301 resultados para isothermal titration calorimetry


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Some recent observations at Pic-du-Midi (Mulleret al., 1992a) suggest that the photospheric footpoints of coronal magnetic field lines occasionally move rapidly with typical velocities of the order 3 km s–1 for about 3 or 4 min. We argue that such occasional rapid footpoint motions could have a profound impact on the heating of the quiet corona. Qualitative estimates indicate that these occasional rapid motions can account for the entire energy flux needed to heat the quiet corona. We therefore carry out a mathematical analysis to study in detail the response of a vertical thin flux tube to photospheric footpoint motions in terms of a superposition of linear kink modes for an isothermal atmosphere. We find the resulting total energy that is asymptotically injected into an isothermal atmosphere (i.e., an atmosphere without any back reflection). By using typical parameter values for fast and slow footpoint motions, we show that, even if the footpoints spend only 2.5% of the time undergoing rapid motions, still these rapid motions could be more efficient in transporting energy to the corona than the slow motions that take place most of the time.

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Based on an isothermal, isobaric simulation the structure and properties of the plastic crystalline phases of C60 and neopentane have been examined. Instantaneous cooling of the plastic crystalline phases of both C60 and neopentane leads to orientational glassy phases. These are accompanied by significant slowing down of reorientational motion. Constant pressure quench experiments on C60 yield a glass transition temperature of around 80 K.

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The isothermal sections of the phase diagram for the system Ca-Cu-0 at 1073 and 1223 K have been determined. Several compositions in the ternary system were quenched after equilibration, and the phases present were identified by optical microscopy, X-ray diffraction, and electron probe microanalysis. Two ternary compounds Ca2CuO3 and Cao.8&uO1.9s were identified at 1073 K. However, only Ca2CuO3 was found to be stable at 1223 K. The thermodynamic properties of the two ternary compounds were determined using solid-state cells incorporating either an oxide or a fluoride solid electrolyte. The results for both types of cells were internally consistent. The compound C ~ O . ~ & U Ow~h.i~ch~ c, a n also be represented as Ca15Cu18035h, as been identified in an earlier investigation as Cao.828CuOz. Using a novel variation of the galvanic cell technique, in which the emf of a cell incorporating a fluoride electrolyte is measured as a function of the oxygen potential of the gas phase in equilibrium with the condensed phase electrodes, it has been confirmed that the compound Cao.828CuO1.93 (Ca15Cu18035d) oes not have significant oxygen nonstoichiometry. Phase relations have been deduced from the thermodynamic data as a function of the partial pressure of oxygen for the system Ca-Cu-0 at 873, 1073, and 1223 K.

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The supramolecular structures of eight aryl protected ethyl-6-methyl-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidine- 5-carboxylates have been analyzed to determine the role of different functional groups on the molecular geometry, conformational characteristics and the packing of these molecules in the crystal lattice. Out of these the para fluoro substituted compound on the aryl ring exhibits conformational polymorphism, due to the different conformation of the ester moiety. This behaviour has been characterized using both powder and single-crystal X-ray diffraction, optical microscopy and differential scanning calorimetry performed on both these polymorphs. The compounds pack via the cooperative interplay of strong N-H center dot center dot center dot O=C intermolecular dimers and chains forming a sheet like structure. In addition, weak C-H center dot center dot center dot O=C and C-H center dot center dot center dot pi interactions impart additional stability to the crystal packing.

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The liquid and the glassy phases of 2,2-dimethylbutane have been investigated by isothermal isobaric ensemble Monte Carlo simulation. Thermodynamic Properties and radial distribution functions for both the liquid and the glass have been obtained. The radial distribution functions have been classified into three types based on the accessibility of the group. It has been shown that the structure of the Iiquid and the glass can be understood in terms of the above classification of the radial distribution functions. Molecular reorientation plays an important role in the structural rearrangement accompanying glass formation. As much as 35% of the contribution to the increase in the intermolecular interaction energy on vitrification is due to the reorientation of the neighbouring pairs of molecules. The observed changes in the dimerisation energy and the bonding energy distribution function are consistent with the observed structural changes.

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In this paper we report the measurements of specific heats of five glass formers as they are cooled through the glass-transition region. The measurements are compared with other specific-heat measurements such as adiabatic-calorimetry and ac-calorimetry measurements. The data are then analyzed using a model of enthalpy relaxation and nonequilibrium cooling, which can track the nonequilibrium relaxation time tau(S). The relevant parameters that describe tau(S) are obtained, allowing us to compare the enthalpy-relaxation times obtained from this method with other methods. We display the clear connection of the unrelaxed enthalpy with the nonequilibrium relaxation time and also show the role played by the delayed heat release from the unrelaxed enthalpy in the glass-transition region. We have also made certain definite observations regarding the equilibrium configurational specific heat and the Vogel-Fulcher law, which describes tau(S).

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NiTi thin films deposited by DC magnetron sputtering of an alloy (Ni/Ti:45/55) target at different deposition rates and substrate temperatures were analyzed for their structure and mechanical properties. The crystalline structure, phase-transformation and mechanical response were characterized by X-ray diffraction (XRD), Differential Scanning Calorimetry (DSC) and Nano-indentation techniques, respectively. The films were deposited on silicon substrates maintained at temperatures in the range 300 to 500 degrees C and post-annealed at 600 degrees C for four hours to ensure film crystallinity. Films deposited at 300 degrees C and annealed for 600 degrees C have exhibited crystalline behavior with Austenite phase as the prominent phase. Deposition onto substrates held at higher deposition temperatures (400 and 500 degrees C) resulted in the co-existence of Austenite phase along with Martensite phase. The increase in deposition rates corresponding to increase in cathode current from 250 to 350 mA has also resulted in the appearance of Martensite phase as well as improvement in crystallinity. XRD analysis revealed that the crystalline film structure is strongly influenced by process parameters such as substrate temperature and deposition rate. DSC results indicate that the film deposited at 300 degrees C had its crystallization temperature at 445 degrees C in the first thermal cycle, which is further confirmed by stress temperature response. In the second thermal cycle the Austenite and Martensite transitions were observed at 75 and 60 degrees C respectively. However, the films deposited at 500 degrees C had the Austenite and Martensite transitions at 73 and 58 degrees C, respectively. Elastic modulus and hardness values increased from 93 to 145 GPa and 7.2 to 12.6 GPa, respectively, with increase in deposition rates. These results are explained on the basis of change in film composition and crystallization. (C) 2010 Published by Elsevier Ltd

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Nanocrystalline metals frequently exhibit poor thermal stability, and the exothermic peak in differential scanning calorimetry is usually attributed to grain growth. We show from experiments on electrodeposited nano-Ni with varying levels of S, and tests with microcrystalline Ni and S powders, that the exothermic peak is associated with the formation of a nickel sulfide phase and concurrent grain growth. Analysis suggests that segregation plays a more important role in limiting grain growth than second-phase particles in nano-Ni. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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Click chemistry has been successfully extended into the field of molecular design of novel amphiphatic adducts. After their syntheses and characterizations, we have studied their aggregation properties in aqueous medium. Each of these adducts forms stable suspensions in water. These suspensions have been characterized by dynamic light scattering (DLS) studies and transmission electron microscopy (TEM). The presence of inner aqueous compartments in such aggregates has been demonstrated using dye (methylene blue) entrapment studies. These aggregates have been further characterized using X-ray diffraction (XRD), which indicates the existence of bilayer structures in them. Therefore, the resulting aggregates could be described as vesicles. The temperature-induced order-to-disorder transitions of the vesicular aggregates and the accompanying changes in their packing and hydration have been examined using high-sensitivity differential scanning calorimetry, fluorescence anisotropy, and generalized polarization measurements using appropriate membrane-soluble probe, 1,6-diphenylhexatriene, and Paldan, respectively. The findings of these studies are consistent with each other in terms of the apparent phase transition temperatures. Langmuir monolayer studies confirmed that these click adducts also form stable monolayers on buffered aqueous subphase at the air-water interface.

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Two series of cholesterol-based cationic gemini lipids with and without hydroxyl functions at the headgroups possessing different lengths of polymethylene -(CH2)(n)-] (n = 3, 4, 5, 6, 12) spacer have been synthesized. Each gemini lipid formed stable suspension in water. The suspensions of these gemini lipids in water were investigated using transmission electron microscopy, dynamic light scattering, zeta potential measurements and X-ray diffraction to characterize the nature of the individual aggregates formed therein. The aggregation properties of these gemini lipids in water were found to strongly depend upon the length of the spacer and the presence of hydroxyl group at the headgroup region. Lipoplex formation (DNA binding) and the release of the DNA from such lipoplexes were performed to understand the nature of interactions that prevail between these cationic cholesterol aggregates and duplex DNA. The interactions between such gemini lipids and DNA depend both on the presence of OH on the headgroups and the spacer length between the headgroups. Finally, we studied the effect of incorporation of each cationic gemini lipid into dipalmitoyl phosphatidylcholine vesicles using differential scanning calorimetry. The properties of the resulting mixed membranes were found again to depend upon the nature of the headgroup and the spacer chain length.

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The sulphide capacity as originally defined by Fincham and Richardson is a strong function of composition in pseudobinary oxide melts of interest in extractive metallurgy. From an analysis of data available in the literature, it is shown that sulphide capacity is directly proportional to the activity of the basic oxide in the melt, within the uncertainty of experimental data. A single parameter is sufficient to describe the sulphide capacity of a binary slag system under isothermal and isobaric conditions. The correlation indicates that the activity coefficient of the sulphide ion or the neutral base metal sulphide dissolved in the melt is independent of composition in pseudobinary melts within experimental uncertainty. Structural variations in the melt with composition do not seem to affect the activity coefficient of the sulphide. A modified sulphide capacity function is defined which makes the treatment more elegant and greatly simplifies data storage and retrieval. The modified function is not based on any model for the melt.

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An improved flux draining technique for the extraction of grown YBCO crystals from its solvent is reported. This simple and efficient technique facilitates in-situ flux separation in the isothermal region of the furnace. Consequently, the crystals are spared from thermal shock and subsequent damage. Flux-free surfaces of these crystals were studied by optical microscopy. Transmission X-ray topographs of the crystals reveal the dislocations present in them as well as the stresses developed as a result of ferroelastic phase transition occurring during cooling.

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Single crystals (up to 1 cm size) of K, Rb and Cs periodates have been grown in silica gel. In general, good quality crystals were obtained in gel of specific gravity 1.04 and pH 4. The metal/iodine ratios were determined and compared with calculated values. Morphological studies were carried out using a bicircle optical goniometer. Other characterization methods include X-ray diffraction, optical absorption, differential scanning calorimetry and optical microscopy. Microscopic examination of CsIO4 crystals in particular has revealed the existence of ferroelastic domains in the crystal. The structural basis for the occurence of ferroelasticity in this crystal is discussed and the high temperature space group is predicted.

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Zinc-10 and 20 wt pct Pb alloys have been rapidly solidified by melt spinning to obtain a very fine scale dispersion of nanometer-sized Pb particles embedded in Zn matrix. The microstructure and crystallography of the Pb particles have been studied using transmission electron microscopy (TEM). Each embedded Pb particle is a single crystal, with a truncated hexagonal biprism shape with the 6/mmm Zn matrix point group symmetry surrounded by and { 0001 á },\text { \text10[`\text1] \text0 },\text and { \text10[`\text1] \text1 }0001 1010 and 1011 facets. The Pb particles solidify with a well-defined orientation relationship with the Zn matrix of ( 0001 )Zn ||(111)Pb\text and\text [ \text11[`\text2] \text0 ]Zn| ||[ 1[`1] 0 ]Pb 0001Zn(111)Pb and 1120Zn110Pb . The melting and solidification behavior of the Pb particle have been studied using differential scanning calorimetry (DSC). The Pb particles solidify with an undercooling of approximately 30 K, by heterogeneous nucleation on the {0001} facets of the surrounding Zn matrix, with an apparent contact angle of 23 deg.

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The kinetics of the oxidation of electrodeposited boron powder and the boron powder produced by the reduction process were studied using thermogravimetry (TG). The oxidation was carried out by heating boron powder in a stream of oxygen. Both isothermal and non-isothermal methods were used to study the kinetics. Model-free isoconversional method was used to derive the kinetics parameters. A two step oxidation reaction (exothermic) was observed. The oxidation reaction could not be completed due to the formation of glassy layer of boric oxide on the surface of boron powder which acts as a barrier for further diffusion of oxygen into the particle. The activation energy obtained using model-free method for electrodeposited boron is 122 +/- 7 kJ mol(-1) whereas a value of 205 +/- 9 kJ mol(-1) was obtained for boron produced by the reduction process (commercially procured boron). Mechanistic interpretation of the oxidation reaction was done using model based method. The activation energy was found to depend on the size distribution of the particles and specific surface area of the powder. (C) 2010 Elsevier B.V. All rights reserved.