An automated laboratory EXAFS spectrometer of Johansson type: indigenous development and testing

An automated linear laboratory EXAFS spectrometer of the Johansson type has been indigenously developed. Only two translational motions are required to achieve the necessary Rowland circle configuration for the (fixed) X-ray source, the dispersing and focusing bent crystal and the receiving slit. With the available crystals the spectral region from 5 to 25 keV can be scanned. The linear motions of the crystal and receiving slit including the detector assembly are achieved by employing software-controlled DC motors and utilizing optical encoders for position sensing. The appropriate rotation of the crystal is achieved by the geometry of the instrument. There is a facility to place the sample alternately in the path of the X-ray beam and out of the path to record both the incident X-ray intensityI ₀ and the transmitted intensityI employing the scintillation detector. An arrangement with a two-window proportional detector before the sample to measureI ₀ and the scintillation detector to recordI is also developed; in this case it is not necessary to oscillate the sample. Fast electronic circuits are employed to minimize counting errors. The instrument is user-friendly and it is operated through a menu-driven IBM compatible PC. EXAFS spectra of high resolution have been recorded using the spectrometer and employing the Si(111) reflecting planes; the X-ray source being a Rigaku 12 kW rotating anode with Cu target. We describe the spectrometer and discuss its performance with a few representative spectra.     

Study on curing of novolac epoxy resin

The optimization of proportions of novolac epoxy resin, Dobeckot E4 and polyamide hardener, EH411 has been established by DSC and the data indicates that resin-polyamide, 100∶40 and 100∶50, appear to be optimum where ‘extent of cure’ is maximum. The kinetic parameters for these formulations have been evaluated using isothermal and dynamic modes by employing DSC. The rate constants have been evaluated for curing process of these formulations using isothermal DSC mode in the temperature range of 70°–90°C. These have also been predicted at 20°±1°C (room temperature) by extrapolating the data obtained at elevated temperatures. A comparison of the predicted values with the experimental values shows that there is a good agreement between them.     

Structure and dynamics of water at the interface with phospholipid bilayers

We have performed two molecular-dynamics simulations to study the structural and dynamical properties of water at the interface with phospholipid bilayers. In one of the simulations the bilayer contained neutral phospholipid molecules, dioleoylphosphatidylcholine (DOPC); in the second simulation the bilayer contained charged lipid molecules, dioleoylphosphatidylserine (DOPS). From the density profile of water we observe that water next to the DOPS bilayer is more perturbed as compared to water near the DOPC bilayer. Using an energetic criterion for the determination of hydrogen bonding we find that water molecules create strong hydrogen bonds with the headgroups of the phospholipid molecules. Due to the presence of these bonds and also due to the confinement of water, the translational and orientational dynamics of water at the interface are slowed down. The degree of slowing down of the dynamics depends upon the location of water molecules near a lipid headgroup.     

Application of hollow fiber supported liquid membrane for the separation of americium from the analytical waste

Americium from analytical solid waste containing U and metallic impurities was separated using hollow fiber supported liquid membrane (HFSLM) technique impregnated with DHOA–TODGA from nitric acid medium. An aliquot of 5 g of the solid waste containing Am (19.95 mg) as minor actinide and of U (2,588 mg), Fe (1,360 mg), Ca (1,810 mg) and Na (3,130 mg) as major impurities was processed. The feed solution obtained after the dissolution of the residue in ~4 M HNO₃ was passed through HFSLM module. In the first stage using 1 M DHOA–dodecane U was recovered while Am and other impurities were left in the raffinate. In the second stage, 0.5 M DHOA + 0.1 M TODGA/dodecane was used for the separation of Am from other impurities. Though, majority of the elements were separated in this cycle, Ca was co extracted along with the americium. CMPO extraction chromatographic technique was used for further separation of americium from Ca. Significant decontamination factors were achieved in this three step separation process with respect to U, Fe, Na and Ca with ~77 % recovery of americium.     

Electrothermal AAS studies of Sm, Eu, Dy, and Er separated from uranium

Summary Studies were conducted on the assay of Sm, Eu, Dy and Er separated from uranium using aqueous standards by electrothermal AAS with Massmann type graphite furnace. The working curves were found to be linear in the ranges Sm (1–10 g/ml), Eu (0.05–0.6 g/ml), Dy (0.1–0.8 g/ml) and Er (0.1–1.0 g/ml). The values obtained for synthetic samples agreed favourably with those obtained by emission spectrographic method. Experiments using pyrolytic carbon coated tubes with and without pretreatment by La, Ta and Y have shown an enhancement with treatment upto a maximum of 15% and improve the memory effect marginally. The effect of Ta treatment was found to be singularly useful in improving the general behaviour of Sm. The interference effects of lanthanides, other than the analyte, were found to be negligible. However, the presence of uranium was found to affect the absorbance. The absorbance of Eu was found to be nearly independent of uranium after an initial increase. On the other hand, the absorbance of other elements studied was found to drastically decrease after an initial enhancement. Detailed investigations of temperature dependence of absorbance were carried out using Eu, Dy and Er. The differences in the behaviour of these elements is attributed to probable differences in the modes of their atomization.

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Untersuchung von aus Uran abgetrenntem Samarium, Europium, Dysprosium und Erbium durch elektrothermische Atomabsorptions-Spektralphotometrie

Zusammenfassung Die Untersuchungen wurden mit Hilfe des Graphitrohrofens nach Maßmann durchgeführt. In folgenden Bereichen ergaben sich lineare Eichkurven: Sm 1–10 g/ml, Eu 0,05–0,6 g/ml, Dy 0,1–0,8 g/ml, Er 0,1-1,0 g/ml. Die aus synthetischen Proben erhaltenen Ergebnisse stimmten gut mit den durch Emissionsspektrographie erhaltenen überein. Versuche wurden mit Röhren mit pyrolytischen Kohlenstoffüberzug mit und ohne Vorbehandlung durch La, Ta und Y durchgeführt und ergaben eine bis 15%ige Steigerung durch die Behandlung sowie eine mäßige Besserung des Memoryeffektes. Eine Behandlung mit Ta war besonders für Sm vorteilhaft. Störungen durch andere Lanthanide waren vernachlässigbar. Uran beeinflußte jedoch die Absorption. Im Falle von Eu zeigte sich nach anfänglicher Zunahme fast eine Unabhängigkeit, während bei den anderen untersuchten Elementen nach anfänglicher Zunahme eine beträchtliche Abnahme auftrat. Mit Eu, Dy und Er wurde ebenfalls die Temperaturabhängigkeit der Absorption untersucht. Festgestellte Unterschiede im Verhalten werden auf unterschiedliche Atomisierung zurückgeführt.

     

Diffusion of hydrocarbons in confined media: Translational and rotational motion

Diffusion of monatomic guest species within confined media has been understood to a good degree due to investigations carried out during the past decade and a half. Most guest species that are of industrial relevance are actually polyatomics such as, for example, hydrocarbons in zeolites. We attempt to investigate the influence of non-spherical nature of guest species on diffusion. Recent molecular dynamics (MD) simulations of motion of methane in NaCaA and NaY, benzene in NaY and one-dimensional channels AlPO₄−5, VPI−5 and carbon nanotube indicate interesting insights into the influence of the host on rotational degrees of freedom and orientational properties. It is shown that benzene in one-dimensional channels where the levitation parameter is near unity exhibits translational motion opposite to what is expected on the basis of molecular anisotropy. Rotational motion of benzene also possesses rotational diffusivities aroundC ₆ and C₂axes opposite to what is expected on the basis of molecular geometry. Methane shows orientational preference for 2+ 2 or 1 + 3 depending on the magnitude of the levitation parameter.     

Synthesis of compounds related to santonin

Proceedings - Mathematical Sciences - Following the methods used in the synthesis of santonin the synthesis of compounds related to santonin has been described.     

Thermal studies of N-(p-Hexyloxybenzylidene)-p-Toluidene (HBT)

The effect of quenching on phase transitions in monotropic liquid crystal HBT is investigated using DSC, DTA, X-ray diffraction and microscopic techniques. The phases which are normally seen only during the cooling cycle are observed when the substance is quenched from the isotropic liquid phase at appropriate rate.