Rubber-Layered Clay Nanocomposites

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

On the Synthesis and Multifunctional Properties of some Nanocrystalline Spinel Ferrites and Magnetic Nanocomposites

This thesis lays importance in the preparation and characterization of a few selected representatives of the ferrite family in the nanoregime. The candidates being manganese zinc ferrite and cobalt ferrite prepared by coprecipitation and sol-gel combustion techniques respectively. The thesis not only stresses importance on the preparation techniques and optimization of the reaction conditions, but emphasizes in investigating the various properties namely structural, magnetic and electrical. Passivated nickel nanocomposites are synthesized using polystyrene beads and adopting a novel route of ion exchange reduction. The structural and magnetic properties of these magnetic nanocomposites are correlated. The magnetocaloric effect (MCE) exhibited by these materials are also investigated with a view to finding out the potential of these materials as magnetic refrigerants. Calculations using numerical methods are employed to evaluate the entropy change on selected samples.

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.

Nonlinear optical characteristics of nanocomposites of ZnO–TiO2–SiO2

In this article we present the nonlinear optical properties of ZnO–TiO2–SiO2 nanocomposites prepared by colloidal chemical synthesis. Nonlinear optical response of these samples is studied using nanosecond laser pulses at an off-resonance wavelength. The nonlinearity of the silica colloid is low and its nonlinear response can be improved by making composites with ZnO and TiO2. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behaviour. The nonlinear refractive index and the nonlinear absorption increases with increasing ZnO volume fraction. The observed nonlinear absorption is explained by two photon absorption followed by weak free carrier absorption and nonlinear scattering. ZnO–TiO2–SiO2 is a potential nanocomposite material for the development of nonlinear optical devices with a relatively small limiting threshold.

Spectral and nonlinear optical characteristics of nanocomposites of ZnO–Ag

In this Letter we present the spectral and nonlinear optical properties of ZnO–Ag nanocomposites prepared by colloidal chemical synthesis. Obvious enhancement of ultraviolet (UV) emission of the samples is observed and the strongest UV emission is over three times than that of pure ZnO. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behaviour which increases with increasing Ag volume fraction. The observed nonlinear absorption is explained through two photon absorption followed by free carrier absorption. ZnO–Ag is a potential nanocomposite material for the UV light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Linear and nonlinear optical characteristics of ZnO-SiO2 nanocomposites.

We present the spectral and nonlinear optical properties of ZnO-SiO2 nanocomposites prepared by colloidal chemical synthesis. Obvious enhancement of ultraviolet (UV) emission of the samples is observed, and the strongest UV emission of a typical ZnO-SiO2 nanocomposite is over three times stronger than that of pure ZnO. The nonlinearity of the silica colloid is low, and its nonlinear response can be improved by making composites with ZnO. These nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior. The observed nonlinear absorption is explained through two photon absorption followed by weak free carrier absorption and nonlinear scattering. The nonlinear refractive index and the nonlinear absorption increase with increasing ZnO volume fraction and can be attributed to the enhancement of exciton oscillator strength. ZnO-SiO2 is a potential nanocomposite material for the UV light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Enhanced luminescence and nonlinear optical properties of nanocomposites of ZnO–Cu

In this article, we present the spectral and nonlinear optical properties of ZnOCu nanocomposites prepared by colloidal chemical synthesis. The emission consisted of two peaks. The 385-nm ultraviolet (UV) peak is attributed to ZnO and the 550-nm visible peak is attributed to Cu nanocolloids. Obvious enhancement of UV and visible emission of the samples is observed and the strongest UV emission of a typical ZnOCu nanocomposite is over three times stronger than that of pure ZnO. Cu acts as a sensitizer and the enhancement of UV emission are caused by excitons formed at the interface between Cu and ZnO. As the volume fraction of Cu increases beyond a particular value, the intensity of the UV peak decreases while the intensity of the visible peak increases, and the strongest visible emission of a typical ZnOCu nanocomposite is over ten times stronger than that of pure Cu. The emission mechanism is discussed. Nonlinear optical response of these samples is studied using nanosecond laser pulses from a tunable laser in the wavelength range of 450650 nm, which includes the surface plasmon absorption (SPA) band. The nonlinear response is wavelength dependent and switching from reverse saturable absorption (RSA) to saturable absorption (SA) has been observed for Cu nanocolloids as the excitation wavelength changes from the low absorption window region to higher absorption regime near the SPA band. However, ZnO colloids and ZnOCu nanocomposites exhibit induced absorption at this wavelength. Such a changeover in the sign of the nonlinearity of ZnOCu nanocomposites, with respect to Cu nanocolloids, is related to the interplay of plasmon band bleach and optical limiting mechanisms. The SA again changes back to RSA when we move over to the infrared region. The ZnOCu nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behavior. The nonlinear refractive index and the nonlinear absorption increases with increasing Cu volume fraction at 532 nm. The observed nonlinear absorption is explained through two-photon absorption followed by weak free-carrier absorption and interband absorption mechanisms. This study is important in identifying the spectral range and composition over which the nonlinear material acts as a RSA-based optical limiter. ZnOCu is a potential nanocomposite material for the light emission and for the development of nonlinear optical devices with a relatively small limiting threshold.

Studies on the fracture behaviour of polymer blends with special reference to PP/HDPE and PS/HIPS blends

Investigations on the fracture behaviour of polymer blends is the topic of this thesis. The blends selected are PP/HDPE and PS/HIPS. PP/HDPE blend is chosen due to its commercial importance and PS/HIPS blend is selected to study the transition from brittle fracture to ductile fracture.PP/HDPE blends were prepared at different compositions by melt blending at 180°C and fracture failure process was investigated by conducting notch sensitivity test and tensile test at different strain rates. The effects of two types of modifiers (particulate and elastomer) on the fracture behaviour and notch sensitivity of PP/HDPE blends were studied. The modifiers used are calcium carbonate, a hard particulate filler commonly used in plastics and Ethylene Propylene Diene Monomer (EPDM). They were added in 2%, 4% and 6% by weight of the blends.The study shows that the mechanical properties of PP/HDPE blends can be optimized by selecting proper blend compositions. The selected modifiers are found to alter and improve the fracture behaviour and notch sensitivity of the blends. Particulate fillers like calcium carbonate can be used for making the mechanical behaviour more stable at the various blend compositions. The resistance to notch sensitivity of the blends is found to be marginally lower in the presence of calcium carbonate. The elastomeric modifier EPDM produces a better stability of the mechanical behaviour. A low concentration of EPDM is sufficient to effect such a change. EPDM significantly improves the resistance to notch sensitivity of the blends. The study shows that judicious selection of modifiers can improve the fracture behaviour and notch sensitivity of PP/HDPE blends and help these materials to be used for critical applications.For investigating the transition in fracture behaviour and failure modes, PS/HIPS blends were selected. The blends were prepared by melt mixing followed by injection moulding to prepare the specimens for conducting tensile, impact and flexure tests. These tests were used to simulate the various conditions which promote failure.The tensile behaviour of unnotched and notched PS/HIPS blend samples were evaluated at slow speeds. Tensile strengths and moduli were found to increase at the higher testing speed for all the blend combinations whereas maximum strain at break was found to decrease. For a particular speed of testing, the tensile strength and modulus show only a very slight decrease as HIPS content is increased up to about 40%. However, there is a drastic decrease on increasing the HIPS content thereafter.The maximum strain at break shows only a very slight change up to about 40% HIPS content and thereafter shows a remarkable increase. The notched specimens also follow a comparable trend even though the notch sensitivity is seen high for PS rich blends containing up to 40% HIPS. The notch sensitivity marginally decreases with increase in HIPS content. At the same time, it is found to increase with the increase in strain rate. It is observed that blends containing more than 40% HIPS fail in ductile mode.The impact characteristics of PSIHIPS blends studied were impact strength, the energy absorbed by the test specimen and impact toughness. Remarkable increase in impact strength is observed as HIPS content in the blend exceeds 40%. The energy absorbed by the test specimens and the impact toughness also show a comparable trend.Flexural testing which helps to characterize the load bearing capacity was conducted on PS/HIPS blend samples at the two different testing speeds of 5mmlmin and 10 mm/min. The flexural strength increases with increase in testing speed for all the blend compositions. At both the speeds, remarkable reduction in flexural strength is observed as HIPS content in the blend exceeds 40%. The flexural strain and flexural energy absorbed by the specimens are found to increase with increase in HIPS content. At both the testing speeds, brittle fracture is observed for PS rich blends whereas HIPS rich blends show ductile mode of failure.Photoelastic investigations were conducted on PS/HIPS blend samples to analyze their failure modes. A plane polariscope with a broad source of light was utilized for the study. The coloured isochromatic fringes formed indicate the presence of residual stress concentration in the blend samples. The coverage made by the fringes on the test specimens varies with the blend composition and it shows a reducing trend with the increase in HIPS content. This indicates that the presence of residual stress is a contributing factor leading to brittle fracture in PS rich blends and this tendency gradually falls with increase in HIPS content and leads to their ductile mode of failure.

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 Natural Rubber/Clay Nanocomposites: Effect of Maleic Anhydride Grafting of Rubber

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

Structural tuning of Montmorillonite clays by pillaring: Designing of shape selective solid acid catalysts and PANI - Montmorillonite nanocomposites

Green chemistry boots eco-friendly,natural clays as catalysts in the chemical as well as in the pharmaceutical industry.Industry demands thermal stability,mechanical strength etc for the catalyst and there the modification methods becomes important.Pillaring tunes clays as efficient catalytic templates for shape selective organic synthesis.Here pillared clays are used as promising alternatives for the environmentally hazardous homogeneous catalysts in some industrially important Friedel-Crafts alkylation reactions of arenes with lower alchohols and higher olefins.The layer structure is enhanced upon pillaring and allows the nanocomposite formation with polyaniline to develop today’s nanoscale diameter devices.Present work gives an entry of pillared clays to the world of conducting composite nanofibers.

Synthesis of nickel–rubber nanocomposites and evaluation of their dielectric properties

Nanocomposites based on natural rubber and nano-sized nickelwere synthesized by incorporating nickel nanoparticles in a natural rubber matrix for various loadings of the filler. Structural, morphological, magnetic and mechanical properties of the compositeswere evaluated along with a detailed study of dielectric properties. Itwas found that nickel particleswere uniformly distributed in the matrix without agglomeration resulting in a magnetic nanocomposite. The elastic properties showed an improvement with increase in filler content but breaking stress and breaking strain were found to decrease. Dielectric permittivity was found to decrease with increase in frequency, and found to increase with increase in nickel loading. The decrease in permittivity with temperature is attributed to the high volume expansivity of rubber at elevated temperatures. Dielectric loss of blank rubber as well as the composites was found to increase with temperature.

Evidence for blueshift by weak exciton confinement and tuning of bandgap in superparamagnetic nanocomposites

Superparamagnetic nanocomposites based on Y-Fe2O3 and sulphonated polystyrene were synthesised by ion-exchange process and the structural characterisation has been carried out using X-ray diffraction technique. Doping of cobalt in to the Y-Fe2O3 lattice was effected in situ and the doping was varied in the atomic percentage range 1–10. The optical absorption studies show a band gap of 2.84 eV, which is blue shifted by 0.64 eV when compared to the reported values for the bulk samples (2.2 eV). This is explained on the basis of weak quantum confinement. Further size reduction can result in a strong confinement, which can yield transparent magnetic nanocomposites because of further blue shifting. The band gap gets red shifted further with the addition of cobalt in the lattice and this red shift increases with the increase in doping. The observed red shift can be attributed to the strain in the lattice caused by the anisotropy induced by the addition of cobalt. Thus, tuning of bandgap and blue shifting is aided by weak exciton confinement and further red shifting of the bandgap is assisted by cobalt doping.

Spectroscopic and photoluminescence studies on optically transparent magnetic nanocomposites based on sol–gel glass: Fe3O4

Sol–gel glasses with Fe3O4 nanoparticles having particle sizes laying in the range 10–20 nm were encapsulated in the porous network of silica resulting in nanocomposites having both optical and magnetic properties. Spectroscopic and photoluminescence studies indicated that Fe3O4 nanocrystals are embedded in the silica matrix with no strong Si–O–Fe bonding. The composites exhibited a blue luminescence. The optical absorption edge of the composites red shifted with increasing concentration of Fe3O4 in the silica matrix. There is no obvious shift in the position of the luminescence peak with the concentration of Fe3O4 except that the intensity of the peak is decreased. The unique combinations of magnetic and optical properties are appealing for magneto–optical applications.