Thermal cycling of Mg-MMCs

Creep resistant Mg alloy QE22 reinforced with maftec(R), saffil(R) or supertec(R) short fibres is cycled between room temperature and 308degreesC at different ramp rates in the longitudinal and transverse directions. From the careful analysis of the strain vs. temperature thermal cycling curves true material behaviour and artifacts from the dilatometer are deciphered. From this analysis true coefficient of thermal expansion and relaxation processes are deduced. Hysteresis at higher temperatures is attributed to the relaxation process, whereas hysteresis at low temperatures giving a tilt-ground shape to the thermal cycling curves is again an artifact due to the instrument. The change in ramp rate highlights this effect. Finally, the effect of thermal cycling on microstructure is examined.

Andaman Postseismic Deformation Observations: Still Slipping after All These Years?

More than six years after the great (M-w 9.2) Sumatra-Andaman earthquake, postevent processes responsible for relaxation of the coseismic stress change remain controversial. Modeling of Andaman Islands Global Positioning System (GPS) displacements indicated early near-field motions were dominated by slip down-dip of the rupture, but various researchers ascribe elements of relaxation to dominantly poroelastic, dominantly viscoelastic, and dominantly fault slip processes, depending primarily on their measurement sampling and modeling tools used. After subtracting a pre-2004 interseismic velocity, significant transient motion during the 2008.5-2010.5 epoch confirms that postseismic relaxation processes continue in Andaman. Modeling three-component velocities as viscoelastic flow yields a weighted root-mean-square (wrms) misfit that always exceeds the wrms of the measured signal (26.3 mm/yr). The best-fitting models are those that yield negligible deformation, indicating the model parameters have no real physical meaning. GPS velocities are well fit (wrms 4.0 mm/yr) by combining a viscoelastic flow model that best fits the horizontal velocities with similar to 50 cm/yr thrust slip down-dip of the coseismic rupture. Both deep slip and flow respond to stress changes, and each can significantly change stress in the realm of the other; it therefore is reasonable to expect that both transient deep slip and viscoelastic flow will influence surface deformation long after a great earthquake.

Glassy dynamics in a confined monatomic fluid

Molecular dynamic simulations of a strongly inhomogeneous system reveals that a single-component soft-sphere fluid can behave as a fragile glass former due to confinement. The self-intermediate scattering function, F-s(k,t), of a Lennard-Jones fluid confined in slit-shaped pores, which can accomodate two to four fluid layers, exhibits a two-step relaxation at moderate temperatures. The mean-squared displacement data are found to follow time-temperature superposition and both the self-diffusivity and late a relaxation times exhibit power-law divergences as the fluid is cooled. The system possesses a crossover temperature and follows the scalings of mode coupling theory for the glass transition. The temperature dependence of the self-diffusivity can be expressed using the Vogel-Fulcher-Tammann equation, and estimates of the fragility index of the system indicates a fragile glass former. At lower temperatures, signatures of additional relaxation processes are observed in the various dynamical quantities with a three-step relaxation observed in the F-s(k,t).

Dielectric relaxations above room temperature in DMPU derived polyaniline film

Dielectric measurements carried out on drop casted from solution of emeraldine base form of polyaniline films in the temperature range 30-300 degrees C revealed occurrence of two maxima in the loss tangent as a function of temperature. The activation energies corresponding to these two relaxation processes were found to be similar to 0.5 eV and similar to 1.5 eV. The occurrence of one relaxation peak in the dispersion curve of the imaginary part of the electric modulus suggests the absence of microphase separation in the film. Thermogravimetric analysis and infrared spectroscopic measurements showed that the films retained its integrity up to 300 degrees C. The dielectric relaxation at higher temperatures with large activation energy of 1.5 eV is attributed to increase in the barrier potential due to decrease in the polymer conjugation as a result of wide amplitude motion of the chain segments well above the glass transition temperature. (c) 2012 Elsevier B.V. All rights reserved.

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton-phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5-4.2 nm have been synthesized where emission is in the NIR region of 650-855 nm. Temperature-dependent (15-300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1-2.8 x 10(-4) eV K-1. The strength of the electron-phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17-1.68 for QDs with a size of 2.5-4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140-300 K), traps of low (13-25 meV) and high (65-140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton-acoustic phonon scattering and exciton-longitudinal optical (LO) phonon coupling. The exciton-acoustic phonon scattering coefficient is found to be enhanced up to 55 MU eV K-1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices.

Proton spin lattice relaxation in lithium ammonium sulphate LiNH4SO4

Lithium ammonium sulphate (LAS) undergoes a phase transition at TC1=459.5K from a paraelectric phase (phase I) to a ferroelectric phase (phase II) and again at TC2=283K to a polar ferroelastic phase (phase III). Proton spin lattice relaxation time measured at 10 MHz in powdered LAS in the temperature range 480 to 77K shows discontinuous changes at the two transitions.

Proline ring conformations corresponding to a bistable jump model from 13C spin-lattice relaxation times

A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.

Proton Spin-Lattice Relaxation in Sodium Ammonium Selenate Dihydrate:NaNHaSeOa.2He0

Proton spin-lattice relaxation studies in sodium ammonium selenate dihydrate carried out in the temperature range 130 to 300 K at 10 MHz show a continuous change in T, at T, indicating a second order phase transition. This compound is a typical case of a highly hindered solid wherein the thermally activated reorientations of ammonium ions freeze well above 77 K, as seen by NMR.Untersuchimgen der Protonen-Spin-Gitter-Relaxation in Natriuni-Ammoniumselenat-Dihydrat bei 10 MHz im Temperaturbereich 130 bis 300 K zeigen eine kontinuierliche Andernng in TI bei T, und ergeben einen Phasenubergang zweiter Art. Diese Verbindung ist ein typischer Fall eines stark ,,behinderten" Festkarpers, in dein die thermisch aktivierten Reorientierungen der Ammoniumionen weit oberhalb 77 H einfrieren, wie die NMR-Ergebnisse zeigen.

Pyrrolidine ring conformations in prolyl peptides from 13C spin-lattice relaxation times

A method was developed in the framework of a bistable jump model to obtain the pyrrolidine ring conformations in proline peptides from 13C spin-lattice relaxation times. Equations are presented expressing the ring torsions in terms of the 13C spin-lattice relaxation times of the ring carbons. This method was applied to 26 pyrrolidine ring systems and acceptable conformations were obtained.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

Temperature- and pressure-dependent study of Cl-35 NQR frequency and spin lattice relaxation time in 2,3-dichloroanisole

The temperature and pressure dependence of Cl-35 NQR frequency and spin lattice relaxation time (T-1) were investigated in 2,3-dichloroanisole. Two NQR signals were observed throughout the temperature and pressure range studied. T-1 were measured in the temperature range from 77 to 300 K and from atmospheric pressure to 5 kbar. Relaxation was found to be due to the torsional motion of the molecule and also reorientation f motion of the CH3 group. T-1 versus temperature data were analyzed on the basis of Woessner and Gutowsky model, and the activation energy for the reorientation of the CH3 group was estimated. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities were also obtained. NQR frequency shows a nonlinear behavior with pressure, indicating both dynamic and static effects of pressure. The pressure coefficients were observed to be positive for both the lines. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. The variation of spin lattice time with pressure was very small, showing that the relaxation is mainly due to the torsional motions of the molecules. Copyright (C) 2010 John Wiley & Sons, Ltd.

Carbon-13 relaxation study of chain segmental motion and side-chain internal rotations of poly(isobutyl methacrylate) in solution

The dynamics of poly(isobutyl methacrylate) in toluene 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 using the Dejean-Laupretre-Monnerie (DLM) model, which describes the dynamical processes in the backbone in terms of conformational transitions and bond librations. The relaxation data of the side chain nuclei have been analyzed by assuming different motional models, namely, unrestricted rotational diffusion, three site jumps, and restricted rotational diffusion. The different models have been compared for their ability to reproduce the experimental spin-lattice relaxation times and also to predict the behavior of NOE as a function of temperature. Conformational energy calculations have been carried out on a model compound by using the semiempirical quantum chemical method, AM1, and the results confirm the validity of the motional models used to describe the side-chain motion.

Temperature dependence study of chlorine NQR frequency and spin-lattice relaxation time in 2-amino,-3,5-dichloropyridine

Chlorine-35 NQR frequency and spin-lattice relaxation time measurements as a function of temperature in the range 77-300 K were carried out on 2-amino-3,5-dichloropyridine. Two NQR signals were observed and were assigned to the two chlorines present in the molecule using the additive model for substituent effects. The temperature dependence of the NQR frequency was analysed in terms of the torsional oscillations of the molecule and the torsional frequencies and their temperature dependence were calculated numerically using a two-mode approximation. The temperature dependence of the NQR spin-lattice relaxation time was found to be mainly due to the torsional oscillations of the molecule, with anharmonicity effects showing up at higher temperatures. Copyright (C) 1999 John Wiley & Sons, Ltd.