonly used because of their chance for premature vulcanization during processing. The proposed study is to develop a novel accelerator system for the low temperature vulcanization of rubbers having enough processing safely. lt is also proposed to develop a method for the prevulcanisation of natural rubber latex at room temperature. As already mentioned the manufacture of rubber products at low temperature will improve its quality and appearance. Also, energy consumption can be reduced by low temperature vulcanization. in addition, low temperature vulcanization will be extremely useful in the area of repair of defective products, since subjecting finished products to high temperatures during the process of repair will adversely affect the quality of the product. Further. room temperature curing accelerator systems will find extensive applications in surface coating industries.

On the magnetic, mechanical and rheological properties of rubber–nickel nanocomposites

Rubber–nickel nanocomposites were synthesized by incorporating freshly prepared nanometric nickel particles in two different matrices namely natural rubber and neoprene rubber according to specific recipes for various loadings of nano nickel and the cure characteristics of these composites were evaluated. The maximum torque values register an increase with the increase in loading of nickel in both composites and this is attributed to the non-interacting nature of nickel nanoparticles with rubber matrices. The cure time of natural rubber composites decreases with increase in the content of nickel, and in neoprene rubber cure, time increases with increase in filler content. In natural rubber, the curing reaction seems to be activated by the presence of nickel particles. The magnetization studies of the composites reveal that the magnetic properties of nickel are retained in the composite samples. The elastic modulus of natural rubber and neoprene rubber are largely improved by the incorporation of nickel particles

Modification of Unsaturated Polyester Resin by Polyurethane Prepolymers

Unsaturated polyester resins (UPRs) are extensively used by the fiber-reinforced plastic (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, UPRs were chemically modified by reactive blending with polyurethane prepolymers having terminal isocyanate groups. Hybrid networks were formed by copolymerisation of unsaturated polyesters with styrene and simultaneous reaction between terminal hydroxyl groups of unsaturated polyester and isocyanate groups of polyurethane prepolymer. The prepolymers were based on toluene diisocyanate (TDI) and each of hydroxy-terminated natural rubber (HTNR), hydroxy- terminated polybutadiene (HTPB), polyethylene glycol (PEG), and castor oil. Properties like tensile strength, toughness, impact resistance, and elongation-at-break of the modified UPRs show considerable improvement by this modification. The thermal stability of the copolymer is also marginally better

Block Copolymers of Unsaturated Polyesters and Functional Elastomers

Block copolymers of unsaturated polyester were prepared by condensation polymerization of hydroxyl or carboxyl terminated liquid rubbers with maleic anhydride, phthalic anhydride, and propylene glycol. The condensate obtained was mixed with styrene monomer to get an unsaturated polyester resin formulation. In this study, copolymers of unsaturated polyesters with hydroxy terminated polybutadiene, carboxy terminated nitrile rubber, and hydroxy terminated natural rubber were prepared. Mechanical properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were evaluated after the resin was cured in appropriate molds for comparison with the control resin. The fracture toughness and impact resistance of CTBN-modified unsaturated polyester show substantial improvement by this copolymerization without seriously affecting any other property

A study on the performance of flexible pavements on mature soil subgrades

The country has witnessed tremendous increase in the vehicle population and increased axle loading pattern during the last decade, leaving its road network overstressed and leading to premature failure. The type of deterioration present in the pavement should be considered for determining whether it has a functional or structural deficiency, so that appropriate overlay type and design can be developed. Structural failure arises from the conditions that adversely affect the load carrying capability of the pavement structure. Inadequate thickness, cracking, distortion and disintegration cause structural deficiency. Functional deficiency arises when the pavement does not provide a smooth riding surface and comfort to the user. This can be due to poor surface friction and texture, hydro planning and splash from wheel path, rutting and excess surface distortion such as potholes, corrugation, faulting, blow up, settlement, heaves etc. Functional condition determines the level of service provided by the facility to its users at a particular time and also the Vehicle Operating Costs (VOC), thus influencing the national economy. Prediction of the pavement deterioration is helpful to assess the remaining effective service life (RSL) of the pavement structure on the basis of reduction in performance levels, and apply various alternative designs and rehabilitation strategies with a long range funding requirement for pavement preservation. In addition, they can predict the impact of treatment on the condition of the sections. The infrastructure prediction models can thus be classified into four groups, namely primary response models, structural performance models, functional performance models and damage models. The factors affecting the deterioration of the roads are very complex in nature and vary from place to place. Hence there is need to have a thorough study of the deterioration mechanism under varied climatic zones and soil conditions before arriving at a definite strategy of road improvement. Realizing the need for a detailed study involving all types of roads in the state with varying traffic and soil conditions, the present study has been attempted. This study attempts to identify the parameters that affect the performance of roads and to develop performance models suitable to Kerala conditions. A critical review of the various factors that contribute to the pavement performance has been presented based on the data collected from selected road stretches and also from five corporations of Kerala. These roads represent the urban conditions as well as National Highways, State Highways and Major District Roads in the sub urban and rural conditions. This research work is a pursuit towards a study of the road condition of Kerala with respect to varying soil, traffic and climatic conditions, periodic performance evaluation of selected roads of representative types and development of distress prediction models for roads of Kerala. In order to achieve this aim, the study is focused into 2 parts. The first part deals with the study of the pavement condition and subgrade soil properties of urban roads distributed in 5 Corporations of Kerala; namely Thiruvananthapuram, Kollam, Kochi, Thrissur and Kozhikode. From selected 44 roads, 68 homogeneous sections were studied. The data collected on the functional and structural condition of the surface include pavement distress in terms of cracks, potholes, rutting, raveling and pothole patching. The structural strength of the pavement was measured as rebound deflection using Benkelman Beam deflection studies. In order to collect the details of the pavement layers and find out the subgrade soil properties, trial pits were dug and the in-situ field density was found using the Sand Replacement Method. Laboratory investigations were carried out to find out the subgrade soil properties, soil classification, Atterberg limits, Optimum Moisture Content, Field Moisture Content and 4 days soaked CBR. The relative compaction in the field was also determined. The traffic details were also collected by conducting traffic volume count survey and axle load survey. From the data thus collected, the strength of the pavement was calculated which is a function of the layer coefficient and thickness and is represented as Structural Number (SN). This was further related to the CBR value of the soil and the Modified Structural Number (MSN) was found out. The condition of the pavement was represented in terms of the Pavement Condition Index (PCI) which is a function of the distress of the surface at the time of the investigation and calculated in the present study using deduct value method developed by U S Army Corps of Engineers. The influence of subgrade soil type and pavement condition on the relationship between MSN and rebound deflection was studied using appropriate plots for predominant types of soil and for classified value of Pavement Condition Index. The relationship will be helpful for practicing engineers to design the overlay thickness required for the pavement, without conducting the BBD test. Regression analysis using SPSS was done with various trials to find out the best fit relationship between the rebound deflection and CBR, and other soil properties for Gravel, Sand, Silt & Clay fractions. The second part of the study deals with periodic performance evaluation of selected road stretches representing National Highway (NH), State Highway (SH) and Major District Road (MDR), located in different geographical conditions and with varying traffic. 8 road sections divided into 15 homogeneous sections were selected for the study and 6 sets of continuous periodic data were collected. The periodic data collected include the functional and structural condition in terms of distress (pothole, pothole patch, cracks, rutting and raveling), skid resistance using a portable skid resistance pendulum, surface unevenness using Bump Integrator, texture depth using sand patch method and rebound deflection using Benkelman Beam. Baseline data of the study stretches were collected as one time data. Pavement history was obtained as secondary data. Pavement drainage characteristics were collected in terms of camber or cross slope using camber board (slope meter) for the carriage way and shoulders, availability of longitudinal side drain, presence of valley, terrain condition, soil moisture content, water table data, High Flood Level, rainfall data, land use and cross slope of the adjoining land. These data were used for finding out the drainage condition of the study stretches. Traffic studies were conducted, including classified volume count and axle load studies. From the field data thus collected, the progression of each parameter was plotted for all the study roads; and validated for their accuracy. Structural Number (SN) and Modified Structural Number (MSN) were calculated for the study stretches. Progression of the deflection, distress, unevenness, skid resistance and macro texture of the study roads were evaluated. Since the deterioration of the pavement is a complex phenomena contributed by all the above factors, pavement deterioration models were developed as non linear regression models, using SPSS with the periodic data collected for all the above road stretches. General models were developed for cracking progression, raveling progression, pothole progression and roughness progression using SPSS. A model for construction quality was also developed. Calibration of HDM–4 pavement deterioration models for local conditions was done using the data for Cracking, Raveling, Pothole and Roughness. Validation was done using the data collected in 2013. The application of HDM-4 to compare different maintenance and rehabilitation options were studied considering the deterioration parameters like cracking, pothole and raveling. The alternatives considered for analysis were base alternative with crack sealing and patching, overlay with 40 mm BC using ordinary bitumen, overlay with 40 mm BC using Natural Rubber Modified Bitumen and an overlay of Ultra Thin White Topping. Economic analysis of these options was done considering the Life Cycle Cost (LCC). The average speed that can be obtained by applying these options were also compared. The results were in favour of Ultra Thin White Topping over flexible pavements. Hence, Design Charts were also plotted for estimation of maximum wheel load stresses for different slab thickness under different soil conditions. The design charts showed the maximum stress for a particular slab thickness and different soil conditions incorporating different k values. These charts can be handy for a design engineer. Fuzzy rule based models developed for site specific conditions were compared with regression models developed using SPSS. The Riding Comfort Index (RCI) was calculated and correlated with unevenness to develop a relationship. Relationships were developed between Skid Number and Macro Texture of the pavement. The effort made through this research work will be helpful to highway engineers in understanding the behaviour of flexible pavements in Kerala conditions and for arriving at suitable maintenance and rehabilitation strategies. Key Words: Flexible Pavements – Performance Evaluation – Urban Roads – NH – SH and other roads – Performance Models – Deflection – Riding Comfort Index – Skid Resistance – Texture Depth – Unevenness – Ultra Thin White Topping

Implication of Trade, Livelihood and Employment Exclusion among Workers in Plantation Sector in Kerala

The first part of the study has focused on the trends in area, production and productivity comparing the state’s performance with of national level performance. Also an attempt was made to understand the trends in commodity price over the years especially in the post liberalization period from the early 1990s. Plantation commodities occupy an important share in the country’s export basket and thereby earning foreign exchange to the national exchequer. Taking into consideration the competitive dimension of natural rubber, cardamom and pepper in the export market was analyzed to see penetration of these commodities in the world market.The second part of the study has tried to understand the plantation workers livelihood by understand the employment generation in the sector. Livelihood assets of plantation workers were analyzed to understand the nature of ownership of various assets. Understanding the poor quality and ownership of various livelihood assets and their relative deprivation the study also tried to understand the income-expenditure patterns and the nature of indebtedness among workers and the factors responsible for deprivation and thereby social exclusion.Area, Production and productivity trends of rubber, pepper and cardamom show a mixed picture. Area, Production trends are impacted greatly by the commodity price of the plantation crops.High correlation exists between commodity price and area and production trends of plantation crops in the state.In terms of Natural Rubber, Kerala experienced a steady growth over the years in terms of area production and productivity as the price of rubber has increasedIn terms of black pepper, the state witnessed a deceleration in growth.In the case of cardamom the area of cultivation declined whereas production increasedProductivity of natural rubber, pepper and cardamom has increased substantially over the yearsEmployment pattern in rubber and spices sub-sector has been analyzed by looking in to the commodity prices so as to see the changes in employment pattern over the years. The study has helped to understand that commodity price and employment generation in plantations are interconnected to such an extent that a fall in the commodity price have greater reverberations on the employment pattern in plantations.Livelihood analysis both in the small and large holdings show that workers belonging to rubber (large and small rubber) plantations have shown better possession of livelihood assets when compared to spices plantation workers as 16.2 percent of the spices sub-sector workers claimed about ownership of house which is considered to be an important and primary livelihood asset.In the case of natural assets like accessibility, availability and duration of water for drinking and other household purposes, the situation of workers in spices plantation still remain poor as around 80 percent of workers depending on public well public taps and canals as source of drinking water.Evaluating financial assets also give clear indication that the road to secure financial assets still remains a distant dream for the workers in plantation sectorEvaluating income and expenditure trends pinpoints to the fact that disparity in terms of income exist among the plantation workersWhile observing the employment though wage levels have improved because of improvement in commodity price of plantation crops, significant improvements are not visible in their livelihood and they remain excluded compared to other sections of the society.

Biobased composites from tannin-phenolic polymers reinforced with coir fibers

Tannin-phenolic polymers prepared using tannin, a macromolecule obtained from natural sources, were used in the preparation of composites reinforced with coir fibers. The composites based on tannin-phenolic polymers (50% (w/w) of tannin as substitute of the phenol) were prepared using the coir fibers as reinforcement (30-70% (w/w), 3.0-6.0 cm, randomly distributed). The Izod impact strength of the composites showed an improvement in this property due to the incorporation of coir fibers in the tannin-phenolic matrices. The SEM images showed excellent adhesion at the fiber/matrix interface. The coir fiber had bundles regularly spaced, which enhanced the diffusion of the resin into the fiber. In addition, the high lignin content of this fiber results in a high concentration of aromatic rings, which increased the compatibility with the matrix. The values of the diffusion coefficient of water, determined using Fick`s laws, show that there was no correlation between the fiber percentage and the water diffusion. The DMTA curves showed that the storage moduli of the composites reinforced with coir fibers were considerably higher than that of the thermoset, and the increase in the proportion of fibers led to a proportional increase in the storage moduli of these materials. The biobased composites obtained have potential for non-structural applications, such as in the internal parts of automotives vehicles. To our knowledge, this is the first study on this kind of biobased composites. (C) 2010 Elsevier B.V. All rights reserved.

Slurry pump side-liner wear : comparison of some laboratory and field results

The current work compares some slurry pump lab wear results with the wear found across different field applications with d₈₅ particle size ranging from 100 to 4000mm. Side-liner wear life data has been collected for two different impeller geometries and two different material classes (cast iron and natural rubber). Different field wear patterns have been photographed and categorised on the basis of particle size. The field wear patterns showed close similarity to the lab wear patterns particularly in the areas of localised gouging. Wear rates are also compared for the different geometries. Overall trend of wear with particle size for the white iron parts was similar to the grey iron lab tests albeit at significantly lower wear rates. In general, the wear with the rubber side-liner was less at smaller particle sizes but greater for particles larger than d8The current work compares some slurry pump lab wear results with the wear found across different field applications with d₈₅ particle 10 size ranging from 100 to 4000mm. Side-liner wear life data has been collected for two different impeller geometries and two different 11 material classes (cast iron and natural rubber). Different field wear patterns have been photographed and categorised on the basis of particle 12 size. The field wear patterns showed close similarity to the lab wear patterns particularly in the areas of localised gouging. Wear rates are 13 also compared for the different geometries. Overall trend of wear with particle size for the white iron parts was similar to the grey iron lab 14 tests albeit at significantly lower wear rates. In general, the wear with the rubber side-liner was less at smaller particle sizes but greater for 15 particles larger than d₈₅ of about 700mm. © 2001 Elsevier Science B.Y. All rights reserved.

Hypoallergenic variants of the major latex allergen Hev b 6.01 retaining human T lymphocyte reactivity

Hev b 6.01 is a major allergen of natural rubber latex with sensitization of 70–86% of latex glove-allergic subjects. Recently, we mapped the immunodominant T cell sites of Hev b 6.01 to the highly IgE-reactive hevein (Hev b 6.02) domain. Hev b 6.01 contains 14 cysteine residues with multiple disulphide bridges stabilizing tertiary conformation. With the goal of a standardized specific immunotherapy we developed hypoallergenic Hev b 6.01 mutants by site-directed mutagenesis of selected cysteine residues (3, 12, 17, and 41) within the Hev b 6.02 domain. Peptides corresponding to the Hev b 6.02 domain of two of the mutants were also synthesized. These mutants and peptide variants showed markedly decreased or ablated latex-allergic patient serum IgE binding by immunoblotting and ELISA. Basophil activation testing confirmed markedly decreased activation with successive cysteine substitutions of the mutants and complete abrogation with the Hev b 6.02 (Cys 3, 12, 17, 41 Ala) peptide. Retention of T cell reactivity is crucial for effective specific immunotherapy and all mutants and peptide variants maintained their latex-specific T cell reactivity. The ablated allergenicity but retained T cell reactivity of the Hev b 6.02 (Cys 3, 12, 17, 41 Ala) peptide suggests this peptide is a suitable candidate for inclusion in a latex immunotherapy preparation.

Economic linkages across commodity futures : hedging and trading implications

We investigate cross-market trading dynamics in futures contracts written on seemingly unrelated commodities that are consumed by a common industry. On the Tokyo Commodity Exchange, we find such evidence in natural rubber (NR), palladium (PA) and gasoline (GA) futures markets. The automobile industry is responsible for more than 50% of global demand for each of these commodities. VAR estimation reveals short-run cross-market interaction between NR and GA, and from NR to PA. Cross-market influence exerted by PA is felt in longer dynamics, with PA volatility (volume) affecting NR (GA) volume (volatility). Our findings are robust to lag-specification, volatility measure, and consistent with full BEKK-GARCH estimation results. Further analysis, which benchmarks against silver futures market, TOCOM index and TOPIX transportation index, confirms that our results are driven by a common industry exposure, and not a commodity market factor. A simple trading rule that incorporates short-run GA and long-run PA dynamics to predict NR return yields positive economic profit. Our study offers new insights into how commodity and equity markets relate at an industry level, and implications for multi-commodity hedging.

Common industry exposure in seemingly unrelated commodities

We propose and document robust evidence of cross-market return, volatility, and volume interactions among futures contracts written seemingly unrelated commodities exposed to a common industry. On the Tokyo Commodity Exchange, we find such evidence in natural rubber (NR), aluminum (AL) and gasoline (GA) futures markets, which are complementary commodities heavily consumed by Japan's automobile industry. Our VAR results indicate that (i) for shorter dynamics, NR and GA volatility both influence AL volatility; GA volume affects NR volatility and volume; the GA market is immune to both NR and AL trading activities; (ii) for longer dynamics, AL volume affects both NR volume and GA volatility; NR volume influences GA volume. These results are robust to lag-specifications, volatility measures and are consistent with full BEKK-GARCH estimates. Further analysis using the silver contract, TOCOM and TOPIX transportation indices, shows that a commodity market factor cannot explain our result. Our results offer insights into how commodity and equity markets relate at an industry level.

Comparing different economic linkages among commodity futures

Gasoline (GA) and kerosene (KO) are extracted from crude oil (CO), such that the three fuel commodities share a chemical link. On the other hand, GA also shares an industrial link with natural rubber (NR) and palladium (PA) as complementary commodities that are heavily consumed by the automobile industry. We contrast the information content embedded in the two economic linkages. Focusing on TOCOM futures contracts written on the five commodities and centering on GA, we confirm that incremental information provided by either CO, KO or NR, PA over a buy-and-hold strategy and a naive forecast, are both statistically and economically significant. While the chemical link forecast is more profitable, a double-link forecast generated from a VECM with two cointegrating vectors (KO-GA and GANR prices) outperforms both single-link forecasts based on risk-adjusted profit net of transaction costs. Further comparisons against the profitability of commodity-based momentum strategies documented in Erb and Harvey (2006) and Miffre and Rallis (2007) show that the double-link forecast holds its own against the most profitable of the 75 momentum strategies considered. This strongly suggests that not only are there incremental profits to be gained from harnessing and combining economic links among commodity futures, the resultant incremental profits are economically significant against other proven commodity-based trading strategies in the existing literature.

Primary prevention of latex related sensitisation and occupational asthma : a systematic review

Eight primary prevention intervention studies on natural rubber latex (NRL) published since 1990 were identified and reviewed. This is the largest evidence base of primary prevention studies for any occupational asthmagen. Review of this small and largely observational evidence base supports the following evidence statement: Substitution of powdered latex gloves with low protein powder‐free NRL gloves or latex‐free gloves greatly reduces NRL aeroallergens, NRL sensitisation, and NRL‐asthma in healthcare workers. Evidence in support of this statement is ranked SIGN level 2+, referring to well conducted case‐control or cohort studies with a low risk of confounding, bias, or chance and a moderate probability that the relationship is causal. Substitution of powdered latex gloves with low protein powder‐free NRL gloves or latex‐free gloves promises benefits to both workers' health and cost and human resource savings for employers. This message should be broadly disseminated beyond the hospital sector to include other healthcare settings (such as aged care facilities) as well as food service and other industries where latex gloves might be used.