Mechanical Properties of Short-Isora-Fiber-Reinforced Natural Rubber Composites: Effects of Fiber Length, Orientation, and Loading; Alkali Treatment;and Bonding Agent

A series of short-isora-fiber-reinforced natural rubber composites were prepared by the incorporation of fibers of different lengths (6, 10, and 14 mm) at 15 phr loading and at different concentrations (10, 20, 30, and 40 phr) with a 10 mm fiber length. Mixes were also prepared with 10 mm long fibers treated with a 5% NaOH solution. The vulcanization parameters, processability, and stress-strain properties of these composites were analyzed. Properties such as tensile strength, tear strength, and tensile modulus were found to be at maximum for composites containing longitudinally oriented fibers 10 mm in length. Mixes containing fiber loadings of 30 phr with bonding agent (resorcinol-formaldehyde [RF] resin) showed mechanical properties superior to all other composites. Scanning electron microscopy (SEM) studies were carried out to investigate the fiber surface morphology, fiber pullout, and fiber-rubber interface. SEM studies showed that the bonding between the fiber and rubber was improved with treated fibers and with the use of bonding agent.

Alkali insoluble glucan extracted from Acremonium diospyri is a more potent immunostimulant in the Indian White Shrimp, Fenneropenaeus indicus than alkali soluble glucan

E¡ect of an extraction method on the structure of glucan and its immunostimulatory response in Fenneropenaeus indicus was investigated. Here we extracted alkali insoluble glucan (AIG) and alkali soluble glucan (ASG) from a ¢lamentous fungi Acremonium diospyri following alkali^acid hydrolysis and the sodium hypochlorite oxidation and dimethyl sulphoxide extraction method respectively. Structural analysis showed that 85% of glucan in AIG was a (1 !3)-b-D-glucan and it increased the prophenoloxidase and reactive oxygen intermediate activity when administered to F. indicus. On the other hand, ASG, which contained 93% (1 !3)-a-glucan, did not induce signi¢cant immune response in shrimp. Here we report that the di¡erence in immunostimulatory potential between AIG and ASG is due to the di¡erence in the percentage of (1 !3)-b-D-glucans present in each preparation, which varies with the method of extraction employed. Also our observations suggest that glucan can be used as a potential immunostimulant to shrimp, provided it contains (1 !3)-b-D-glucan as the major fraction.

Investigations on the cation induced liquid crystalline phases of high molecular weight DNA

Liquid Crystalline DNA is emerging as an active area of research, due to its potential applications in diverse fields, ranging from nanoelectronics to therapeutics. Since, counter ion neutralization is an essential requirement for the expression of LC DNA, and the present level of understanding on the LC phase behavior of high molecular weight DNA is inadequate, a thorough investigation is required to understand the nature and stability of these phases under the influence of various cationic species. The present study is, therefore mainly focused on a comparative investigation of the effect of metal ions of varying charge, size, hydration and binding modes on the LC phase behavior of high molecular weight DNA. The main objectives of the works are investigations on the induction and stabilization of LC phases of high molecular weight DNA by alkali metal ions, investigations on the induction and stabilization of LC phases of high molecular weight DNA by alkaline earth metal ions, effects of multivalent, transition and heavy metal ions on the LC phase behavior of high molecular weight DNA and investigations on spermine induced LC behavior of high molecular weight DNA in the presence of alkali and alkaline earth metal ions. The critical DNA concentration (CD) required for the expression of LC phases, phase transitions and their stability varied considerably when the binding site of the metal ions changed from phosphate groups to the nitrogenous bases of DNA, with Li+ giving the highest stability. Multiple LC phases with different textures, sometimes diffused and unstable or otherwise mainly distinct and clear, were observed on mixing metal ions with DNA solutions, which in turn depended on the charge, size, hydration factor, binding modes, concentration of the metal ions and time. Molecular modeling studies on binding of selected metal ions to DNA supported the experimental findings

Effect of curing temperature , fibre loading and bonding agent on the equilibrium swelling of isora-natural rubbercomposites

Isora fibre-reinforced natural rubber (NR) composites were cured at 80, 100, 120 and 150°C using a low temperature curing accelerator system. Composites were also prepared using a conventional accelerator system and cured at 150°C. The swelling behavior of these composites at varying fibre loadings was studied in toluene and hexane. Results show that the uptake of solvent and volume fraction of rubber due to swelling was lower for the low temperature cured vulcanizates which is an indication of the better fibre/rubber adhesion. The uptake of aromatic solvent was higher than that of aliphatic solvent, for all the composites. As the fibre content increased, the solvent uptake decreased, due to the superior solvent resistance of the fibre and good fibre-rubber interactions. The bonding agent improved the swelling resistance of the composites due to the strong interfacial adhesion. Due to the improved adhesion between the fibre and rubber, the ratio of the change in volume fraction of rubber due to swelling to the volume fraction of rubber in the dry sample (V,) was found to decrease in the presence of bonding agent. At a fixed fibre loading, the alkali treated fibre composite showed a lower percentage swelling than untreated one for both systems showing superior rubber-fibre interactions.

Swelling behaviour of isora/natural rubber composites in oils used in automobiles

Natural rubber/isora fibre composites were cured at various temperatures. The solvent swelling characteristics of natural rubber composites containing both untreated and alkali treated fibres were investigated in aromatic and aliphatic solvents like toluene, and n-hexane. The diffusion experiments were conducted by the sorption gravimetric method. The restrictions on elastomer swelling exerted by isora fibre as well as the anisotropy of swelling of the composite have been confirmed by this study. Composite cured at 100°C shows the lowest percentage swelling. The uptake of aromatic solvent is higher than that of aliphatic solvent for the composites cured at all temperatures. The effect of fibre loading on the swelling behaviour of the composite was also investigated in oils like petrol, diesel, lubricating oil etc. The % swelling index and swelling coefficient of the composite were found to decrease with increase in fibre loading. This is due to the increased hindrance exerted by the fibres at higher fibre loadings and also due to the good fibre-rubber interactions. Maximum uptake of solvent was observed with petrol followed by diesel and then lubricating oil. The presence of bonding agent in the composites restrict the swelling considerably due to the strong interfacial adhesion. At a fixed fibre loading, the alkali treated fibre composite showed lower percentage swelling compared to the untreated one.

Rubber Solution Adhesives for Wood-to-Wood Bonding

Rubber solutions were prepared and used for bonding wood pieces. The effect of the variation of chlorinated natural rubber (CNR) and phenolformaldehyde (PF) resin in the adhesive solutions on lap shear strength was determined. Natural rubber and neoprene-based adhesive solutions were compared for their lap shear strength. The storage stability of the adhesive prepared was determined. The change in lap shear strength before and after being placed in cold water, hot water, acid, and alkali was tested. The bonding character of these adhesives was compared with different commercially available solution adhesives. The room-temperature aging resistance of wood joints was also determined. In all the studies, the adhesive prepared in the laboratory was found to be superior compared to the commercial adhesives.

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.

Anisotropy in elastic properties of lithium sodium sulphate hexahydrate single crystal—An ultrasonic study

The double sulfate family (ABSO4), where A and B are alkali metal cations, is the object of great interest owing to the complexity and richness of its sequence of phase transition induced by temperature variation. A new sulfate salt characterized by the presence of water molecule in the unit cell with the chemical formula, Li2Na3(SO4)2⋅6H2O (LSSW), was obtained. The ultrasonic velocity measurement was done with pulse echo overlap technique [PEO]. All the six second order elastic stiffness constants, C11 = C22, C33, C44 = C55, C12, C14 and C13 = C23 are reported for the first time. The anisotropy in the elastic properties of the crystal are well explained by the pictorial representation of the polar plots of phase velocity, slowness, Young’s modulus and linear compressibility in a–b and a–c planes.

Sorptional Behaviour of Metals on the Sediments and Humic acid of Mangrove Ecosystem

Humic substances are complex polymeric structures.No other polymers with such a wide range of properties are so widely distributed in nature.But still their moleculer structures are unknown. A structural knowledge is essential in determining their reactivity with metals.In the present work structural elucidation of humic acids from three different mangrove ecosystems of Cochin area is done with the available data from functional group analysis and various spectroscopic methods.13C NMR spectra of the solid samples with CPMAS,IR and SEM are very promising in revealing the complex structures of these polymeric substances.Sorptional studies on the sediment and humic acid of mangrove ecosystem reveals that the major portion of the organic matter is not extractable with Sodium hydroxide and humic acid only a small portion of the total organic matter. Humic acid is a good complexing agent and scavenger. Due to the nonextractable nature of the organic matter present with the sediment left after alkali extraction it is a better scavenger.

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.

Consequence modelling,vulnerability assessment and fuzzy fault tree analysis of hazardous storages in an industrial area

The hazards associated with major accident hazard (MAH) industries are fire, explosion and toxic gas releases. Of these, toxic gas release is the worst as it has the potential to cause extensive fatalities. Qualitative and quantitative hazard analyses are essential for the identitication and quantification of the hazards associated with chemical industries. This research work presents the results of a consequence analysis carried out to assess the damage potential of the hazardous material storages in an industrial area of central Kerala, India. A survey carried out in the major accident hazard (MAH) units in the industrial belt revealed that the major hazardous chemicals stored by the various industrial units are ammonia, chlorine, benzene, naphtha, cyclohexane, cyclohexanone and LPG. The damage potential of the above chemicals is assessed using consequence modelling. Modelling of pool fires for naphtha, cyclohexane, cyclohexanone, benzene and ammonia are carried out using TNO model. Vapor cloud explosion (VCE) modelling of LPG, cyclohexane and benzene are carried out using TNT equivalent model. Boiling liquid expanding vapor explosion (BLEVE) modelling of LPG is also carried out. Dispersion modelling of toxic chemicals like chlorine, ammonia and benzene is carried out using the ALOHA air quality model. Threat zones for different hazardous storages are estimated based on the consequence modelling. The distance covered by the threat zone was found to be maximum for chlorine release from a chlor-alkali industry located in the area. The results of consequence modelling are useful for the estimation of individual risk and societal risk in the above industrial area.Vulnerability assessment is carried out using probit functions for toxic, thermal and pressure loads. Individual and societal risks are also estimated at different locations. Mapping of threat zones due to different incident outcome cases from different MAH industries is done with the help of Are GIS.Fault Tree Analysis (FTA) is an established technique for hazard evaluation. This technique has the advantage of being both qualitative and quantitative, if the probabilities and frequencies of the basic events are known. However it is often difficult to estimate precisely the failure probability of the components due to insufficient data or vague characteristics of the basic event. It has been reported that availability of the failure probability data pertaining to local conditions is surprisingly limited in India. This thesis outlines the generation of failure probability values of the basic events that lead to the release of chlorine from the storage and filling facility of a major chlor-alkali industry located in the area using expert elicitation and proven fuzzy logic. Sensitivity analysis has been done to evaluate the percentage contribution of each basic event that could lead to chlorine release. Two dimensional fuzzy fault tree analysis (TDFFTA) has been proposed for balancing the hesitation factor invo1ved in expert elicitation .

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.

Studies on Non-Resonant Multiphoton Processes in Atomic Hydrogen

In the present thesis we have formulated the Dalgarno-Lewis procedure for two-and three-photon processes and an elegant alternate expressions are derived. Starting from a brief review on various multiphoton processes we have discussed the difficulties coming in the perturbative treatment of multiphoton processes. A small discussion on various available methods for studying multiphoton processes are presented in chapter 2. These theoretical treatments mainly concentrate on the evaluation of the higher order matrix elements coming in the perturbation theory. In chapter 3 we have described the use of Dalgarno-Lewis procedure and its implimentation on second order matrix elements. The analytical expressions for twophoton transition amplitude, two-photon ionization cross section, dipole dynamic polarizability and Kramers-Heiseberg are obtained in a unified manner. Fourth chapter is an extension of the implicit summation technique presented in chapter 3. We have clearly mentioned the advantage of our method, especially the analytical continuation of the relevant expressions suited for various values of radiation frequency which is also used for efficient numerical analysis. A possible extension of the work is to study various multiphoton processcs from the stark shifted first excited states of hydrogen atom. We can also extend this procedure for studying multiphoton processes in alkali atoms as well as Rydberg atoms. Also, instead of going for analytical expressions, one can try a complete numerical evaluation of the higher order matrix elements using this procedure.

Short Nylon-6 Fibre/Rubber-Toughened Polystyrene Composites

The thesis describes studies on development of short Nylon-6 fibre composites based on rubber-toughened polystyrene (PS). Toughening was done using natural rubber (NR), styrene-butadiene rubber (SBR) and whole tyre reclaim (WTR). The composites were prepared by melt mixing in an internal mixer at 170 oC. It was found that the optimum blend ratio was 85/15 for PS/NR, 90/10 for PS/SBR and 90/22 for PS/WTR blends. The effect of dynamic vulcanisation on 85/15 PS/NR and 90/10 PS/SBR blends using dicumyl peroxide (DCP) at various concentrations were also studied. The dynamic crosslinking improved the tensile properties, flexural properties, impact strength and dynamic mechanical properties of both the blends. The effect of unmodified and resorcinol formaldehyde latex (RFL)-coated short Nylon-6 fibres on the mechanical properties, morphology and dynamic mechanical properties of 85/15 PS/NR, 90/10 PS/SBR and 90/22 PS/WTR blends were studied. Fibre loading was varied from 0 to 3 wt.%. For 85/15 PS/NR blend, there was a significant enhancement in tensile properties, flexural properties and impact strength with 1 wt.% of both unmodified and RFL-coated fibres. Dynamic mechanical analysis revealed that the storage modulus at room temperature was maximum at 1 wt.% fiber loading for both composites. The surface functionality of the fiber was improved by giving alkali treatment. Maleic anhydride-grafted-polystyrene (MA-g-PS) was prepared and used as a compatibiliser. The effect of MA-g-PS on the composites was investigated with respect to mechanical properties, morphology and dynamic mechanical properties. The compatibiliser loading was varied from 0 to 2 wt.%. The properties were enhanced significantly in the case of treated and untreated fibre composites at a compatibiliser loading of 0.75 wt.%. SEM analysis confirmed better bonding between the fibre and the matrix. Dynamic mechanical studies showed that the storage modulus at room temperature improved for treated fibre composites in the presence of compatibiliser. In the case of 90/10 PS/SBR composites, the addition of short Nylon-6 fibres at 1 wt.% loading improved the tensile modulus, flexural properties and impact strength while the tensile strength was marginally reduced. The surface treated fibers along with compatibiliser at 0.5 wt.% improved the tensile properties, flexural properties and impact strength. DMA reveale that the storage modulus at room temperature was better for composites containing untreated fibre and the compatibiliser. In the case of 90/22 PS/WTR blends, 1 wt.% unmodified fibre and 0.5 wt.% RFL-coated fibres improved tensile modulus, flexural properties and impact strength. Tensile strength was improved marginally. The surface treatment of Nylon fibre and the addition of compatibiliser at 0.5 wt.% enhanced the tensile properties, flexural properties and impact strength. The dynamic mechanical analysis showed that the storage modulus at room temperature was better for untreated fibre composites in conjunction with the compatibiliser. The thermal stability of PS/NR was studied by TGA. Thermal stability of the blends improved with dynamic vulcanisation and with the incorporation of RFL-coated Nylon fibres. The untreated and partially hydrolyzed fibre composites in conjunction with the compatibiliser enhanced the thermal stability. Kinetic studies showed that the degradation of the blends and the composites followed first order kinetics.

Dose/frequency: A critical factor in the administration of glucan as immunostimulant to Indian white shrimp Fenneropenaeus indicus

The immunostimulatory effect of an alkali insoluble glucan extracted from marine yeast isolate Candida sake S165 was tested in Fenneropenaeus indicus. Post larvae (PL) of F. indicus, fed glucan incorporated diet at varying concentrations (0.05, 0.1, 0.2, 0.3, 0.4 g glucan/100 g feed) for 21 days were challenged orally with white spot syndrome virus (WSSV). Maximum survival was observed in PL fed the 0.2% glucan incorporated diet. Subsequently the feed incorporated with 0.2% glucan was fed to F. indicus post larvae at different feeding intervals, i.e. daily, once every two days, once every five days, once every seven days and once every ten days. After 40 days, the prawns were challenged orally with WSSV and post challenge survival was recorded. Shrimp feed containing 0.2% glucan when administered once every seven days gave maximum survival. This was supported by haematological data obtained from adult F. indicus, i.e. total haemocyte count, phenoloxidase activity and nitroblue tetrazolium reduction (NBT). The present observation confirms the importance of dose and frequency of administration of immunostimulants in shrimp health management