Modification of Polypropylene/Glass Fiber Composites with Nanosilica

Poly(propylene) (PP) reinforced with short glass fiber was modified with precipitated nanosilica (pnS) by melt mixing. The weight of the glass fiber was varied by keeping the pnS at optimum level. The properties of the composites were studied using universal testing machine, dynamic mechanic analyser (DMA), differential Scanning calorimetry (DSC) and thermo gravimetric analyser (TGA). The amount of the glass fiber required for a particular modulus could be reduced by the addition of nanosilica.

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.

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.

Polypropylene/metal oxide nanocomposites: fiber spinning and evaluation”

PP has been getting much attention over the years because it is a very durable polymer commonly used in aggressive environments including automotive battery casings, fuel containers etc. They are used to make bottles, fibers for clothing, components in cars etc. However, it has some shortcomings such as low dimensional and thermal stability. Materials such as metal oxides with sizes of the order 1–50 nm have received a great deal of attention because of their versatile applications in polymer/ inorganic nanocomposites, optoelectronic devices, biomedical materials, and other areas. They are stable under harsh process conditions and also regarded as safe materials to human beings and animals. In the present investigation, PP is modified by incorporating metal oxide nanoparticles such as ZnO and TiO2 by simple melt mixing method. Melt spinning method was used to prepare PP/metal oxide nanocomposite fibers. Various studies have been carried out on these composites and fibers. In the first part of the study, ZnO nanoparticles were prepared from ZnCl2 and NaOH in presence of chitosan, PVA, ethanol and starch. This is a simple and inexpensive method compared to other methods. Change in morphology and particle size of ZnO were studied. Least particle size was obtained in chitosan medium. The particles were characterized by using XRD, SEM, TEM, TGA and EDAX. Antibacterial properties of ZnO prepared in chitosan medium (NZO) and commercial zinc oxide (CZO) were evaluated using a gram positive and a gram negative bacteria

Utilization of waste expanded polystyrene: Blends with silica-filled natural rubber

Expanded polystyrene (EPS) constitutes a considerable part of thermoplastic waste in the environment in terms of volume. In this study, this waste material has been utilized for blending with silica-reinforced natural rubber (NR). The NR/EPS (35/5) blends were prepared by melt mixing in a Brabender Plasticorder. Since NR and EPS are incompatible and immiscible a method has been devised to improve compatibility. For this, EPS and NR were initially grafted with maleic anhydride (MA) using dicumyl peroxide (DCP) to give a graft copolymer. Grafting was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy. This grafted blend was subsequently blended with more of NR during mill compounding. Morphological studies using Scanning Electron Microscopy (SEM) showed better dispersion of EPS in the compatibilized blend compared to the noncompatibilized blend. By this technique, the tensile strength, elongation at break, modulus, tear strength, compression set and hardness of the blend were found to be either at par with or better than that of virgin silica filled NR compound. It is also noted that the thermal properties of the blends are equivalent with that of virgin NR. The study establishes the potential of this method for utilising waste EPS

Short Nylon Fibre Reinforced PP: Melt Rheology

Short fiber reinforced thermoplastics have generated much interest these days since fibrous materials tend to increase both mechanical and thermal properties, such as tensile strength, flexural strength, flexural modulus, heat deflection temperature, creep resistance, and some times impact strength of thermoplastics. If the matrix and reinforcement are both based on polymers the composite are recyclable. The rheological behavior of recyclable composites based on nylon fiber reinforced polypropylene (PP) is reported in this paper. The rheological behavior was evaluated both using a capillary rheometer and a torque rheometer. The study showed that the composite became pseudoplastic with fiber content and hence fiber addition did not affect processing adversely at higher shear rates. The torque rheometer data resembled that obtained from the capillary rheometer. The energy of mixing and activation energy of mixing also did not show much variation from that of PP alone.

Carbon Nanotubes-Reinforced PET Nanocomposite by Melt-Compounding

Poly(ethylene terephthalate) (PET) nanocomposites with single-walled carbon nanotubes (SWNTs) have been prepared by a simple melt compounding method. With increasing concentration (0-3 wt %) of SWNTs, the mechanical and dynamic mechanical properties improved, corresponding to effective reinforcement. Melt rheological characterization indicated the effective entanglements provided by SWNTs in the melt state as well. Thermogravimetric analysis suggested no influence of SWNTs on the thermal stability of PET. Electrical conductivity measurements on the composite films pointed out that the melt compounded SWNTs can result in electrical percolation albeit at concentrations exceeding 2 wt %.

Z-scan and Degenerate Four Wave Mixing Studies in Certain Photonic Materials

International School of Photonics, Cochin University of Science & Technology

Modification of Polyethylenes by Reactive Extrusion

The main aim of the study was to optimise the reactive extrusion conditions in the conventional modification processes of polyethylenes in a single screw extruder.The optimum conditions for peroxide crosslinking of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blend were determined in a torque rheometer. The actual reactive extrusion was performed in a laboratory single screw extruder using the optimum parameters. The influence of the coagent, triaUyl cyanurate (TAC), on the cross linking of low density polyethylene in the presence of peroxide was also investigated. The peroxide crosslinking was found to improve the mechanical properties and the thermal stability of the polyethylenes. The efficiency of crosslinking was found to be improved by the addition of coagent such as TAC.The optimum conditions for silane grafting viz temperature, shear rate, silane and DCP concentrations were determined on a torque rheometer in the case of LDPE, LLDPE and their blend. Silane grafting of LDPE in the presence of peroxide was performed with and without addition of water. Compounding of such mixtures in the melt at high temperatures caused decomposition of the peroxide and grafting of alkoxy silyl groups to the polyethylene chains.The optimum parameters for maleic anhydride modification of LDPE, LLDPE and their blend were determined. The grafting reaction was confinned by FTIR spectroscopy. Modification of polyethylenes with maleic anhydride in the presence of dicumyl peroxide was found to be useful in improving mechanical properties. The improvement was found to be mainly due to the grafting of carboxyl group and formation of crosslinks between the chains. The cross linking initiated improvements indicate extended property profiles and new application fields for polyethylenes.On the whole the study shows that the optimum conditions for modifying polyethylenes can be determined on a torque rheometer and actual modification can be performed in a single screw extruder by employing the optimum parameters for improved mechanical! thermal behaviour without seriously affecting their processing behaviour.

Degenerate four wave mixing in some metal phthalocyanines and naphthalocyanines

Here we report measurements of third-order susceptibility χ(3), figure of merit F defined as χ(3)/α (where α is the absorption coefficient) and second hyperpolarizability 〈γ〉 of some metal substituted phthalocyanines and a naphthalocyanine in solutions of dimethyl formamide using degenerate four wave mixing at 532 nm under nanosecond excitation. It was found that among samples investigated, bis-naphthalocyanine possessed the highest value of 〈γ〉 followed by the bis-phthalocyanine. This observation is explained on the basis that bis-naphthalocyanine followed by bis-phthalocyanine has higher degree of π electron conjugation.

Third order nonlinear optical studies in europium naphthalocyanine using degenerate four wave mixing and Z-scan

Third order nonlinear susceptibility χ(3) and second hyperpolarizability (γ) of a bis-naphthalocyanine viz. europium naphthalocyanines, Eu(Nc)2, were measured in dimethyl formamide solution using degenerate four wave mixing at 532 nm under nanosecond pulse excitation. Effective nonlinear absorption coefficient, βeff and imaginary part of nonlinear susceptibility, Im(χ(3)) were obtained using open aperture /Z-scan technique at the same wavelength. Optical limiting property of the sample was also investigated. The role of excited state absorption in deciding the nonlinear properties of this material is discussed.

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.

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Characteristics of Arabian Sea mini warm pool and Indian summer monsoon

Arabian Sea Mini Warm Pool (ASMWP) is a part of the Indian Ocean Warm Pool and formed in the eastern Arabian Sea prior to the onset of the summer monsoon season. This warm pool attained its maximum intensity during the pre-monsoon season and dissipated with the commencement of summer monsoon. The main focus of the present work was on the triggering of the dissipation of this warm pool and its relation to the onset of summer monsoon over Kerala. This phenomenon was studied utilizing NCEP/NCAR (National Center for Environmental Prediction/National Center for Atmospheric and Research) re-analysis data, TRMM Micro wave Imager (TMI) and observational data. To define the ASMWP, sea surface temperature exceeding 30.25 C was taken as the criteria. The warm pool attained its maximum dimension and intensity nearly 2 weeks prior to the onset of summer monsoon over Kerala. Interestingly, the warm pool started its dissipation immediately after attaining its maximum core temperature. This information can be included in the present numerical models to enhance the prediction capability. It was also found that the extent and intensity of the ASMWP varied depending on the type of monsoon i.e., excess, normal, and deficient monsoon. Maximum core temperature and wide coverage of the warm pool observed during the excess monsoon years compared to normal and deficient monsoon years. The study also revealed a strong relationship between the salinity in the eastern Arabian Sea and the nature of the monsoon

Effect of Feeding Rate in Polymer Extrusion ”

Starve feeding of single screw extruder was described as an important means of improving the performance characteristics of the extruder. In addition to such improvement with versatility, the starve feeding technique also may affect the mechanical properties of the extrudate since the heat transfer an(l mixing characteristics in the starve fed and Hood fed extruders are not the same. Since the material is more loosely packed in the channels of the starve fed extruder, there may be greater bed mobility and uniformity. Further, the. thermal an(l shear induced degradation are also less since possibilities of developing local high temperatures are less compared to a densely compacted extruder bed. This study has been undertaken mainly to explore the effect of feeding rate on the mechanical properties of rubber and plastic extrudates since the effect of feeding rate has not been analysed from this angle so far.