Surface properties and catalytic activity of ferrospinels of nickel, cobalt and copper, prepared by soft chemical methods

Ferrospinels of nickel, cobalt and copper and their sulphated analogues were prepared by the room temperature coprecipitation route to yield samples with high surface areas. The intrinsic acidity among the ferrites was found to decrease in the order: cobalt> nickel> copper. Sulphation caused an increase in the number of weak and medium strong acid sites, whereas the strong acid sites were left unaffected. Electron donor studies revealed that copper ferrite has both the highest proportion of strong sites and the lowest proportion of weak basic sites. All the ferrite samples proved to be good catalysts for the benzoy lation of toluene with benzoyl chloride. copper and cobalt ferrites being much more active than nickel ferrite. The catalytic activity for benzoylation was not much influenced by sulphation, but it increased remarkably with calcination temperature of the catalyst. Surface Lewis acid sites, provided by the octahedral cations on the spinel surface, are suggested to be responsible for the catalytic activity for the benzoylation reaction.

Surface properties and catalytic activity of phosphate modified zirconia

Preparation and physico-chemical characterization or phosphate modified zirconia systems and their application to Friedel-Crafts benzylation and benzoylation of toluene have been reported. The influence of transition metals on the surface properties and catalytic activity has also been discussed.

Surface electron properties and catalytic activity of Sr doped lanthana

The electron donating properties, surface acidity/basicity and catalytic activity of lanthana for various dopant concentrations of strontium are reported at two activation temperatures. The catalytic activity has been correlated with electron donating properties and surface acidity/basicity of the oxide.

The surface acidity/basicity and catalytic activity of ternary oxides of La, Ce and AI

The surface acidity and basicity of ternary oxides of La, Ce and AI have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cycIohexanone in 2-propanol.

Surface acidity/basicity and catalytic activity of ternary oxides of Al, Ce and Dy

The surface acidity and basicity of ternary oxides of AI, Ce and Dy have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cyclohexanone in 2-propanol. The reaction is favoured by the higher basicity of the ternary oxide.

Surface acidity/basicity and catalytic activity of mixed oxides of Zr, La and Al

The surface acidity/basicity of binary oxides of Zr and La and the ternary oxides of Zr, La and Al are reported. The data have been correlated with their catalytic activity towards liquid phase reduction of cyclohexanone.

Influence of surface and acid properties of vanadia supported on ceria promoted with rice husk silica on cyclohexanol decomposition

Cyclohexanol decomposition activity of supported vanadia catalysts is ascribed to the high surface area, total acidity and interaction between supported vanadia and the amorphous support. Among the supported catalysts, the effect of vanadia over various wt% V2O5 (2–10) loading indicates that the catalyst comprising of 6 wt% V2O5 exhibits higher acidity and decomposition activity. Structural characterization of the catalysts has been done by techniques like energy dispersive X-ray analysis, X-ray diffraction and BET surface area. Acidity of the catalysts has been measured by temperature programmed desorption using ammonia as a probe molecule and the results have been correlated with the activity of catalysts.

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.

Photothermal beam deflection for non-destructive evaluation of semiconductor thin films

Non-destructive testing (NDT) is the use of non-invasive techniques to determine the integrity of a material, component, or structure. Engineers and scientists use NDT in a variety of applications, including medical imaging, materials analysis, and process control.Photothermal beam deflection technique is one of the most promising NDT technologies. Tremendous R&D effort has been made for improving the efficiency and simplicity of this technique. It is a popular technique because it can probe surfaces irrespective of the size of the sample and its surroundings. This technique has been used to characterize several semiconductor materials, because of its non-destructive and non-contact evaluation strategy. Its application further extends to analysis of wide variety of materials. Instrumentation of a NDT technique is very crucial for any material analysis. Chapter two explores the various excitation sources, source modulation techniques, detection and signal processing schemes currently practised. The features of the experimental arrangement including the steps for alignment, automation, data acquisition and data analysis are explained giving due importance to details.Theoretical studies form the backbone of photothermal techniques. The outcome of a theoretical work is the foundation of an application.The reliability of the theoretical model developed and used is proven from the studies done on crystalline.The technique is applied for analysis of transport properties such as thermal diffusivity, mobility, surface recombination velocity and minority carrier life time of the material and thermal imaging of solar cell absorber layer materials like CuInS2, CuInSe2 and SnS thin films.analysis of In2S3 thin films, which are used as buffer layer material in solar cells. The various influences of film composition, chlorine and silver incorporation in this material is brought out from the measurement of transport properties and analysis of sub band gap levels.The application of photothermal deflection technique for characterization of solar cells is a relatively new area that requires considerable attention.The application of photothermal deflection technique for characterization of solar cells is a relatively new area that requires considerable attention. Chapter six thus elucidates the theoretical aspects of application of photothermal techniques for solar cell analysis. The experimental design and method for determination of solar cell efficiency, optimum load resistance and series resistance with results from the analysis of CuInS2/In2S3 based solar cell forms the skeleton of this chapter.

Studies on the Surface Properties and Catalytic Activity of Metal Chromites on Thermal Decomposition of Ammonium Perchlorate

Department of Applied Chemistry, Cochin University of Science and Technology

Thermal diffusivity of some polymer supported halogeno benzimidazole complexes of cobalt(II) and copper(II) - a photoacoustic study

The thermal diffusivities of some polystyrene supported Schiff complexes of Co(II) and Cu(II) were determined by the laser induced photoacoustic technique. The effect of metal as well as the halogen part on thermal diffusivity of polymer supported complexes was studied. The thermal diffusivity of Co complexes increases while it decreases in Cu complexes with Cl, Br and I substitutions, respectively.

Evaluation of electrical conductivity and thermal diffusivity of vanadyl naphthalocyanine

The electrical conductivity and thermal diffusivity of pristine and iodine doped vanadyl naphthalocyanine (VONc) were studied. In the pristine sample, the temperature dependence was very weak below 300 K. The increase in conductivity at higher temperature must be due to an enhancement in carrier density with increase in thermal energy. The electrical conductivity of VONc increased when doped with iodine. The behavior of VONcI indicated that considerable changes have occurred in the electronic environment of the molecule as a result of doping. Iodine doping enhanced the thermal diffusivity of VONc. The increase in thermal diffusivity of the iodine doped sample may be due to the disorder of iodine atoms occupying the channels in one dimensional lattices.

Thermal diffusivity measurements in organic liquids using transient thermal lens calorimetry

Thermal diffusivity measurements are carried out in certain organic liquids using the pulsed dual beam thermal lens technique. The 532 nm pulses from a frequency doubled Q-switched Nd:YAG laser are used as the heating source and an intensity stabilized He-Ne laser serves as the probe beam. Experimental determination of the characteristic time constant of the transient thermal lens signal is verified theoretically. Measured thermal diffusivity values are in excellent agreement with literature values.

Effect of Te doping on thermal diffusivity of Bi2Se3 crystals: A study using open cell photoacoustic technique

An open cell configuration has been employed for the photoacoustic measurement of the thermal diffusivity of undoped Bi2Se3 crystals and Bi2Se3 crystals doped with various concentrations of Te. The amplitude of the photoacoustic signal obtained under heat transmission configuration as a function of chopping frequency is used to evaluate the numerical value of thermal diffusivity, α. Doped samples show a substantial reduction in the value of α compared to undoped samples. The variations in the thermal diffusivity of the doped samples are explained in terms of the phonon assisted heat transfer mechanism. It is seen that α is very sensitive to structural variations arising from doping. The experimentally observed results are correlated with X-ray diffraction studies.