Kinetics and mechanism of urea - formaldehyde and related reactions

Urea-formaldehyde resins find numerous applications in adhesive, textile finishing and moulded plastic industries. Kinetic investigations of the reactions of urea and its related compounds with formaldehyde in aqueous acid, alkaline and neutral media have been carried out. A thin—layer chromatographic method was developed for the separation and estimation of the products of these reactions. Using this technique the various initial steps in the reactions were analysed and the rate constants have been determined.

" Studies on Laser induced Phatothermal Phenomena in Selected Organic Compounds and Fullerenes"

In the pre—laser era it was difficult to believe that the optical properties of a medium depend upon the intensity of the radiation incident on it. The basis for this conclusion is that the electric field strength associated with the conventional light sources used before the advent of lasers was much smaller than (103 V/cm) the field sttrengths of atomic or interatomic fields (2 107 —- 10” V/cm). The radiation with such low intensity is not able to affect atomic fields to the extent of changing optical parameters. The invention of laser in 1960 was a turning point. The high degree of coherence of the laser radiation provides high spatial concentration of optical power. With the availability of the femtosecond lasers it has become possible to get extremely high peak powers 2 1013 W/cmz). At such high fields, the relationship between electric ‘polarization P and the electric field strength E ceases to be linear and several nonlinear effects begin to occur. Nonlinear absorption, a branch of nonlinear optics, refers to the interaction between radiation and matter accompanied by absorption of more than one photon. Nonlinear absorption has acquired great importance after the invention of high power lasers. One of the objectives of the present work is to investigate the nonlinear absorption processes occurring in fullerene, selected organic solvents and laser dyes. Fullerenes and laser dyes were chosen because of their highly nonlinear behaviour. Fullerenes, the most beautiful among molecules, offer fascinating field of research owinglto their significant structural properties. As toluene, benzene and carbon disulphide are themost widely used solvents for fullerenes, it seems important to study the nonlinear properties of these liquids as well. Like fullerenes, laser dyes also possess highly delocalized 7r electrons which are responsible for their nonlinear absorption. Dye lasers were the fulfillment of an experimenter’s pipe dream - to have a laser that is easily tunable over a wide range of wavelengths. A better understandingof the photophysical properties of laser dyes can significantly enhance the development and technology of dye lasers. We studied the nonlinear absorption properties of two rhodamine dyes to have some insight into their nonlinear optical properties.

“Studies on short polyester fiber - polyurethane elastomer composite with different interfacial bonding agents”

The work presented in this thesis is regarding the development and evaluation of new bonding agents for short polyester fiber - polyurethane elastomer composites. The conventional bonding system based on hexamethylenetetramine, resorcinol and hydrated silica was not effective as a bonding agent for the composite, as the water eliminated during the formation of the RF resin hydrolysed the urethane linkages. Four bonding agents based on MDI/'I‘DI and polypropyleneglycol, propyleneglycol and glycerol were prepared and the composite recipe was optimised with respect to the cure characteristics and mechanical properties. The flow properties, stress relaxation pattern and the thermal degradation characteristics of the composites containing different bonding agents were then studied in detail to evaluate the new bonding systems. The optimum loading of resin was 5 phr and the ratio of the -01 to isocyanate was 1:1. The cure characteristics showed that the optimum combination of cure rate and processability was given by the composite with the resin based on polypropyleneglycol/ glycerol/ 4,4’diphenylmethanediisocynate (PPG/GL/MDI). From the rheological studies of the composites with and without bonding agents it was observed that all the composites showed pseudoplastic nature and the activation energy of flow of the composite was not altered by the presence of bonding agents. Mechanical properties such as tensile strength, modulus, tear resistance and abrasion resistance were improved in the presence of bonding agents and the effect was more pronounced in the case of abrasion resistance. The composites based on MDI/GL showed better initial properties while composites with resins based on MDI/PPG showed better aging resistance. Stress relaxation showed a multistage relaxation behaviour for the composite. Within the-strain levels studied, the initial rate of relaxation was higher and the cross over time was lesser for the composite containing bonding agents. The bonding agent based on MDI/PPG/GL was found to be a better choice for improving stress relaxation characteristics with better interfacial bonding. Thennogravimetirc analysis showed that the presence of fiber and bonding agents improved the thennal stability of the polyurethane elastomer marginally and it was maximum in the case of MDI / GL based bonding agents. The kinetics of degradation was not altered by the presence of bonding agents

Template-Assisted Synthesis and Characterization of Passivated Nickel Nanoparticles

Potential applications of nickel nanoparticles demand the synthesis of self-protected nickel nanoparticles by different synthesis techniques. A novel and simple technique for the synthesis of self-protected nickel nanoparticles is realized by the inter-matrix synthesis of nickel nanoparticles by cation exchange reduction in two types of resins. Two different polymer templates namely strongly acidic cation exchange resins and weakly acidic cation exchange resins provided with cation exchange sites which can anchor metal cations by the ion exchange process are used. The nickel ions which are held at the cation exchange sites by ion fixation can be subsequently reduced to metal nanoparticles by using sodium borohydride as the reducing agent. The composites are cycled repeating the loading reduction cycle involved in the synthesis procedure. X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron microscopy, Energy Dispersive Spectrum, and Inductively Coupled Plasma Analysis are effectively utilized to investigate the different structural characteristics of the nanocomposites. The hysteresis loop parameters namely saturation magnetization and coercivity are measured using Vibrating Sample Magnetometer. The thermomagnetization study is also conducted to evaluate the Curie temperature values of the composites. The effect of cycling on the structural and magnetic characteristics of the two composites are dealt in detail. A comparison between the different characteristics of the two nanocomposites is also provided

Design and Development of a Remotely Operated Underwater Multi-Robot Manipulator Controller

For the scientific and commercial utilization of Ocean resources, the role of intelligent underwater robotic systems are of great importance. Scientific activities like Marine Bio-technology, Hydrographic mapping, and commercial applications like Marine mining, Ocean energy, fishing, aquaculture, cable laying and pipe lining are a few utilization of ocean resources. As most of the deep undersea exploration are beyond the reachability of divers and also as the use of operator controlled and teleoperated Remotely Operated Vehicles (ROVs) and Diver Transport Vehicles (DTVs) turn out to be highly inefficient, it is essential to have a fully automated system capable providing stable control and communication links for the unstructured undersea environment.

Epoxy-modiWed, unsaturated polyester hybrid networks

Hybrid polymer networks (HPNs) based on unsaturated polyester resin (UPR) and epoxy resins were synthesized by reactive blending. The epoxy resins used were epoxidised phenolic novolac (EPN), epoxidised cresol novolac (ECN) and diglycidyl ether of bisphenol A (DGEBA). Epoxy novolacs were prepared by glycidylation of the novolacs using epichlorohydrin. The physical, mechanical, and thermal properties of the cured blends were compared with those of the control resin. Epoxy resins show good miscibility and compatibility with the UPR resin on blending and the co-cured resin showed substantial improvement in the toughness and impact resistance. Considerable enhancement of tensile strength and toughness are noticed at very low loading of EPN. Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and diVerential scanning calorimetry (DSC) were employed to study the thermal properties of the toughened resin. The EPN/ UPR blends showed substantial improvement in thermal stability as evident from TGA and damping data. The fracture behaviour was corroborated by scanning electron microscopy (SEM). The performance of EPN is found to be superior to other epoxy resins

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

Epoxidized Phenolic Novolac: A Novel Modifier for Unsaturated Polyester Resin

Unsaturated polyester resins (UPRs) are used widely in the fiber-reinforced plastics (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, hybrid polymer networks (HPNs) based on UPR and epoxidized phenolic novolacs (EPNs) were prepared by reactive blending. A HPN is composed of a backbone polymer containing two types of reactive groups that can take part in crosslinking reactions via different mechanisms. EPNs were prepared by glycidylation of novolacs using epichlorohydrin. The novolacs had varying phenol: formaldehyde ratios. Blends of unsaturated polyester with EPN were then prepared. The physical properties of the cured blends were compared with those of the control resin. EPN shows good miscibility and compatibility with the resin and improves the toughness and impact resistance substantially. Considerable enhancement of tensile strength is also noticed at about 5% by weight of epoxidized novolac resin. TGA, DMA, and DSC were used to study the thermal properties of the toughened resin and the fracture behavior was studied using SEM. The blends are also found to have better thermal stability. Blending with EPN can be a useful and cost-effective technique for modification of UPR