Synthesis and characterization of novel citric acid-based polyester elastomers

In this paper we report successful simple synthesis of unique elastic polyesters by carrying out catalyst-free polyesterification of multifunctional non-toxic monomers: 1,8-octanediol (OD), citric acid (CA) and sebacic acid (SA). The chemical, physical, and surface chemical properties of the resulting copolyester polyoctanediol citrate/sebacate [p(OCS)] have been investigated. This new material was characterized by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF-MS), nuclear magnetic resonance spectroscopy (NMR), thermal analysis (TA), mechanical tests, photo-acoustic Fourier-transform infrared spectroscopy (PA-FTIR), X-ray photoelectron spectroscopy (XPS) and swelling experiments. We demonstrate that the chemical structure, morphology, physical integrity and surface chemistry of the synthesized co-polymer can be controlled by simply varying the initial acid concentration (CA/SA) in the pre-polymer. This novel p(OCS) polymer exhibits versatility in mechanical properties, hydration and hydrolytic degradation as determined by the chemical structure of the polyester elastomer.     

Asymmetrically loaded annular ring antenna

A numerical model for resonant frequency using asymmetric loading is presented using cavity model. In asymmetric loaded antenna, the posts are not equispaced on annular ring antenna and resonant frequency is independent of the angular location of posts. The posts are located away from the centre of patch. The diameter of post is thin as compared to the diameter of annular ring antenna. The first few dominant modes calculated for asymmetric loading are compared to symmetric loading where the posts are to be located at specific angular locations. The theoretical model is compared to the simulated results of IE3D based on Method of Moments. The numerical model developed can also be verified further by the full wave analysis.     

Stress analysis & life prediction of a cryogenic rocket engine thrust chamber considering low cycle fatigue, creep and thermal ratchetting

The paper deals with stress analysis, cyclic and creep life prediction of a cryogenic rocket engine thrust chamber, being used in one of the satellite launch vehicles of ISRO. The thrust chamber is of double walled construction wherein high conductivity copper alloy is used for the inner wall and stainless steel for the outer. Regenerative cooling of the chamber is achieved by passing the fuel through rectangular coolant passages milled on outer surface of the inner wall. The inner and outer walls are bonded together by brazing at high temperature. Failure of a double walled chamber occurs due to thinning of the inner wall and bulging into the chamber due to three mechanisms viz. (i) low cycle fatigue (ii) thermal ratchetting and (iii) creep. To capture the structural behaviour of the chamber in a complete sequence of operation of the engine, axisymmetric modeling and cyclic stress analysis is carried out using the ANSYS finite element analysis software package. High temperature mechanical properties, low cycle fatigue and creep properties of copper are characterised. Results of creep tests conducted at various temperatures are utilized for evaluating creep constants of Norton secondary creep model available in ANSYS. Analysis is performed in a seven load step sequence simulating one complete hot test of the engine. Life prediction is done using the cumulative damage accumulation methodology, considering the above three damage mechanisms. Allowable number of hot runs permissible is then arrived at after assigning suitable factors of safety for each damage mode.     

Heterogenized copper catalysts for the amination of arylhalide: Synthesis,characterization and catalytic applications

This research investigated the synthesis, characterization and catalytic activity of heterogenized copper complexes for the selective amination of aryl halides. Amination reactions using homogeneous copper catalyst systems are not generally selective and it is also difficult to recover the catalyst from the homogeneous system for recycling. To overcome these difficulties, our efforts were directed towards the development of cheaper heterogeneous catalyst systems, which can be easily recovered and recycled. Heterogenized analogs of the homogenous Cu complexes were prepared using two methods: (a) encapsulation of copper complexes in zeolite-Y and (b) tethering of copper complexes on various supports like zeolite-Y, silica, charcoal, or clay. The encapsulated and tethered copper catalysts on zeolite-Y were characterized using EPR, Diffused reflectance UV–vis, XRD, IAS, ICPES, SEM, and TEM. The results confirmed that the copper complexes were truly heterogenized in zeolite-Y support. Encapsulated and tethered copper complexes were tested for amination of aryl iodide. The effects of various reaction parameters were examined using tethered Cu(Phen)(PPh₃)Br-PTA-Y catalyst to determine optimum conditions. A recycle study of encapsulated and tethered Cu catalyst was carried out to test their robustness for possible commercial exploitation.     

Understanding interfacial polycondensation: Experiments on polyurea system and comparison with theory

Interfacial polycondensation, with its multiphase character and the involvement of several rate and equilibrium processes, presents unique challenges to our ability to understand and design processes for achieving desired properties. In a recent study [1], we have presented a detailed model for the process and shown that it explains the salient features as reported in the literature for several interfacial systems. In the present paper, we report extensive experimental studies on the polyurea system and their comparison with the model. Two geometries - the spherical geometry of the microcapsule and the flat-film geometry - have been used to study qualitative and quantitative features of the polycondensation and the nature of the film that forms. While some aspects, such as the manner in which the solvent influences the kinetics, confirm earlier findings, inadequacies have been identified in the sample preparation protocols followed in earlier work, because of which property estimations may carry a large error. Improved protocols have accordingly been developed and used to study the development of film properties in time and as a function of the important preparation variables. Detailed molecular weight distributions have been determined using a GPC technique and used to derive important properties of the polyurea (such as Mark-Houwink parameters) as well as to gain insights into mechanisms. The data have been used to determine the rate parameters in the Dhumal and Suresh [1] model. The predictions of the model, as far as trends are concerned, are shown to be satisfactory given the level of uncertainty about parameter values and the complexity of the system being studied. Where discrepancies exist, the reasons have been established and the areas for improvement of the model identified. The findings reported are of interest to applications such as controlled release and membrane separations, in which permeation rate through the membrane is of importance and depends upon various membrane properties like crystallinity, morphology, etc.     

Investigation of the Applicability of Ion Exchange Resins as a Sustained Release Drug Delivery System Forpropranolol Hydrochloride

The purpose of this study was to investigate the application of six strongly acidic cation exchange resins as a sustained release drug delivery system. Propranolol hydrochloride was chosen as the model drug to study the in vitro adsorption and desorption characteristics of the resins because of its chemical structure and pharmacokinetie properties which make it a good candidate for a sustained release formulation. The exchange rate constants and diffusion coefficients for the adsorption and desorption experiments were determined for each resin using the equations derived by Boyd, Adamson and Myers. Only one cation exchange resin showed potential as a sustained release drug delivery system for propranolol hydrochloride.     

Thermally-stimulated spontaneous currents from metal-iodine doped polyvinyl pyrrolidone-metal system

A study of the spontaneous response currents from the metal-iodine doped polyvinyl pyrrolidone-metal (MPM) systems, on thermal stimulation at a constant rate, has been made with similar (Al-Al, Ag-Ag and Au-Au) and dissimilar (Al-Cu/Ag/Ni/PbZn) electrode systems. Thermograms of spontaneous current emission of iodine-doped PVP films exhibit two maxima around 90 ± 10°C and 130–160°C in the first heating run, whereas with the second heating run a single peak is found around 140–170°C. The magnitude and direction of current depend on the choice and combination of electrode materials. The position of the current peak in the thermal spectrum shifts with different heating run. A temperature dependence of open-circuit voltage (OCV) is also reported and it was found that OCV varied linearly with the difference in electrode work functions. The active centres of PVP are the carbonyl group of double-bond tertiary nitrogen atom (> N-C=O), and thus the charge transfer complexes are formed with iodine in PVP. The spontaneously-generated current is discussed in terms of weak complex formation with the water molecules and the liberation of different types of charges.