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.

Studies all transport and magnetic properties of nano particle doped MgB2 superconductor for technological applications

This thesis Entitled Studies on transport and magnetic properties of nano particle doped mgb2 superconductor for technological applications.The thesis ahead focuses on the establishment of enhanced superconducting properties in bulk MgB2 via nano particle doping and its conversion into mono/multifilamentary wires. Further, an attempt has also been made to develop prototypes of MgB2 coil and conduction cooled current lead for technological applications. The thesis is configured into 6 chapters. The opening chapter gives an idea on the phenomenon of superconductivity, the various types of superconductors and its applications in different fields. The second chapter is an introduction on MgB2 superconductor and its relevance which includes crystal and electronic structure, superconducting mechanism, basic superconducting properties along with its present international status. The third chapter provides details on the preparation and characterization techniques followed through out the study on MgB2. Fourth chapter discusses the effect of processing temperature and chemical doping using nano sized dopants on the superconducting properties of MgB2• Fifth chapter deals with the optimization of processing parameters and novel preparation techniques for wire fabrication. Sixth chapter furnishes the preparation of multifilamentary wires with various filament configurations, their electromechanical properties and it also incorporates the development of an MgB2 coil and a general purpose conduction cooled current lead.

On the Growth Mechanism of Nickel and Cobalt Nanowires and Comparison of Their Magnetic Properties

Magnetic nanowires (NWs) are ideal materials for the fabrication of various multifunctional nanostructures which can be manipulated by an external magnetic fi eld. Highly crystalline and textured nanowires of nickel (Ni NWs) and cobalt (Co NWs) with high aspect ratio (~330) and high coercivity have been synthesized by electrodeposition using nickel sulphate hexahydrate (NiSO4·6H2O) and cobalt sulphate heptahydrate (CoSO4·7H2O) respectively on nanoporous alumina membranes. They exhibit a preferential growth along〈110〉. A general mobility assisted growth mechanism for the formation of Ni and Co NWs is proposed. The role of the hydration layer on the resulting one-dimensional geometry in the case of potentiostatic electrodeposition is verified. A very high interwire interaction resulting from magnetostatic dipolar interactions between the nanowires is observed. An unusual low-temperature magnetisation switching for fi eld parallel to the wire axis is evident from the peculiar high fi eld M(T) curve

Large enhanced dielectric permittivity in polyaniline passivated core-shell nano magnetic iron oxide by plasma polymerization

Commercial samples of Magnetite with size ranging from 25–30nm were coated with polyaniline by using radio frequency plasma polymerization to achieve a core shell structure of magnetic nanoparticle (core)–Polyaniline (shell). High resolution transmission electron microscopy images confirm the core shell architecture of polyaniline coated iron oxide. The dielectric properties of the material were studied before and after plasma treatment. The polymer coated magnetite particles exhibited a large dielectric permittivity with respect to uncoated samples. The dielectric behavior was modeled using a Maxwell–Wagner capacitor model. A plausible mechanism for the enhancement of dielectric permittivity is proposed

Structural, topographical and magnetic evolution of RF-sputtered Fe-Ni alloy based thin films with thermal annealing

Metglas 2826 MB having a nominal composition of Fe40Ni38Mo4B18 is an excellent soft magnetic material and finds application in sensors and memory heads. However, the thin-film forms of Fe40Ni38Mo4B18 are seldom studied, although they are important in micro-electro-mechanical systems/nano-electromechanical systems devices. The stoichiometry of the film plays a vital role in determining the structural and magnetic properties of Fe40Ni38Mo4B18 thin films: retaining the composition in thin films is a challenge. Thin films of 52 nm thickness were fabricated by RF sputtering technique on silicon substrate from a target of nominal composition of Fe40Ni38Mo4B18. The films were annealed at temperatures of 400 °C and 600 °C. The micro-structural studies of films using glancing x-ray diffractometer (GXRD) and transmission electron microscope (TEM) revealed that pristine films are crystalline with (FeNiMo)23B6 phase. Atomic force microscope (AFM) images were subjected to power spectral density analysis to understand the probable surface evolution mechanism during sputtering and annealing. X-ray photoelectron spectroscopy (XPS) was employed to determine the film composition. The sluggish growth of crystallites with annealing is attributed to the presence of molybdenum in the thin film. The observed changes in magnetic properties were correlated with annealing induced structural, compositional and morphological changes

Magnetic cloud distortion resulting from propagation through a structured solar wind: Models and observations

Numerical simulations of magnetic clouds (MCs) propagating through a structured solar wind suggest that MC-associated magnetic flux ropes are highly distorted by inhomogeneities in the ambient medium. In particular, a solar wind configuration of fast wind from high latitudes and slow wind at low latitudes, common at periods close to solar minimum, should distort the cross section of magnetic clouds into concave-outward structures. This phenomenon has been reported in observations of shock front orientations, but not in the body of magnetic clouds. In this study an analytical magnetic cloud model based upon a kinematically distorted flux rope is modified to simulate propagation through a structured medium. This new model is then used to identify specific time series signatures of the resulting concave-outward flux ropes. In situ observations of three well studied magnetic clouds are examined with comparison to the model, but the expected concave-outward signatures are not present. Indeed, the observations are better described by the convex-outward flux rope model. This may be due to a sharp latitudinal transition from fast to slow wind, resulting in a globally concave-outward flux rope, but with convex-outward signatures on a local scale.

New magnetic nano-absorbent for the determination of n-octanol/water partition coefficients

A novel and generic miniaturization methodology for the determination of partition coefficient values of organic compounds in noctanol/water by using magnetic nanoparticles is, for the first time, described. We have successfully designed, synthesised and characterised new colloidal stable porous silica-encapsulated magnetic nanoparticles of controlled dimensions. These nanoparticles absorbing a tiny amount of n-octanol in their porous silica over-layer are homogeneously dispersed into a bulk aqueous phase (pH 7.40) containing an organic compound prior to magnetic separation. The small size of the particles and the efficient mixing allow a rapid establishment of the partition equilibrium of the organic compound between the solid supported n-octanol nano-droplets and the bulk aqueous phase. UV-vis spectrophotometry is then applied as a quantitative method to determine the concentration of the organic compound in the aqueous phase both before and after partitioning (after magnetic separation). log D values of organic compounds of pharmaceutical interest (0.65-3.50), determined by this novel methodology, were found to be in excellent agreement with the values measured by the shake-flask method in two independent laboratories, which are also consistent with the literature data. It was also found that this new technique gives a number of advantages such as providing an accurate measurement of log D value, a much shorter experimental time and a smaller sample size required. With this approach, the formation of a problematic emulsion, commonly encountered in shake-flask experiments, is eliminated. It is envisaged that this method could be applicable to the high throughput log D screening of drug candidates. (c) 2005 Elsevier B.V. All rights reserved.

Colloidal stable silica encapsulated nano-magnetic composite as a novel bio-catalyst carrier

A colloidal stable silica-encapsulated magnetic nano-composite of a controlled dimension is, for the first time, employed to carry beta-lactamase via chemical linkage on the silica overlayer: activity study reflects that this new type of immobilisation allows site (enzyme) isolation, accessibility as good as free enzyme and recovery & reusability upon application of magnetic separation.

Magnetic spectroscopy and microscopy of functional materials

Heusler intermetallics Mn$_{2}Y$Ga and $X_{2}$MnGa ($X,Y$=Fe, Co, Ni) undergo tetragonal magnetostructural transitions that can result in half metallicity, magnetic shape memory, or the magnetocaloric effect. Understanding the magnetism and magnetic behavior in functional materials is often the most direct route to being able to optimize current materials and design future ones.rnrnSynchrotron soft x-ray magnetic spectromicroscopy techniques are well suited to explore the the competing effects from the magnetization and the lattice parameters in these materials as they provide detailed element-, valence-, and site-specific information on the coupling of crystallographic ordering and electronic structure as well as external parameters like temperature and pressure on the bonding and exchange.rnrnFundamental work preparing the model systems of spintronic, multiferroic, and energy-related compositions is presented for context. The methodology of synchrotron spectroscopy is presented and applied to not only magnetic characterization but also of developing a systematic screening method for future examples of materials exhibiting any of the above effects. rnrnChapters include an introduction to the concepts and materials under consideration (Chapter 1); an overview of sample preparation techniques and results, and the kinds of characterization methods employed (Chapter 2); spectro- and microscopic explorations of $X_2$MnGa/Ge (Chapter 3); spectroscopic investigations of the composition series Mn$_{2}Y$Ga to the logical Mn$_3$Ga endpoint (Chapter 4); and a summary and overview of upcoming work (Chapter 5). Appendices include the results of a “Think Tank” for the Graduate School of Excellence MAINZ (Appendix A) and details of an imaging project now in progress on magnetic reversal and domain wall observation in the classical Heusler material Co$_2$FeSi (Appendix B).

Colloidal Nano-apatite Particles with Active Luminescent and Magentic Properties for Biotechnology Applications

Colloidal Nano-apatite Particles with Active Luminescent and Magentic Properties for Biotechnology Applications. The synthesis of functional nano-materials is a burgeoning field that has produced remarkable and consistent breakthroughs over the last two decades. Individual particles have become smaller and shown potential for well defined functionality. However, there are still unresolved problems, a primary one being the loss of functionality and novelty due to uncontrolled aggregation driven by surface energy considerations. As such the first design criteria to harness the true potential of nanoparticles is to prevent unwanted agglomeration by: (1) improving, and, if possible, (2) controlling aggregation behavior. This requires specific knowledge of the chemistry of the immediate locale of the intended application; especially for biologically relevant applications. The latter criterion is also application driven but should be considered, generally, to diversify the range of functional properties that can be achieved. We have now reason to believe that such a novel system with multifunctional capabilities can be synthesized rather conveniently and have far reaching impact in biotechnology and other applications in the near future. We are presently experimenting with the syntheses of spheroidal, metal-doped, colloidal apatite nano-particles (~10 nm) for several potential biomedical applications.

Advances in femtosecond micromachining and inscription of micro and nano photonic devices

This thesis has focused on three key areas of interest for femtosecond micromachining and inscription. The first area is micromachining where the work has focused on the ability to process highly repeatable, high precision machining with often extremely complex geometrical structures with little or no damage. High aspect ratio features have been demonstrated in transparent materials, metals and ceramics. Etch depth control was demonstrated especially in the work on phase mask fabrication. Practical chemical sensing and microfluidic devices were also fabricated to demonstrate the capability of the techniques developed during this work. The second area is femtosecond inscription. Here, the work has utilised the non-linear absorption mechanisms associated with femtosecond pulse-material interactions to create highly localised refractive index changes in transparent materials to create complex 3D structures. The techniques employed were then utilised in the fabrication of Phase masks and Optical Coherence Tomography (OCT) phantom calibration artefacts both of which show the potential to fill voids in the development of the fields. This especially the case for the OCT phantoms where there exists no previous artefacts of known shape, allowing for the initial specification of parameters associated with the quality of OCT machines that are being taken up across the world in industry and research. Finally the third area of focus was the combination of all of the techniques developed through work in planar samples to create a range of artefacts in optical fibres. The development of techniques and methods for compensating for the geometrical complexities associated with working with the cylindrical samples with varying refractive indices allowed for fundamental inscription parameters to be examined, structures for use as power monitors and polarisers with the optical fibres and finally the combination of femtosecond inscription and ablation techniques to create a magnetic field sensor with an optical fibre coated in Terfenol-D with directional capability. Through the development of understanding, practical techniques and equipment the work presented here demonstrates several novel pieces of research in the field of femtosecond micromachining and inscription that has provided a broad range of related fields with practical devices that were previously unavailable or that would take great cost and time to facilitate.