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.

Modification of Natural Rubber using Thermoset Resins

This thesis presents the findings of a study on incorporating vanous thermoset resins into natural rubber for property improvement. Natural rubber is an important elastomer with the unique attribute of being a renewable agricultural product. The study was undertaken to investigate the extent to which the drawbacks of natural rubber, especially its poor thermal and oil resistance propel1ies could be nullified by blending with common thermoset resins. A thorough and comparative understanding of the perfonnance of different resins from this viewpoint will be beneficial for both natural IUbber processors and consumers. In this study the thennoset resins used were epoxy resin, phenolics, epoxidised phenolics and unsaturated polyester resin.The resins were incorporated into NR during compounding and their effects on the properties of NR were studied after vulcanization. Properties were studied for both gum and filled N R compounds. The important properties studied are cure characteristics, mechanical properties, ageing propel1ies, thermal propel1ies, crosslink density and extractability. Characterization studies were also conducted using FTIR, TGA and DSC.Improvement in mechanical properties was noticed in many cases. The results show that most resins lead to a reduction in the cure time of NR. The perfonnance of epoxy resin is most noticeable in this respect. Mechanical properties of the modified IUbber show maximum improvement in the case of epoxidised novolacs. Most resins are seen to improve the thermal and oil resistance propel1ies of NR. Epoxy novolacs show maximum effect in this respect also. However the presence of tillers is found to moderate the positive effects of the thermoset resins considerably.

EPDM/CIIR Blends: Compatibility, Morphology and Physical Properties

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

Rubber-Layered Clay Nanocomposites

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

Novel adhesive systems based on neoprene-phenolic blends

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

Compatibilisation of Powdered Nitrile Rubber Toughened Polystyrene

The present study aims at the preparation of an ABS (acrylonitrile-butadiene-styrene) type toughened thermoplastic by melt blending polystyrene (PS) and powdered nitrile rubber (NBR). The product is an interesting class of toughened thermoplastic, which would combine the superior mechanical and processing characteristics of PS and the excellent oil-resistant properties of NBR. In this thesis an attempt has been made to investigate systematically the effect of compatibilisation and dynamic vulcanisation on the morphology and properties of powdered nitrile rubber toughened polystyrene.

Modification of Polypropylene and Polystyrene Using Nanosilica

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

Studies on in situ precipitated silica filled rubber composites with special reference to NR, NBR and SBR

Precipitated silica is the most promising alternative for carbon black in tyre tread compounds due to its improved performance in terms of rolling resistance and wet grip.But its poor processability is a serious limitation to its commercial application.This thesis suggests a novel route for the incorporation of silica in rubbers,i.e.,precipitation of silica in rubber latex followed by coagulation of the latex to get rubber-silica maseterbatch.Composites with in situ precipitated silica showed improved processability and mechanical properties,when compared to conventional silica composites.

Applications of cardanol in rubber processing

This research project explores the utilization of cardanol in various capacities for rubber processing. Cardanol is a phenol with a long side chain in the meta position of the benzene ring. It is obtained by the vacuum distillation of cashew Hut shell liquid (CNSL) which is a cheap agro-byproduct. In this study, the plasticizer property of cardanol was investigated in silica filled and HAF black filled NR, NBR, EPDM and CR by comparing cure characteristics and mechanical properties of vulcanizates containing conventional plasticizer with those containing cardanol as plasticizer. The co-activator, antioxidant and accelerator properties were investigated in gum samples of NR, NBR, EPDM and CR by comparing the properties of vulcanizates which contain conventional co-activator, antioxidant and accelerator with those in which each of them was replaced by cardanol. The general effectiveness of cardanol was investigated by determination of cure time , measurement of physical and mechanical properties, ageing studies, crosslink density, extractability, FTIR spectra, TGA etc.The results show that cardanol can be a substitute for aromatic oil in both silica filled and HAF black filled NR. Again, it can replace dioctyl phthalate in both silica filled and HAF black filled NBR. Similarly, cardanol Can replace naphthenic oil in silica filled as well as HAF black filled EPDM and CR. The cure characteristics and mechanical properties are comparable in all the eight cases. The co-activator property of cardanol is comparable to stearic acid in all the four rubbers. The cure characteristics and mechanical properties in this case are also comparable. The antioxidant ,property of cardanol is comparable to TQ in all the four rubbers. The antioxidant property of cardanol is comparable to TQ in all the four case of NBR and EPDM.The accelerator property of cardarlol is comparable with CBS in the case of NBR and EPDM. No accelerator property is observed in the case of NR. The accelerator property of cardanol in CR is not negligible when compared with TMTD.

NANO - ZINC OXIDE: A Novel Modifier for Thermoplastics

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

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.

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

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

Magnetic, Dielectric and Physicomechanical Properties of Rubber Ferrite Nanocomposites

In the present study the preparation and characterisation of rubber ferrite composites containing nickel ferrite and gamma ferric oxide have been dealt with.Synthetic rubbers viz. ethylene propylene diene rubber and neoprene rubber were used for the incorporation of nickel ferrite and gamma ferric oxide for the synthesis of RFCs. Incorporation of ferrites were carried out according to a specific recipe for various loadings of the magnetic fillers. The ferrites used for the preparation of RFCs were synthesised using sol-gel method and structural characterisation was carried out. Experimental techniques like X-ray diffraction, Transmission electron microscopy and other analytical techniques were used for this. Precharaterised ferrites were then incorporated at different loading into rubber according to conventional mixing methods. The cure characteristics, mechanical, dielectric, magnetic and microwave properties of these composites were evaluated. The effect of carbon black on these properties of RFCs were carried out.

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

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

Isora Fibre Reinforced Polyester and Epoxy Composites

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