Temperature and pressure dependence of 35Cl NQR in NaClO3 and Ba(ClO3)2·H2O

Pressure and temperature dependence of 35Cl nuclear quadrupole resonance (NQR) has been investigated in NaClO3 and Ba(ClO3)2·H2O. NQR frequencies are measured in the temperature range 77–300 K and up to 5 kbar pressure. The torsional frequency of the ClO3 pyramid and its variation with both pressure and temperature are evaluated from the NQR frequencies under the harmonic approximation. In general, the pressure effect on the internal motions is found to be less in Ba (ClO3)2·H2O compared to NaClO3. When the samples are cooled to 77 K the pressure coeffecient of NQR frequency becomes nearly zero in sodium chlorate, whereas it retains a value of 6 kHz kbar−1 in barium chlorate. This behaviour follows from the fact that at 77K, the torsional frequency in NaClO3 is unaffected by the application of pressure while it increases at the rate 12 cm−1 kbar−1 in Ba(ClO3)2·H2O.

Nuclear-quadrupole resonance in coordination chemistry- identification of bridiging and therminal chlorines in the mercuric chloride-4-picoline n-oxide complex

The temperature dependence of the chlorine-35 n.q.r. in the mercuric chloride-4-picoline N-oxide complex has been studied from 77 K to room temperature, and the results are used to assign the observed frequencies to terminal and bridging chlorines.

Circular dichroism and 13C nuclear magnetic resonance spectroscopy of pennisetin from pearl millet

The conformation and stability of pearl millet prolamin (pennisetin) were examined by using circular dichroism and C-13 nuclear magnetic resonance spectroscopy. The far UV spectrum of pennisetin in 70% (v/v) aqueous ethanol showed the presence of predominant alpha-helical structure and its occurrence in the alpha + beta class of protein. The far and near UV spectra of pennisetin in ethanol: trifluoroethanol also supported this observation. However pennisetin showed the presence of some helical structure in 8 M urea which is known to be a highly unordered structure forming solvent. A decrease in alpha helical content of native pennisetin was observed with rise in temperature from 5-75-degrees-C and this effect of temperature was found to be reversible. A C-13 NMR spectrum of pennisetin in 70% ethanol suggested a high degree of molecular mobility in ethanol. Comparison of the cross polarization spectrum with the single pulse excitation spectrum suggested pennisetin to be a heterogeneous protein.

Combustion synthesis of oxide materials for nuclear waste immobilization

Oxide materials like perovskite, zirconolite, hollandite, pyrochlore, NASICON and sphene which are used for nuclear waste immobilization have been prepared by a solution combustion process. The process involves the combustion of stoichiometric amount of corresponding metal nitrates and carbohydrazide/tetraformyl trisazine/diformyl hydrazide at 450 degrees C. The combustion products have been characterized using powder X-ray diffraction, infrared spectroscopy, and Si-29 MAS-NMR. The fine particle nature of the combustion derived powders has been studied using density, particle size, BET surface area measurements and scanning electron microscopy. Sintering of combustion derived powder yields 85-95% dense ceramics in the temperature range 1000 degrees-1300 degrees C.

Hot-working characteristics of Zircaloy-2 in the temperature range of 650–950°C

The hot-working characteristics of Zircaloy-2 have been studied in the temperature range of 650 to 950°C and in the strain-rate range of 10−3 to 102 s−1 using power dissipation maps which describe the variation of the efficiency of power dissipation, η = 2m /(m + 1) where m is the strain-rate sensitivity of flow stress. The individual domains exhibited by the map have been interpreted and validated by detailed metallographic investigations. Dynamic recrystallization occurs in the temperature range of 730 to 830°C and in the strain-rate range of 10−2 to 2 s−1. The peak efficiency occurs at 800°C and 0.1 s−1 which may be considered as the optimum hot-working parameters in the α-phase field of Zircaloy-2. Superplastic behaviour, characterized by a high efficiency of power dissipation is observed at temperatures greater than 860°C and at strain rates lower than 10−2 s−1. When deformed at 650°C and 10−3 s−1, the primary restoration mechanism is dynamic recovery, while at rates higher than 2s−1, the material exhibits microstructural instabilities in the form of localized shear bands.

Bloch-Nordsieck thermometers: One-loop exponentiation in finite temperature QED

We study the scattering of hard external particles in a heat bath in a real-time formalism for finite temperature QED. We investigate the distribution of the 4-momentum difference of initial and final hard particles in a fully covariant manner when the scale of the process, Q, is much larger than the temperature, T. Our computations are valid for all T subject to this constraint. We exponentiate the leading infra-red term at one-loop order through a resummation of soft (thermal) photon emissions and absorptions. For T > 0, we find that tensor structures arise which are not present at T = 0. These carry thermal signatures. As a result, external particles can serve as thermometers introduced into the heat bath. We investigate the phase space origin of log (Q/M) and log (Q/T) terms.

Dynamic Behavior of Poly(2-vinylpyridine) in Solution Studied by 13C Nuclear Magnetic Relaxation

Abstract: The dynamics of poly(2-vinylpyridine) in chloroform solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed in terms of six motional models. Among these models, the models which consider conformational transitions and bond librations for the backbone were found to be more successful. Pyridyl ring motion has been modeled as a restricted rotation with the rotational amplitude varying with temperature. The activation energy parameters obtained from the relaxation data of the pyridyl ring carbon have been compared with the energy barrier for ring rotation estimated from conformational energy calculations using the AM1 semiempirical quantum chemical method. The results of the conformational energy calculations support the description of pyridyl ring motion as a restricted rotation.

Low-temperature specific heat of antiferromagnetic EuNi5P3 and mixed-valent EuNi2P2 in magnetic fields to 7 T

he specific heats of EUNi(5)P(3), an antiferromagnet, and EuNi2P2, a mixed-valence compound, have been measured between 0.4 and 30 K in magnetic fields of, respectively, 0, 0.5, 1, 1.5, 2.5, 5, and 7 T, and 0 and 7 T. In zero field the specific heat of EuNi5P3 shows a h-like anomaly with a maximum at 8.3 K. With increasing field in the range 0-2.5 T, the maximum shifts to lower temperatures, as expected for an antiferromagnet. In higher fields the antiferromagnetic ordering is destroyed and the magnetic part of the specific heat approaches a Schottky anomaly that is consistent with expectations for the crystal-field/Zeeman levels. In low fields and for temperatures between 1.5 acid 5 K the magnetic contribution to the specific heat is proportional to the temperature, indicating a high density of excited states with an energy dependence that is very unusual for an antiferromagnet. The entropy associated with the magnetic ordering is similar to R In8, confirming that only the Eu2+-with J=7/2, S=7/2, L=0-orders below 30 R. In zero field approximately 20% of the entropy occurs above the Neel temperature, consistent. with the usual amount of short-range order observed in antiferromagnets. The hyperfine magnetic field at the Eu nuclei in EUNi(5)P(3) is 33.3 T, in good agreement with a value calculated from electron-nuclear double resonance measurements. For EuNi2P2 the specific heat is nearly field independent and shows no evidence of magnetic ordering or hyperfine fields. The coefficient of the electron contribution to the specific heat is similar to 100 mJ/mol K-2.

Radiation induced modifications on microstructure and related properties of high temperature superconductor YBCO

Role of swift heavy ion irradiation on the modification of transport and structural properties of high temperature superconductors is studied. Good quality YBCO thin films prepared by high pressure oxygen sputtering and laser ablation were used in this investigation. Resistivity and atomic force microscopy (AFM) were mainly used to probe superconducting and microstructural modifications resulted from the irradiation of high energy and heavy ions like 100 MeV oxygen and 200 MeV silver. Radiation induced sputtering or erosion is likely to be a major disastrous component of such high energy irradiation that could be powerful in masking phase coherence effects, atleast in grain boundaries. The extent of damage/nature of defects other than columnar defects produced by swift heavy ions is discussed in the light of AFM measurements. The effect of high energy oxygen ion irradiation is anomalous. A clear annealing effect at higher doses is seen. (C) 1999 Elsevier Science B.V. All rights reserved.

Cl-35 NQR frequency and spin lattice relaxation time in 3,4-dichlorophenol as a function of pressure and temperature

The pressure dependences of Cl-35 nuclear quadrupole resonance (NQR) frequency, temperature and pressure variation of spin lattice relaxation time (T-1) were investigated in 3,4-dichlorophenol. T-1 was measured in the temperature range 77-300 K. Furthermore, the NQR frequency and T-1 for these compounds were measured as a function of pressure up to 5 kbar at 300 K. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities W-1 and W-2 for the Delta m = +/- 1 and Delta m = +/- 2 transitions were also obtained. A nonlinear variation of NQR frequency with pressure has been observed and the pressure coefficients were observed to be positive. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. An attempt is made to compare the torsional frequencies evaluated from NQR data with those obtained by IR spectra. On selecting the appropriate mode from IR spectra, a good agreement with torsional frequency obtained from NQR data is observed. The previously mentioned approach is a good illustration of the supplementary nature of the data from IR studies, in relation to NQR studies of compounds in solid state.

Mono layer to Interdigitated Partial Bilayer Smectic C Transition in Thiophene-Based Spacer Mesogens: X-ray Diffraction and C-13 Nuclear Magnetic Resonance Studies

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state C-13 NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

Low-temperature electrical conductivity of LaNi1-xFexO3

We report the electrical conductivity between 2 and 300 K for LaNi1-xFexO3 across the composition-controlled metal-insulator (m-i) transition. Using a method first suggested by Mobius, we identify the critical concentration x(c) to be 0.3 for the m-i transition. The negative temperature coefficient of resistivity observed at low temperatures in the metallic phase follows a temperature dependence characteristic of disorder effects. The semiconducting compositions (x greater than or equal to 0.3) do not show a simple activation energy but exhibit variable-range hopping at high temperatures confirming that the m-i transition in this system is driven by increasing disorder effects.

High temperature deformation and densification in alumina-yttria composites

Pinning by second phase particles offers a potent means for limiting grain growth and enhancing superplasticity in alumina-based ceramics. In the present study, a colloidal technique was used to produce green bodies of alumina-yttria composites; at elevated temperatures, the yttria particles react with alumina to produce YAG particles. The densification and high temperature deformation characteristics of alumina-YAG composites were studied using conventional free sintering and sinter-forging, which involves the application of a compressive stress without any lateral constraints. It is shown that the YAG particles retard both densification and grain growth. The experiments indicate also that the presence of YAG particles does not significantly alter the stress exponent for creep deformation.

Temperature dependent vibrational lifetimes in supercritical fluids near the critical point

Vibrational relaxation measurements on the CO asymmetric stretching mode (similar to 1980 cm(-1)) of tungsten hexacarbonyl (W(CO)(6)) as a function of temperature at constant density in several supercritical solvents in the vicinity of the critical point are presented. In supercritical ethane, at the critical density, there is a region above the critical temperature (Tc) in which the lifetime increases with increasing temperature. When the temperature is raised sufficiently (similar to T-c + 70 degrees C), the lifetime decreases with further increase in temperature. A recent hydrodynamic/thermodynamic theory of vibrational relaxation in supercritical fluids reproduces this behavior semiquantitatively. The temperature dependent data for fixed densities somewhat above and below the critical density is in better agreement with the theory. In fluoroform solvent at the critical density, the vibrational lifetime also initially increases with increasing temperature. However, in supercritical CO2 at the critical density, the temperature dependent vibrational lifetime decreases approximately linearly with temperature beginning almost immediately above T-c. The theory does not reproduce this behavior. A comparison between the absolute lifetimes in the three solvents and the temperature trends is made.

The high temperature mechanical characteristics of superplastic 3 mol% yttria stabilized zirconia

A detailed study was undertaken to characterize the deformation behavior of a superplastic 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) over a wide range of strain rates, temperatures and grain sizes. The experimental data were analyzed in terms of the following equation for high temperature deformation: Image Full-size image ∞ σn d−pexp(−Q/RT), where Image Full-size image is the strain rate, σ is the flow stress, d is the grain size, Q is the activation energy, R is the gas constant, T is the absolute temperature, and n and p are constants termed the stress exponent and the inverse grain size exponent, respectively. The experimental data over a wide range of stresses revealed a transition in stress exponent. Deformation in the low and high stress regions was associated with n not, vert, similar 3 and p not, vert, similar 1, and n not, vert, similar 2 and p not, vert, similar 3, respectively. The transition stress between the two regions decreased with increasing grain size. The activation energy was similar for both regions with a value of not, vert, similar 550 kJ mol−1. Microstructural measurements revealed that grains remained essentially equiaxed after the accumulation of large strains, and very limited concurrent grain growths occurred in most experiments. Assessment of possible rate controlling creep mechanisms and comparison with previous studied indicate that in the n not, vert, similar 2 region, deformation occurs by a grain boundary sliding process whose rate is independent of impurity content. Deformation in the n not, vert, similar 3 region is controlled by an interface reaction that is highly sensitive to impurity content. It is concluded that an increase in impurity content increases yttrium segregation to grain boundaries, which enhances the rate of the interface reaction, thereby decreasing the apparent transition stress between the n not, vert, similar 2 and n not, vert, similar 3 regions. This unified approach incorporating two sequential mechanisms can rationalize many of the apparently dissimilar results that have been reported previously for deformation of 3YTZ.