Investigations on the preparation of composite polysaccharide films and micro / nanoparticles for novel applications

chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology, CSIR

Diblock and Triblock Copolymers of Styrene and Acetoxymethylstyrene by One-Pot ATRP

We describe the synthesis of diblock and triblock copolymers by sequential atom transfer radical polymerization of styrene and acetoxymethylstyrene. Contrary to the usual block copolymerization involving isolation of the macroinitiator, a convenient one-pot procedure is developed. This is possible because of the preferential polymerization of acetoxymethylstyrene, even in the presence of residual styrene, as inferred from characterization of the intermediate polystyrenes and the block copolymers by size exclusion chromatography, 1H NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and GPEC techniques. The latent acetoxy functionalities in these block copolymers are shown to be easily unmasked to OOH and OBr functionalities, with the potential for block ionomers and dense graft architectures.

Modification of Polypropylene/Glass Fiber Composites with Nanosilica

Poly(propylene) (PP) reinforced with short glass fiber was modified with precipitated nanosilica (pnS) by melt mixing. The weight of the glass fiber was varied by keeping the pnS at optimum level. The properties of the composites were studied using universal testing machine, dynamic mechanic analyser (DMA), differential Scanning calorimetry (DSC) and thermo gravimetric analyser (TGA). The amount of the glass fiber required for a particular modulus could be reduced by the addition of nanosilica.

Compatibility Studies on Sulphur Cured EPDM/CIIR Blends

The principal objective of this study was to explore the compatibility of a blend of two synthetic elastomers viz., ethylene-propylene-diene rubber (EPDM) and chlorobutyl rubber (CIIR). Various commercial grades of EPDM were blended with a specific grade of CIIR at different proportions. The mechanical properties such as tensile strength, tear strength, ageing resistance, etc. were studied. On the basis of the observed physical properties, two particular grades of EPDM were found to be compatible with CIIR. Differential scanning calorimetry and scanning electron microscopy confirmed the results. Chlorosulphonated polyethylene was added as a compatibilizing agent to overcome the phase separation of the other two incompatible grades of EPDM in blending with CIIR. The results revealed that the addition of compatibilizer greatly improves the compatibility and thereby the properties of the blends.

Thermal transport across incommensurate phases in potassium selenate: photo-pyroelectric and calorimetric measurements

The thermal transport properties—thermal diffusivity, thermal conductivity and specific heat capacity—of potassium selenate crystal have been measured through the successive phase transitions, following the photo-pyroelectric thermal wave technique. The variation of thermal conductivity with temperature through the incommensurate (IC) phase of this crystal is measured. The enhancement in thermal conductivity in the IC phase is explained in terms of heat conduction by phase modes, and the maxima in thermal conductivity during transitions is due to enhancement in the phonon mean free path and the corresponding reduction in phonon scattering. The anisotropy in thermal conductivity and its variation with temperature are reported. The variation of the specific heat with temperature through the high temperature structural transition at 745 K is measured, following the differential scanning calorimetric method. By combining the results of photo-pyroelectric thermal wave methods and differential scanning calorimetry, the variation of the specific heat capacity with temperature through all the four phases of K2SeO4 is reported. The results are discussed in terms of phonon mode softening during transitions and phonon scattering by phase modes in the IC phase.

Thermal Properties of Polytetrafluoroethylene/ Sr2Ce2Ti5O16 Polymer/Ceramic Composites

Polytetrafluoroethylene (PTFE) composites filled with Sr2Ce2Ti5O16 ceramic were prepared by a powder processing technique. The structures and microstructures of the composites were investigated by X-ray diffraction and scanning electron microscopy techniques. Differential scanning calorimetry showed that the ceramic filler had no effect on the melting point of the PTFE. The effect of the Sr2Ce2Ti5O16 ceramic content [0–0.6 volume fraction (vf)] on the thermal conductivity, coefficient of thermal expansion (CTE), specific heat capacity, and thermal diffusivity were investigated. As the vf of the Sr2Ce2Ti5O16 ceramic increased, the thermal conductivity of the specimen increased, and the CTE decreased. The thermal conductivity and thermal expansion of the PTFE/Sr2Ce2Ti5O16 composites were improved to 1.7 W m21 8C21 and 34 ppm/8C, respectively for 0.6 vf of the ceramics. The experimental thermal conductivity and CTE were compared with different theoretical models.

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.

Photothermal and photoacoustic investigations on certain polymers and semi conducting materials

Material synthesizing and characterization has been one of the major areas of scientific research for the past few decades. Various techniques have been suggested for the preparation and characterization of thin films and bulk samples according to the industrial and scientific applications. Material characterization implies the determination of the electrical, magnetic, optical or thermal properties of the material under study. Though it is possible to study all these properties of a material, we concentrate on the thermal and optical properties of certain polymers. The thermal properties are detennined using photothermal beam deflection technique and the optical properties are obtained from various spectroscopic analyses. In addition, thermal properties of a class of semiconducting compounds, copper delafossites, arc determined by photoacoustic technique.Photothermal technique is one of the most powerful tools for non-destructive characterization of materials. This forms a broad class of technique, which includes laser calorimetry, pyroelectric technique, photoacollstics, photothermal radiometric technique, photothermal beam deflection technique etc. However, the choice of a suitable technique depends upon the nature of sample and its environment, purpose of measurement, nature of light source used etc. The polynler samples under the present investigation are thermally thin and optically transparent at the excitation (pump beam) wavelength. Photothermal beam deflection technique is advantageous in that it can be used for the detennination of thermal diffusivity of samples irrespective of them being thermally thick or thennally thin and optically opaque or optically transparent. Hence of all the abovementioned techniques, photothemlal beam deflection technique is employed for the successful determination of thermal diffusivity of these polymer samples. However, the semi conducting samples studied are themlally thick and optically opaque and therefore, a much simpler photoacoustic technique is used for the thermal characterization.The production of polymer thin film samples has gained considerable attention for the past few years. Different techniques like plasma polymerization, electron bombardment, ultra violet irradiation and thermal evaporation can be used for the preparation of polymer thin films from their respective monomers. Among these, plasma polymerization or glow discharge polymerization has been widely lIsed for polymer thin fi Im preparation. At the earlier stages of the discovery, the plasma polymerization technique was not treated as a standard method for preparation of polymers. This method gained importance only when they were used to make special coatings on metals and began to be recognized as a technique for synthesizing polymers. Thc well-recognized concept of conventional polymerization is based on molecular processcs by which thc size of the molecule increases and rearrangemcnt of atoms within a molecule seldom occurs. However, polymer formation in plasma is recognized as an atomic process in contrast to the above molecular process. These films are pinhole free, highly branched and cross linked, heat resistant, exceptionally dielectric etc. The optical properties like the direct and indirect bandgaps, refractive indices etc of certain plasma polymerized thin films prepared are determined from the UV -VIS-NIR absorption and transmission spectra. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer. The thermal diffusivity has been measured using the photothermal beam deflection technique as stated earlier. This technique measures the refractive index gradient established in the sample surface and in the adjacent coupling medium, by passing another optical beam (probe beam) through this region and hence the name probe beam deflection. The deflection 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 deflection signal is suitably analyzed for determining the thermal diffusivity.Another class of compounds under the present investigation is copper delafossites. These samples in the form of pellets are thermally thick and optically opaque. Thermal diffusivity of such semiconductors is investigated using the photoacoustic technique, which measures the pressure change using an elcctret microphone. The output of the microphone is fed to a lock-in-amplificr to obtain the amplitude and phase from which the thermal properties are obtained. The variation in thermal diffusivity with composition is studied.

EPDM/CIIR Blends: Compatibility, Morphology and Physical Properties

A detailed study of the blends of ethylene-propylene-diene rubber (EPDM) and chlorobutyl rubber (CIIR) is proposed in this study. These blends may find application in the manufacture of curing diaphragms/curing envelopes for tire curing applications. EPDM possesses better physical properties such as high heat resistance, ozone resistance, cold and moisture resistance, high resistance to permanent defonnation, very good resistance to flex cracking and impact. Because of the low gas and moisture penneability, good weathering resistance and high thermal stability of CIIR, blends of EPDM with CIlR may be attractive, if sufficient mechanical strength can be developed. Although a lot of work has been done on elastomer blends, studies on the blends of EPDM and CIIR rubbers are meagre. Hence in this investigation it is proposed to make a systematic study on the characteristics of EPDM and CIIR rubber blends.The mechanical and physical properties of an elastomer blend depend mainly on the blend compatibility. So in the first part of the study, it is proposed to develop compatible blends of EPDM with CIIR. Various commercial grades of ethylenepropylene- diene rubber are proposed to be blended with a specific grade of chlorobutyl rubber at varying proportions. The extent of compatibility in these blends is proposed to be evaluated based on their mechanical properties such as tensile strength, tear strength and ageing resistance. In addition to the physical property measurements, blend compatibility is also proposed to be studied based on the glass transition behavlour of the blends in relation to the Tg's of the individual components using Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). The phase morphology of the blends is also proposed to be investigated by Scanning Electron Microscopy (SEM) studies of the tensile fracture surfaces. In the case of incompatible blends, the effect of addition of chlorosulfonated polyethylene as a compatibiliser is also proposed to be investigated.In the second part of the study, the effect of sulphur curing and resin curing on the curing behaviour and the vulcanizate properties of EPDM/CIIR blends are planned to be evaluated. Since the properties of rubber vulcanizates are determined by their network structures, it is proposed to determine the network structure of the vulcanizates by chemical probes so as to correlate it with the mechanical properties.In the third part of the work, the effect of partial precuring of one of the components prior to blending as a possible means of improving the properties of the blend is proposed to be investigated. This procedure may also help to bring down the viscosity mismatch between the constituent e1astomers and provide covulcanization of the blend.The rheological characteristics and processability of the blends are proposed to be investigated in the last part of the study. To explore their possible applications, the air permeability of the blend samples at varying temperatures is proposed to be measured. The thermal diffusivity behaviour of EPDM/CIlR blends is also proposed to be investigated using novel laser technique. The thermal diffusivity of the blends along with the thermal degradation resistance may help to determine whether the blends are suitable for high temperature applications such as in the manufacturing of curing envelope.

Novel adhesive systems based on neoprene-phenolic blends

The aim of the investigation is to develop new high performance adhesive systems based on neoprene-phenolic blends. Initially the effect of addition of all possible ingredients like fillers, adhesion promoters, curing agents and their optimum compositions to neoprene solution is investigated. The phenolic resin used is a copolymer of phenol-cardanolformaldehyde prepared in the laboratory. The optimum ratio between phenol and cardanol that gives the maximum bond strength in metal-metal, rubber-rubber and rubber-metal specimens has been identified. Further the ratio between total phenols and formaldehyde is also optimised. The above adhesive system is further modified by the addition of epoxidized phenolic novolacs. For this purpose, phenolic novolac resins are prepared in different stoichiometric ratios and are subsequently epoxidized. The effectiveness of the adhesive for bonding different metal and rubber substrates is another part of the study. To study the ageing behaviour, different bonded specimens are exposed to high temperature, hot water and salt water and adhesive properties have been evaluated. The synthesized resins have been characterized by FTIR , HNMR spectroscopy. The molecular weights of the resins have been obtained by GPC. Thermogravimetric analysis and differential scanning calorimetry are used to study the thermal properties. The fractured surface analysis is studied by scanning electron microscopy. The study has brought to light the influence of phenol/ formaldehyde stoichiometric ratio, addition of cardanol (a renewable resource), adhesion promoters and suitability of the adhesive for different substrates and the age resistance of adhesive joints among other things.

Design and Development of Instrumentation Systems to determine the Dry Rubber Content in Natural Rubber Latex

Hevea latex is a natural biological liquid of very complex composition .Besides rubber hydrocarbons,it contains many proteinous and resinous substances,carbohydrates,inorganic matter,water,and others.The Dry Rubber Content (DRC) of latex varies according to season, tapping system,weather,soil conditions ,clone,age of the tree etc. The true DRC of the latex must be determined to ensure fair prices for the latex during commercial exchange.The DRC of Hevea latex is a very familiar term to all in the rubber industry.It has been the basis for incentive payments to tappers who bring in more than the daily agreed poundage of latex.It is an important parameter for rubber and latex processing industries for automation and verious decesion making processes.This thesis embodies the efforts made by me to determine the DRC of rubber latex following different analytical tools such as MIR absorption,thermal analysis.dielectric spectroscopy and NIR reflectance.The rubber industry is still Looking for a compact instrument that is accurate economical,easy to use and environment friendly.I hope the results presented in this thesis will help to realise this goal in the near future.

Entropy change and magnetocaloric effect in Gd5(SixGe1-x)4

Isothermal magnetization curves up to 23 T have been measured in Gd5Si1.8Ge2.2. We show that the values of the entropy change at the first-order magnetostructural transition, obtained from the Clausius-Clapeyron equation and the Maxwell relation, are coincident, provided the Maxwell relation is evaluated only within the transition region and the maximum applied field is high enough to complete the transition. These values are also in agreement with the entropy change obtained from differential scanning calorimetry. We also show that a simple phenomenological model based on the temperature and field dependence of the magnetization accounts for these results.

Kinetics of martensitic transitions in Cu-Al-Mn under thermal cycling: Analysis at multiple length scales

In this paper we study the evolution of the kinetic features of the martensitic transition in a Cu-Al-Mn single crystal under thermal cycling. The use of several experimental techniques including optical microscopy, calorimetry, and acoustic emission, has enabled us to perform an analysis at multiple scales. In particular, we have focused on the analysis of avalanche events (associated with the nucleation and growth of martensitic domains), which occur during the transition. There are significant differences between the kinetics at large and small length scales. On the one hand, at small length scales, small avalanche events tend to sum to give new larger events in subsequent loops. On the other hand, at large length scales the large domains tend to split into smaller ones on thermal cycling. We suggest that such different behavior is the necessary ingredient that leads the system to the final critical state corresponding to a power-law distribution of avalanches.

Martensitic transitions and the nature of ferromagnetism in the austenitic and martensitic states of Ni-Mn-Sn alloys

Structural and magnetic transformations in the Heusler-based system Ni0.50Mn0.50¿xSnx are studied by x-ray diffraction, optical microscopy, differential scanning calorimetry, and magnetization. The structural transformations are of austenitic-martensitic character. The austenite state has an L21 structure, whereas the structures of the martensite can be 10M , 14M , or L10 depending on the Sn composition. For samples that undergo martensitic transformations below and around room temperature, it is observed that the magnetic exchange in both parent and product phases is ferromagnetic, but the ferromagnetic exchange, characteristic of each phase, is found to be of different strength. This gives rise to different Curie temperatures for the austenitic and martensitic states.