Cure Characteristics of Short Polyester Fiber-PolyurethaneElastomer Composite with Interfacial Bonding Agents Based on Polymeric 4,4'-Diphenylmethanediisocyanate

Cure characteristics of short polyester fiber-polyurethane composites with respect to different bonding agents (MD resins) based on 4, 4' diphenylmethanediisocyanate (MDI) and various diols like propyleneglycol (PG), polypropyleneglycol (PPG) and glycerol (GL) were studied. Tmax. - Tmin. of composites having MD resin were found to be higher than the composite without MD resin. Minimum torque and Tmax. - Tmin., scorch time and optimum cure time were increased with the increase of MDI equivalence. Optimum ratio of MDI / -of in the resin was found to be within the range of 1-1.5. It was observed from the cure characteristics that for getting better adhesion between short polyester fiber and the polyurethane matrix the best choice of MD resin was one based on MDI and 1:1 equivalent mixture of polypropyleneglycol and glycerol.

Synthesis, characterization, and structure of a new cobalt(II) Schiff-base complex with quinoxaline- 2-carboxalidine-2-amino-5-methylphenol

The mononuclear cobalt(II) complex [CoL2] H2O (where HL is quinoxaline-2-carboxalidine- 2-amino-5-methylphenol) has been prepared and characterized by elemental analysis, conductivity measurement, IR, UV-Vis spectroscopy, TG-DTA, and X-ray structure determination. The crystallographic study shows that cobalt(II) is distorted octahedral with each tridentate NNO Schiff base in a cis arrangement. The crystal exhibits a 2-D polymeric structure parallel to [010] plane, formed by O-H...N and O-H... O intermolecular hydrogen bonds and pye stacking interactions, as a racemic mixture of optical enantiomers. The ligand is a Schiff base derived from quinoxaline-2-carboxaldehyde

A Chloride Ion-Selective Potentiometric Sensor Based on a Polymeric Schiff Base Complex

This paper describes the fabrication of an ion-selective electrode in which a polymeric Schiff base complex of cobalt(II) is used as the ionophore.The main advantage of the electrode is that it is mechanically stable upto 3 months..The electrode shows a linear response in the range of 2.5 × 10-5-0.5 × 10-1 mol dm-3. The response time of the electrode is 30 s.The pH range at which the electrode works is 3.8 to 6.8. The electrode was found to be selective towards chloride ion in the presence of ions like Na+, Ca2+, Mn2+, ,Fe3+, Co2+, Ni2+, Cu2+, Zn2+, CH3COO-, NO3-, SO42- ,Br- and NO2-.

Sorptional Behaviour of Metals on the Sediments and Humic acid of Mangrove Ecosystem

Humic substances are complex polymeric structures.No other polymers with such a wide range of properties are so widely distributed in nature.But still their moleculer structures are unknown. A structural knowledge is essential in determining their reactivity with metals.In the present work structural elucidation of humic acids from three different mangrove ecosystems of Cochin area is done with the available data from functional group analysis and various spectroscopic methods.13C NMR spectra of the solid samples with CPMAS,IR and SEM are very promising in revealing the complex structures of these polymeric substances.Sorptional studies on the sediment and humic acid of mangrove ecosystem reveals that the major portion of the organic matter is not extractable with Sodium hydroxide and humic acid only a small portion of the total organic matter. Humic acid is a good complexing agent and scavenger. Due to the nonextractable nature of the organic matter present with the sediment left after alkali extraction it is a better scavenger.

Studies on Metallocene Polyolefin and Polyvinyl Chloride for Blood and Blood Component Storage Applications

Plasticized poly(vinyl chloride) (pPVC), although a major player in the medical field, is at present facing lot of criticism due to some of its limitations like the leaching out of the toxic plasticizer, di ethylhexyl phthalate (DEHP) to the medium and the emission of an environmental pollutant,dioxin gas,at the time of the post use disposal of PVC Products by incineration. Due to these reasons, efforts are on to reduce the use of pPVC considerably in the medical field and to find viable alternative materials. The present study has been undertaken in this context to find a suitable material for the manufacture of medical aids in place of pPVC. The main focus of this study has been to find out a non-DEHP material as plasticizer for pPVC and another suitable material for the complete repalcement of pPVC for blood/ blood component storage applications.Two approaches have been undertaken for this purpose-(1)the controversial plasticizer, DEHP has been partially replaced by polymeric plasticizers(2) an alternative material, namely, metallocene polyolefin (mPO) has been used and suitably modified to match the properties of flexible PVC used for blood and blood component storage applications.

Photothermal Investigations on Certain Plasma Polymerized Thin Films and Near IR Overtone Studies of Some Organic Molecules

Photothermal effect refers to heating of a sample due to the absorption of electromagnetic radiation. Photothermal (PT) heat generation which is an example of energy conversion has in general three kinds of applications. 1. PT material probing 2. PT material processing and 3. PT material destruction. The temperatures involved increases from 1-. 3. Of the above three, PT material probing is the most important in making significant contribution to the field of science and technology. Photothermal material characterization relies on high sensitivity detection techniques to monitor the effects caused by PT material heating of a sample. Photothermal method is a powerful high sensitivity non-contact tool used for non-destructive thermal characterization of materials. The high sensitivity of the photothermal methods has led to its application for analysis of low absorbance samples. Laser calorimetry, photothermal radiometry, pyroelectric technique, photoacoustic technique, photothermal beam deflection technique, etc. come under the broad class ofphotothermal techniques. However the choice of a suitable technique depends upon the nature of the sample, purpose of measurement, nature of light source used, etc. The present investigations are done on polymer thin films employing photothermal beam deflection technique, for the successful determination of their thermal diffusivity. Here the sample is excited by a He-Ne laser (A = 6328...\ ) which acts as the pump beam. Due to the refractive index gradient established in the sample surface and in the adjacent coupling medium, another optical beam called probe beam (diode laser, A= 6500A ) when passed through this region experiences a deflection and is detected using a position sensitive detector and its output is fed to a lock-in amplifier from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the signal is suitably analysed for determining the thermal diffusivity.The production of polymer thin film samples has gained considerable attention for the past few years. Plasma polymerization is an inexpensive tool for fabricating organic thin films. It refers to formation of polymeric materials under the influence of plasma, which is generated by some kind of electric discharge. Here plasma of the monomer vapour is generated by employing radio frequency (MHz) techniques. Plasma polymerization technique results in homogeneous, highly adhesive, thermally stable, pinhole free, dielectric, highly branched and cross-linked polymer films. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer.Near IR overtone investigations on some organic molecules using local mode model are also done. Higher vibrational overtones often provide spectral simplification and greater resolution of peaks corresponding to nonequivalent X-H bonds where X is typically C, N or O. Vibrational overtone spectroscopy of molecules containing X-H oscillators is now a well established tool for molecular investigations. Conformational and steric differences between bonds and structural inequivalence ofCH bonds (methyl, aryl, acetylenic, etc.) are resolvable in the higher overtone spectra. The local mode model in which the X-H oscillators are considered to be loosely coupled anharmonic oscillators has been widely used for the interpretation of overtone spectra. If we are exciting a single local oscillator from the vibrational ground state to the vibrational state v, then the transition energy of the local mode overtone is given by .:lE a......v = A v + B v2 • A plot of .:lE / v versus v will yield A, the local mode frequency as the intercept and B, the local mode diagonal anharmonicity as the slope. Here A - B gives the mechanical frequency XI of the oscillator and B = X2 is the anharmonicity of the bond. The local mode parameters XI and X2 vary for non-equivalent X-H bonds and are sensitive to the inter and intra molecular environment of the X-H oscillator.

Transition Metal Complexes of Schiff Bases with Azide and Thiocyanate as Coligands:Spectral and Structural Investigations

Metallo-organic chemistry,incorporating the frontiers of both inorganic and organic chemical aspects,is a topic of utility concern.The first exploration of coordinated metal complexes dates back to the ninettenth century,during the days of Alfred Werner.Thereafter,inorganic chemistry witnessed a great outflow of coordination compounds,with unique structural characteristics and diverse applicatons.The diversity in structures exhibited by the coordination complexes of multidentate ligands have led to their usage as sensors,models for enzyme mimetic centers,medicines etc.The liganda chosen are of prime importance in determining the properties of coordination compounds.Schiff bases are compounds obtained by the condensation of an aidehyde or ketone with an amine.The chemical properties of Schiff bases and their complexes are widely explored in recent years owing to their pharmacological activity,their catalytic activities and so on.On the other hand pseudohalides like azide and thiocyanate are versatile candidates for the construction of dimeric or polymeric complexes having excellent properties and diverse applications.So a combination of the Schiff bases and the pseudohalogens for the synthesis of metal complexes can bring about interesting results.An attempt into this area is the besis of this Ph.D theis.

Structural Characterization and Non-linear Optical Properties of Metal Complexes of Some Donor-Acceptor Substituted N-salicylidene-N' -aroylhydrazine Ligands

The present work deals with the complexation of Schiff bases of aroylhydrazines with various transition metal ions. The hydrazone systems selected for study have long 7I:-delocalized chain in the ligand molecule itself, which get intensified due to metal-to-ligand or ligand-to-metal charge transfer excitations upon coordination. Complexation with metal ions like copper, nickel, cobalt, manganese, iron, zinc and cadmium are tried. Various spectral techniques are employed for characterization. The structures of some complexes have been well established by single crystal X-ray diffraction studies. The nonIinaer optical studies of the ligands and complexes synthesized have been studied by hyper-Rayleigh scattering technique.The work is presented in seven chapters and the last one deals with summary and conclusion. One of the hydrazone system selected for study proved that it could give rise to polymeric metal complexes. Some of the copper, nickel, zinc and cadmium complexes showed non-linear optical activity. The NLO studies of manganese and iron showed negative result, may be due to the inversion centre of symmetry within the molecular lattice.

Utilisation of Coir Geotextiles for Unpaved Roads and Embankments

The increasing tempo of construction activity the world over creates heavy pressure on existing land space. The quest for new and competent site often points to the needs for improving existing sites, which are otherwise deemed unsuitable for adopting conventional foundations. This is accomplished by ground improvement methods, which are employed to improve the quality of soil incompetent in their natural state. Among the construction activities, a well-connected road network is one of the basic infrastructure requirements, which play a vital role for the fast and comfortable movement of inter- regional traffic in countries like India.One of the innovative ground improvement techniques practised all over the world is the use of geosynthetics, which include geotextiles, geomembranes, geogrids, etc . They offer the advantages such as space saving, enviromnental sensitivity, material availability, technical superiority, higher cost savings, less construction time, etc . Because of its fundamental properties, such as tensile strength, filtering and water permeability, a geotextile inserted between the base material and sub grade can function as reinforcement, a filter medium, a separation layer and as a drainage medium. Though polymeric geotextiles are used in abundant quantities, the use of natural geotextiles (like coir, jute, etc.) has yet to get momentum. This is primarily due to the lack of research work on natural geotextilcs for ground improvement, particularly in the areas of un paved roads. Coir geotextiles are best suited for low cost applications because of its availability at low prices compared to its synthetic counterparts. The proper utilisation of coir geotextilcs in various applications demands large quantities of the product, which in turn can create a boom in the coir industry. The present study aims at exploring the possibilities of utilising coir geotextiles for unpaved roads and embankments.The properties of coir geotextiles used have been evaluated. The properties studied include mass per unit area, puncture resistance, tensile strength, secant modulus, etc . The interfacial friction between soils and three types of coir geotextiles used was also evaluated. It was found that though the parameters evaluated for coir geotextiles have low values compared to polymeric geotextiles, the former are sufficient for use in unpaved roads and embankments. The frictional characteristics of coir geotextile - soil interfaces are extremely good and satisfy the condition set by the International Geosynthetic Society for varied applications.The performance of coir geotextiles reinforced subgrade was studied by conducting California Bearing Ratio (CBR) tests. Studies were made with coir geotextiles placed at different levels and also in multiple layers. The results have shown that the coir geotextile enhances the subgrade strength. A regression analysis was perfonned and a mathematical model was developed to predict the CBR of the coir geotextile reinforced subgrade soil as a function of the soil properties, coir geotextile properties, and placement depth of reinforcement.The effects of coir geotextiles on bearing capacity were studied by perfonning plate load tests in a test tan1e This helped to understand the functioning of geotextile as reinforcement in unpaved roads and embankments. The perfonnance of different types of coir geotextiles with respect to the placement depth in dry and saturated conditions was studied. The results revealed that the bearing capacity of coir-reinforced soil is increasing irrespective of the type of coir geotextiles and saturation condition.The rut behaviour of unreinforced and coir reinforced unpaved road sections were compared by conducting model static load tests in a test tank and also under repetitive loads in a wheel track test facility. The results showed that coir geotextiles could fulfill the functions as reinforcement and as a separator, both under static and repetitive loads. The rut depth was very much reduced whik placing coir geotextiles in between sub grade and sub base.In order to study the use of Coir geotextiles in improving the settlement characteristics, two types of prefabricated COlf geotextile vertical drains were developed and their time - settlement behaviour were studied. Three different dispositions were tried. It was found that the coir geotextile drains were very effective in reducing consolidation time due to radial drainage. The circular drains in triangular disposition gave maximum beneficial effect.In long run, the degradation of coir geotextile is expected, which results in a soil - fibre matrix. Hence, studies pertaining to strength and compressibility characteristics of soil - coir fibre composites were conducted. Experiments were done using coir fibres having different aspect ratios and in different proportions. The results revealed that the strength of the soil was increased by 150% to 200% when mixed with 2% of fibre having approximately 12mm length, at all compaction conditions. Also, the coefficient of consolidation increased and compression index decreased with the addition of coir fibre.Typical design charts were prepared for the design of coir geotextile reinforced unpaved roads. Some illustrative examples are also given. The results demonstrated that a considerable saving in subase / base thickness can he achieved with the use of eoir geotextiles, which in turn, would save large quantities of natural aggregates.

A study on the Immobilizaton of Enzymes on Polymeric Supports

This work was focused to study the immobilization of enzymes on polymers. A large range of polymer matrices have been employed as supports for enzyme immobilization. Here polyaniline (PAN!) and poly(0~toluidine) (POT) were used as supports. PANI and POT provides an excellent support for enzyme immobilization by virtue of its facile synthesis, superior chemical and physical stabilities, and large retention capacity. We selected industrially important starch hydrolyzing enzymes a-amylase and glucoamylase for the study. In this work the selected enzymes were immobilized via adsorption and covalent bonding methods.To optimize the catalytic efficiency and stability of the resulting biocatalysts, the attempt was made to understand the immobilization effects on enzymatic properties. The effect of pH of the immobilization medium, time of immobilization on the immobilization efficiency was observed. The starch hydrolyzing activity of free 0:-amylase and glucoamylase were compared with immobilized forms. Immobilization on solid supports changes the microenvironment of the enzyme there by influences the pH and temperature relationship on the enzymatic activity. Hence these parameters also optimized. The reusability and storage stability of immobilized enzymes an important aspect from an application standpoint, especially in industrial applications. Taking in to consideration of this, the reusability and the long tenn storage stability of the immobilized enzyme investigated.

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.

Synthesis,characterization and application studies of some polymer supported metal complexes

Polymer supports are efficient reagents,substrates and catalysts and they are extensively used for carrying out reactions at controlled rates.Tailor-made polymer supports are highly versatile which have opened an excellent area of research.Now polymer supported chemistry is being exploited at an amazing rate and it seems to join the routine world of organic synthesis.Polymer supported ligands are found to be efficient complexing agents whose high selectivity enables the analysis and removal of heavy metal ions which are toxic to all the living organisms of land and sea.polymer supported membranes function as ion selective potentiometric sensors which allow the exchange of specific ions among other ions of the same charge.In this investigation three series of polymeric schiff bases and three series of metal complexes have been prepared.An attempt is done to develop optimum conditions for the removal of heavy metal ions using polymeric schiff bases.A novel copper sensor electrode have also been prepared from polymer supported metal complex.

Tridentate Schiff Bases of Some Aroylhydrazides and their Metal Complexes: Spectral and Structural Studies

The present work deals with the complexation of Schiff bases of aroylhydrazides with various transition metal ions. The hydrazone systems selected for study are capable of forming bridged polymeric structures which is one of the fascinating subjects in the crystal engineering of coordination polymers owing to their attractive new topologies and intriguing structural features. Complexation with metal ions like copper, manganese, vanadium, nickel, palladium, zinc and cadmium are tried. Various spectral techniques are employed for characterization. The structures of some complexes have been well established by single crystal X-ray diffraction studies.The work is presented in seven chapters and the last section deals with summary and conclusion. The studies reveal that the aroylhydrazone systems vary in their geometrical configuration depending on the substituents. The coordination modes of the ligands also differ upon chelating with metal ions. One of the hydrazone system selected for study proved that it could give rise to polymeric metal complexes.

Nonlinear Optical Properties of Organic and Polymer Systems

Present thesis has discussed the design and synthesis of polymers suitable for nonlinear optics. Most of the molecules that were studied have shown good nonlinear optical activity. The second order nonlinear optical activity of the polymers was measured experimentally by Kurtz and Perry powder technique. The thesis comprises of eight chapters.The theory of NLO phenomenon and a review about the various nonlinear optical polymers has been discussed in chapter 1. The review has provided a survey of NLO active polymeric materials with a general introduction, which included the principles and the origin of nonlinear optics, and has given emphasis to polymeric materials for nonlinear optics, including guest-host systems, side chain polymers, main chain polymers, crosslinked polymers, chiral polymers etc.Chapter 2 has discussed the stability of the metal incorporated tetrapyrrole molecules, porphyrin, chlorin and bacteriochlorin.Chapter 3 has provided the NLO properties of certain organic molecules by computational tools. The chapter is divided into four parts. The first part has described the nonlinear optical properties of chromophore (D-n-A) and bichromophore (D-n-A-A-n-D) systems, which were separated by methylene spacer, by making use of DPT and semiempirical calculations.Chapter 4: A series of polyurethanes was prepared from cardanol, a renewable resource and a waste of the cashew industry by previously designed bifunctional and multifunctional polymers using quantum theoretical approach.Chapter 5: A series of chiral polyurethanes with main chain bis azo diol groups in the polymer backbone was designed and NLO activity was predicted by ZlNDO/ CV methods.In Chapter 7, polyurethanes were first designed by computational methods and the NLO properties were predicted by correction vector method. The designed bifunctional and multifunctional polyurethanes were synthesized by varying the chiral-achiral diol compositions