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.

Pilot Plant Studies On The Utilization Of Industrial Wastes For Industrial Bitumen Manufacture

The main objectives of the investigations reported in the present thesis are the following: (1) to find out some industrial wastes as cheaper additives to augment the air-blowing polymerization process of bitumen. This will bring down the cost of production of industrial bitumen which can be applied for the manufacture of bitumenous paints, roofing and flooring materials etc. (2) to find out suitable promoters for the above additives. This will bring down the consumption of the additives (3) to help in the industrial pollution control (4) to investigate the usefulness of the industrial bitumen produced in the production of bituminous paints (5) to find out thekinetic parameters of the reactions invovled with different additives. This is essential for the design, construction and operation of new industrial bitumen plants using the additives investigated. This will also enable us to establish the mechanism of the reactions involved in the process

”Nonlinear optical properties of polymers containing azomesogens and chiral molecules: theoretical and experimental evaluations."

The present work emphasizes the use of chirality as an efficient tool to synthesize new types of second order nonlinear materials. Second harmonic generation efficiency (SHG) is used as a measure of second order nonlinear response. Nonlinear optical properties of polymers have been studied theoretically and experimentally. Polymers were designed theoretically by ab initio and semiempirical calculations. All the polymeric systems have been synthesized by condensation polymerization. Second harmonic generation efficiency of the synthesized systems has been measured experimentally by Kurtz and Perry powder method

Primary hemocyte culture of Penaeus monodon as an in vitro model for white spot syndrome virus titration, viral and immune related gene expression and cytotoxicity assays

Immortal cell lines have not yet been reported from Penaeus monodon, which delimits the prospects of investigating the associated viral pathogens especially white spot syndrome virus (WSSV). In this context, a method of developing primary hemocyte culture from this crustacean has been standardized by employing modified double strength Leibovitz-15 (L-15) growth medium supplemented with 2% glucose, MEM vitamins (1 ), tryptose phosphate broth (2.95 g l 1), 20% FBS, N-phenylthiourea (0.2 mM), 0.06 lgml 1 chloramphenicol, 100 lgml 1 streptomycin and 100 IU ml 1 penicillin and hemolymph drawn from shrimp grown under a bio-secured recirculating aquaculture system (RAS). In this medium the hemocytes remained viable up to 8 days. 5-Bromo-20-deoxyuridine (BrdU) labeling assay revealed its incorporation in 22 ± 7% of cells at 24 h. Susceptibility of the cells to WSSV was confirmed by immunofluoresence assay using a monoclonal antibody against 28 kDa envelope protein of WSSV. A convenient method for determining virus titer as MTT50/ml was standardized employing the primary hemocyte culture. Expression of viral genes and cellular immune genes were also investigated. The cell culture could be demonstrated for determining toxicity of a management chemical (benzalkonium chloride) by determining its IC50. The primary hemocyte culture could serve as a model for WSSV titration and viral and cellular immune related gene expression and also for investigations on cytotoxicity of aquaculture drugs and chemicals

On the optical and electrical properties of rf and a.c. plasma polymerized aniline thin films

Polyaniline is a widely studied conducting polymer and is a useful material in its bulk and thin film form for many applications, because of its excellent optical and electrical properties. Pristine and iodine doped polyaniline thin films were prepared by a.c. and rf plasma polymerization techniques separately for the comparison of their optical and electrical properties. Doping of iodine was effected in situ. The structural properties of these films were evaluated by FTIR spectroscopy and the optical band gap was estimated from UV-vis-NIR measurements. Comparative studies on the structural, optical and electrical properties of a.c. and rf polymerization are presented here. It has been found that the optical band gap of the polyaniline thin films prepared by rf and a.c. plasma polymerization techniques differ considerably and the band gap is further reduced by in situ doping of iodine. The electrical conductivity measurements on these films show a higher value of electrical conductivity in the case of rf plasma polymerized thin films when compared to the a.c. plasma polymerized films. Also, it is found that the iodine doping enhanced conductivity of the polymer thin films considerably. The results are compared and correlated and have been explained with respect to the different structures adopted under these two preparation techniques

Low k thin films based on rf plasma-polymerized aniline

Thermally stable materials with low dielectric constant (k < 3.9) are being hotly pursued. They are essential as interlayer dielectrics/intermetal dielectrics in integrated circuit technology, which reduces parasitic capacitance and decreases the RC time constant. Most of the currently employed materials are based on silicon. Low k films based on organic polymers are supposed to be a viable alternative as they are easily processable and can be synthesized with simpler techniques. It is known that the employment of ac/rf plasma polymerization yields good quality organic thin films, which are homogenous, pinhole free and thermally stable. These polymer thin films are potential candidates for fabricating Schottky devices, storage batteries, LEDs, sensors, super capacitors and for EMI shielding. Recently, great efforts have been made in finding alternative methods to prepare low dielectric constant thin films in place of silicon-based materials. Polyaniline thin films were prepared by employing an rf plasma polymerization technique. Capacitance, dielectric loss, dielectric constant and ac conductivity were evaluated in the frequency range 100 Hz– 1 MHz. Capacitance and dielectric loss decrease with increase of frequency and increase with increase of temperature. This type of behaviour was found to be in good agreement with an existing model. The ac conductivity was calculated from the observed dielectric constant and is explained based on the Austin–Mott model for hopping conduction. These films exhibit low dielectric constant values, which are stable over a wide range of frequencies and are probable candidates for low k applications.

Conduction mechanism in plasma polymerized aniline thin films

Electrical properties of ac plasma polymerized aniline thin films are investigated with a view of determining the dominant conduction mechanism. The current–voltage (I–V) characteristics in symmetric and asymmetric electrode configuration for polyaniline thin films in the thickness range from 1300 to 2000 A ° are investigated. From the studies on asymmetric electrode configuration, it is found that the dominant conduction mechanism in these films is of Schottky type

Evidence for intergranular tunnelling in polyaniline passivated α-Fe nanoparticles

Nanoparticles are of immense importance both from the fundamental and application points of view. They exhibit quantum size effects which are manifested in their improved magnetic and electric properties. Mechanical attrition by high energy ball milling (HEBM) is a top down process for producing fine particles. However, fineness is associated with high surface area and hence is prone to oxidation which has a detrimental effect on the useful properties of these materials. Passivation of nanoparticles is known to inhibit surface oxidation. At the same time, coating polymer film on inorganic materials modifies the surface properties drastically. In this work a modified set-up consisting of an RF plasma polymerization technique is employed to coat a thin layer of a polymer film on Fe nanoparticles produced by HEBM. Ball-milled particles having different particle size ranges are coated with polyaniline. Their electrical properties are investigated by measuring the dc conductivity in the temperature range 10–300 K. The low temperature dc conductivity (I–V ) exhibited nonlinearity. This nonlinearity observed is explained on the basis of the critical path model. There is clear-cut evidence for the occurrence of intergranular tunnelling. The results are presented here in this paper

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.

Determination of charge carrier transport in radio frequency plasma polymerized aniline thin films

The carrier transport mechanism of polyaniline (PA) thin films prepared by radio frequency plasma polymerization is described in this paper. The mechanism of electrical conduction and carrier mobility of PA thin films for different temperatures were examined using the aluminium–PA–aluminium (Al–PA–Al) structure. It is found that the mechanism of carrier transport in these thin films is space charge limited conduction. J –V studies on an asymmetric electrode configuration using indium tin oxide (ITO) as the base electrode and Al as the upper electrode (ITO–PA–Al structure) show a diode-like behaviour with a considerable rectification ratio

Fabrication of a quantum well heterostructure based on plasma polymerized aniline and its characterization using STM/STS

Two-dimensional electronic systems play a crucial role in modern electronics and offer a multitude of opportunities to study the fundamental phenomena at low dimensional physics. A quantum well heterostructure based on polyaniline (P) and iodine doped polyaniline (I) thin films were fabricated using radio frequency plasma polymerization on indium tin oxide coated glass plate. Scanning probe microscopy and scanning electron microscopy studies were employed to study the morphology and roughness of the polymer thin films. Local electronic density of states (LDOS) of the P–I–P heterostructures is probed using scanning tunnelling spectroscopy (STS). A step like LDOS is observed in the P–I–P heterostructure and is attributed to the quantum well confinement of electrons in the polymer heterostructure.

Dezincification of Epoxy Coated Brass in Cochin Estuary, India

Inhibited α brasses are largely immune to dezincification in most water, but the effect of tin and arsenic addition to α/β brasses is not so reliable or predictable in controlling the problem. There have been many cases of dezincification in duplex brasses in both fresh water and seawater. There is no reliable method of inhibiting the dezincification of two-phase brass despite there are some protection methods such as inhibitors, electro deposition and electro polymerization. Organic coatings are effectively used for the protection of metals due to their capacity to act as a physical barrier between the metal surface and corrosive environment. Hence, epoxy coating on brass was applied and effect of this against dezincification in Cochin estuarine water over a period of one year was studied and reported in this paper

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

Microwave exfoliated reduced graphene oxide epoxy nanocomposites for high performance applications

Graphene has captured the attention of scientific community due to recently emerging high performance applications. Hence, studying its reinforcing effects on epoxy resin is a significant step. In this study, microwave exfoliated reduced graphene oxide (MERGO) was prepared from natural graphite for subsequent fabrication of epoxy nanocomposites using triethylenetetramine (TETA) as a curing agent via insitu polymerization. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), C13 NMR spectroscopy, X-ray photoelectron spectroscopy (XPS) and ultravioletevisible (UVevis) spectroscopy were employed to confirm the simultaneous reduction and exfoliation of graphene oxide. The reinforcing effect of MERGO on epoxy resin was explored by investigating its static mechanical properties and dynamic mechanical analysis (DMA) at MERGO loadings of 0 to 0.5 phr. The micro-structure of epoxy/MERGO nanocomposites was investigated using scanning electron microscope (SEM), transmission electron microscope (TEM) and XRD techniques. The present work reports an enhancement of 32%, 103% and 85% in tensile, impact and flexural strength respectively of epoxy by the addition of even 0.25 phr MERGO. At this loading elastic and flexural moduli also increased by 10% and 65%, respectively. Single-edge-notch three-point-Bending (SEN-TPB) fracture toughness (KIC) measurements were carried out where a 63% increase was observed by the introduction of 0.25 phr MERGO. The interfacial interactions brought about by graphene also benefited the dynamic mechanical properties to a large extent in the form of a significant enhancement in storage modulus and slightly improved glass transition temperature. Considerable improvements were also detected in dielectric properties. The epoxy nanocomposite also attained an ac conductivity of 10 5 S/m and a remarkable increase in dielectric constant. The simple and cost effective way of graphene synthesis for the fabrication of epoxy/MERGO nanocomposites may be extended to the preparation of other MERGO based polymer nanocomposites. This remarkable class of materials has thrown open enormous opportunities for developing conductive adhesives and in microelectronics

Immobilization of Diastase α-amylase on to synthetic and natural polymers

Several natural and synthetic supports have been assessed for their efficiency for enzyme immobilization. Synthetic polymer materials are prepared by chemical polymerization using various monomers. As a kind of important carrier, synthetic polymer materials exhibit the advantages of good mechanical rigidity, high specific surface area, inertness to microbial attack, easy to change their surface characteristics, and their potential for bringing specific functional group according to actual needs. Hence, they have been widely investigated and used for enzyme immobilization. When it comes to the natural polymer materials, much attention has been paid to cellulose and other natural polymer materials owing to their wide range of sources, easy modification, nontoxic, and pollution-free, with a possibility of introducing wide variety of functional groups and good biocompatible properties. In this work report the use of synthetic polymer, polypyrrole and its derivatives and natural polymers coconut fiber and sugarcane bagasse as supports for Diastase α- amylase immobilization. An attempt was also made to functionalize both synthetic and natural polymers using Amino-propyl triethoxysilane. Supports and their immobilized forms were characterized via FT-IR, TG, SEM, XRD, BET and EDS techniques. Immobilization parameters were also optimized so as to prepare stable immobilized biocatalyst for starch hydrolysis.