Studies on short Nylon-6 fiber - elastomer composites with epoxy resin as bonding agent

The thesis describes the development and evaluation of epoxy resin as interfacial bonding agent for short Nylon-6 fiber elastomer composites. Epoxy resin is well known for its adhesive property. The potential use of it as interfacial bonding agent in short fiber composite is not explored yet. Three rubbers viz., acrylonitrile butadiene rubber (NBR), Neoprene rubber (CR) and styrene butadiene rubber (SBR) were selected and different fiber loading were tried. The resin concentration was optimized for each fiber loading with respect to cure characteristics and mechanical properties. Rheological characteristics and thermal degradation of the composites containing different fiber loading and different resin concentrations were studied in detail to find the effect of epoxy resin bonding system. The mechanical properties were studied in detail. The short Nylon -6 fiber improved most of the mechanical properties of all the three rubbers. Tensile strength showed a dip at 10 phr fiber loading in the case of CR while it was continuously increased with fiber loading in the case of NBR and SBR. All the composites showed anisotropy in mechanical properties. The epoxy resin is an effective bonding agent for short Nylon -6 fiber reinforced NBR and CR composites. Epoxy resin improved tensile strength, abrasion resistance and modulus of these composites. SEM studies confirmed the improved bonding of fiber and matrix in the presence of epoxy bonding agent. Epoxy resin was not effective as bonding agent in the case of short Nylon fiber- SBR composite. From the rheological studies of the composites with and without bonding agent it was observed that all the composite exhibited pseudoplasticity, which decreased with temperature. At higher shear rates all the mixes showed plug flow. SEM pictures showed that maximum orientation of fibers occured at a shear rate, just before the onset of plug flow. The presence of fiber reduced the temperature sensitivity of the flow at a given shear rate. Die swell was reduced in the presence of fiber. Shear viscosity of the composite was increased in the presence of resin. Die swell was increased in the presence of epoxy resin for composites at all shear rates. The thermal degradation of NBR and SBR composites with and without bonding agent followed single step degradation pattern. Thermal stability of the composites was improved in the presence of bonding agent. The degradation of virgin elastomer and the composites followed first order kinetics.

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.

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.

Studies on Surface Properties and Catalytic Activity of Some Chromites and Related Spinels

The prime intension of the present work was a synthetic investigation of the preparation, surface properties and catalytic activity of some transition metal substituted copper chromite catalysts. Homogeneous co-precipitation method is employed for the preparation of catalysts. Since the knowledge about the structure and composition of the surface is critical in explaining the reactivity and selectivity of a solid catalyst. a systematic investigation of the physico-chemical properties of the prepared systems was carried out. The catalytic activity of these systems has also been measured in several oxidation reactions of industrial as well as environmental relevance. The thesis is dedicated to several aspects of chromite spinels giving emphasis to its preparation, characterization and catalytic performance towards oxidation reactions.

Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

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.

Curing studies of elastomer blends with special reference to NR/ NBR and NR/BR blends

There are a large number of commercial examples and property advantages of immiscible elastomer blends.73 Blends of natural rubber (NR) and polybutadiene (BR) have shown various advantages including heat stability, improved elasticity and abrasion resistance. Ethylene-propylene-diene-rubber (EPDM) blended with styrene-butadiene rubber (SBR) has shown improvements in ozone and chemical resistance with better compression set properties. Blends of EPDM and nitrile rubber (NBR) have been cited as a compromise for obtaining moderate oil and ozone resistance with improved low temperature properties. Neoprene (CR)/BR blends offer improved low temperature properties and abrasion resistance with better processing characteristics etc. However, in many of the commercial two-phase elastomer blends, segregation of the crosslinking agents, carbon black or antioxidants preferentially into one phase can result in failure to attain optimum properties. Soluble and insoluble compounding ingredients are found to be preferentially concentrated in one phase. The balance of optimum curing of both phases therefore presents a difficult problem. It has been the aim of this study to improve the performance of commercially important elastomer blends such as natural rubber (NR)/styrene-butadiene rubber (SBR) and natural rubber/polybutadiene rubber (BR) by industrially viable procedures

Production of latex reclaim and its utilisation in polymer blends

The overall objective of the present study was to develop a novel and economic reclaiming process that does not adversely affect the quality of rubber and to investigate methods of utilising the reclaim. Since waste latex products represent a potential source of high quality rubber hydrocarbon, it was decided to develop a process based on such latex wastes. The study revealed that latex reclaim could replace raw natural rubber upto about 50 per cent of its weight without any serious deterioration in mechanical properties.

Studies On Thermoplastic Elastomers With Special Reference To Triblock Copolymers And Nbr/Pvc Blends

Thermoplastic elastomers are a relatively new class of materials which compete with thermoset rubbers in some areas and thermoplastic materials in other areas. The main thrust of the present investigation is a comparative study’ on commercially .available triblock. styrene thermoplastic elastomers and those derived from blends of acrylonitrile-butadiene rubber and poly(vinyl chloride). The styrene—based thermoplastic elastomers are gaining acceptance as a replacement for both natural and synthetic rubber‘ in many‘ applications. TPEs based on blends of elastomers and plastics ix: the fastest growing segment of the broad class of thermoplastic elastomers. Broad applicability and simple technology of production are the attractive features of this class of TPES. NBR/PVC thermoplastic elastomers were selected for this investigation due to the versatility of PVC, its number one position, low cost. ability to Ina compounded into various flexible and rigid form with good physical and chemical and weathering properties etc., which will be passed over to PVC blends especially NBR/PVC blends which are known to form miscible systems

High Styrene–Rubber Ionomers, an Alternative to Thermoplastic Elastomers

High styrene rubber ionomers were prepared by sulfonating styrene–butadiene rubber of high styrene content (high styrene rubber) in 1,2-dichloroethane using acetyl sulfate reagent, followed by neutralization of the precursor acids using methanolic zinc acetate. The ionomers were characterized using X-ray fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), dynamic mechanical analysis (DMA), and also by the evaluation of mechanical properties. The FTIR studies of the ionomer reveal that the sulfonate groups are attached to the benzene ring. The NMR spectra give credence to this observation. Results of DMA show an ionic transition (Ti) in addition to glass–rubber transition (Tg). Incorporation of ionic groups results in improved mechanical properties as well as retention of properties after three cycles of processing

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

Amidino Thiourea as a Secondary Accelerator in Rubber Vulcanization

Earlier studies5773 in our laboratory showed that when a nucleophile is used along with disulphide or sulphenamide accelerators the vulcanization is accelerated greatly and the reaction mechanism is generally nucleophilic in nature. However it was observed that it also changes with the systems under review. The present study, deals with the use of unsubstituted amidino thiourea i.e. aminoimino methyl thiourea(AMT) V in the vulcanization studies of different elastorners and their blends. One of the aims of this study was to get further proof with regard to the theory of nucleophilic reaction mechanism in such binary systems.Mixes containing thiourea are used as controls. AMT is more nucleophilic than TU and this is clear from the fact that the fonner can condense with isothiocynate even in the absence of alkali while TU cannot". Also the guanidinyl group in AMT can facilitate the polarization of the C=S bond favouring a nucleophilic reaction

Catalysis by Modified Pillared Clays and Porous Clay Heterostructures

In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are  Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method.  Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications.  The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process.  Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process.  Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays.  The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification.  The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers.  Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs.  In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260  Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions.  For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia.  Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction.  SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials  In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis.  In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR.  In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis.  In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS.  Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261  Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties.  Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol.  Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol.  DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method.  DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.

Modificació de fibres de jute per l'elaboració de plàstics reforçats reciclables

El treball que s'ha dut a terme es centra en la recerca d'agents modificants per a fibres cel·lulòsiques capaços de reduir la polaritat de les funcions alcohol de la seva estructura per formació de funcions ester. Les fibres de jute se sotmeten a reacció en un sistema tancat provist d'atmòsfera de nitrogen a fi d'evitar reaccions laterals que no són del nostre interés.L'obtenció dels resultats perseguits està lligat a les condicions experimentals aplicades durant les reaccions. La influència de les diferents variables escollides facilitarà en major o menor grau la reacció entre les molècules d'agent d'acoblament i cel·lulosa vinculades. Una gran part de l'atenció es centrarà en l'estudi de l'etapa de modificació, sobretot en l'efectivitat dels reactius addicionats per la reacció amb els grups hidroxil. Un cop comparats els experiments realitzats tant amb clorur d'oleïl com amb anhídrid metacrílic, es conclou que la majoria de condicions provades permeten assolir valors de modificació prou significatius. L'excepció ve donada quan la temperatura utilitzada és de 20ºC, llavors les mateixes condicions que a una temperatura de 60ºC condueixen cap a resultats poc satisfactoris. La reactivitat per part dels dos agents d'acoblament utilitzats no ha estat la mateixa. Els resultats per condicions experimentals del mateix tipus han conduït cap a valors força diferents. Pel que fa a la determinació dels paràmetres òptims es conclou que les variables amb les que el grau de modificació millora considerablement són: una temperatura de 60ºC, 10% de catalitzador respecte la quantitat de clorur d'oleïl o anhídrid addicionada, relació OH reactiu estequiomètrica 1:1 i 40mL de solvent. Un cop modificada la fibra, se sotmet a reacció amb el monòmer estirè. Es comprova que el grau de polimerització segueix el valor de modificació prèviament obtingut, a menor quantitat de funcions alcohol lliures major interacció amb el monòmer estirè. Les propietats inicials de la fibra no es corresponen amb les obtingudes després del tractament, l'increment de la resistència a l'atac de microorganismes i a l'absorció d'humitat s'explica per una reducció de la presència de funcions alcohol polars i per la capa d'estirè polimeritzat per unió amb els dobles enllaços introduïts amb els agents d'acoblament. Pel que fa referència a les dues tècniques de caracterització més utilitzades, l'anàlisis elemental permet quantificar d'una manera precisa la reacció de la fibra amb els agents d'acoblament i la posterior reacció de la fibra modificada amb el monòmer estirè. La caracterització per espectroscopia d'infraroig permet comprovar qualitativament la reactivitat del clorur d'oleïl i qualitativament-quantitativament la de l'anhídrid metacrílic amb les funcions alcohol de la cel·lulosa present en les fibres de jute. Els pics més característics apareguts seran utilitzats per avaluar la reactivitat de la funció carbonílica del reactiu modificant amb l'estructura cel·lulòsica i del doble enllaç de la cel·lulosa modificada amb la matriu polimèrica.