Structural and kinetic studies of spin crossover in an Iron(II) complex with a novel tripodal ligand

Configurational and ligand conformational influences on the kinetics of (1)A(1) reversible arrow T-5(2) spin crossover in the Fe(II) complex with the novel tripodal ligand, 1,1,1-tris((N-(2-pyridylmethyl)-N-methylamino)methyl)ethane (tptMetame), have been explored. Despite having six chelate rings and three chiral nitrogen atoms, only one enantiomeric pair of isomers, Delta, SSS, and Lambda, RRR, of the complex ion is observed. The conformation of the three rings forming the upper ''cap'' of the complex structure can be assigned delta or lambda with respect to the 3-fold molecular axis. X-ray data at 300 and 153 K, above and below the critical temperature for the spin transition, show that the conformation of the ligand ''cap'' is the same as the absolute configuration of the complex, with the same Lambda lambda(CAP)(or Delta delta(CAP)) combination prevailing for both the LS ((1)A(1)) and HS (T-5(2)) isomers. Molecular mechanics calculations further show that the ligand energy remains lowest for this Lambda lambda(CAP) (or Delta delta(CAP)) combination at all Fe-N distances over the range spanning the LS and HS isomers. Measurements of the spin crossover relaxation time have been carried out in solution over the temperature range 293-170 K. The observed monophasic relaxation traces are also consistent with the absolute configuration of the complex remaining unaltered during the spin crossover.

Chironomid-based reconstructions of summer air temperature from lake deposits in Lyndon Stream, New Zealand spanning the MIS 3/2 transition

We present chironomid-based temperature reconstructions from lake sediments deposited between ca 26,600 cal yr BP and 24,500 cal yr BP from Lyndon Stream, South Island, New Zealand. Summer (February mean) temperatures averaged 1 1C cooler, with a maximum inferred cooling of 3.7 1C. These estimates corroborate macrofossil and beetle-based temperature inferences from the same site and suggest climate amelioration (an interstadial) at this time. Other records from the New Zealand region also show a large degree of variability during the late Otiran glacial sequence (34,000–18,000 cal yr BP) including a phase of warming at the MIS 2/3 transition and a maximum cooling that did not occur until the global LGM (ca 20,000 cal yr BP). The very moderate cooling identified here at the MIS 2/3 transition confirms and enhances the long-standing discrepancy in New Zealand records between pollen and other proxies. Low abundances (o20%) of canopy tree pollen in records from late MIS 3 to the end of MIS 2 cannot be explained by the minor (o5 1C) cooling inferred from this and other studies unless other environmental parameters are considered. Further work is required to address this critical issue.

A critical evaluation of Raman spectroscopy for the analysis of lipids: fatty acid methyl esters.

The work presented here is aimed at determining the potential and limitations of Raman spectroscopy for fat analysis by carrying out a systematic investigation of C-4-C-24 FAME. These provide a simple, well-characterized set of compounds in which the effect of making incremental changes can be studied over a wide range of chain lengths and degrees of unsaturation. The effect of temperature on the spectra was investigated over much larger ranges than would normally be encountered in real analytical measurements. It was found that for liquid FAME the best internal standard band was the carbonyl stretching vibration nu(C = O), whose position is affected by changes in sample chain length and physical state; in the samples studied here, it was found to lie between 1729 and 1748 cm(-1). Further, molar unsaturation could be correlated with the ratio of the nu(C = O) to either nu(C = C) or delta(H-C = ) with R-2 > 0.995. Chain length was correlated with the delta(CH2)(tw)/nu(C = O) ratio, (where "tw" indicates twisting) but separate plots for odd- and even-numbered carbon chains were necessary to obtain R-2 > 0.99 for liquid samples. Combining the odd- ani even-numbered carbon chain data in a single plot reduced the correlation to R-2 = 0.94-0.96, depending on the band ratios used. For molal unsaturation the band ratio that correlated linearly with unsaturation (R-2 > 0.99) was nu(C = C)/delta(CH2)(SC) (where "sc" indicates scissoring). Other band ratios show much more complex behavior with changes in chemical and physical structure. This complex behavior results from the fact that the bands do not arise from simple vibrations of small, discrete regions of the molecules but are due to complex motions of large sections of the FAME so that making incremental changes in structure does not necessarily lead to simple incremental changes in spectra.

Heat capacities of ionic liquids as a function of temperature at 0.1 MPa. measurement and prediction

Heat capacities of nine ionic liquids were measured from (293 to 358) K by using a heat flux differential scanning calorimeter. The impact of impurities (water and chloride content) in the ionic liquid was analyzed to estimate the overall uncertainty. The Joback method for predicting ideal gas heat capacities has been extended to ionic liquids by the generation of contribution parameters for three new groups. The principle of corresponding states has been employed to enable the subsequent calculation of liquid heat capacities for ionic liquids, based on critical properties predicted using the modified Lydersen-Joback-Reid method, as a function of the temperature from (256 to 470) K. A relative absolute deviation of 2.9% was observed when testing the model against 961 data points from 53 different ionic liquids reported previously and measured within this study.

Temperature-Driven Mixing-Demixing Behavior of Binary Mixtures of the Ionic Liquid Choline Bis(trifluoromethylsulfonyl)imide and Water

The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point = 30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility proper-ties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). H-1 NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G(+)/G(-). These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

CRITICAL PROCESSES, LANGEVIN EQUATION AND UNIVERSALITY

In nature there are ubiquitous systems that can naturally approach critical states, The Langevin equation in the discrete version can be used to describe a class of critical processes, which are characterized by power-law behaviors and scaling relations. As an example, we present a simple model for a clinical thermometer, whose reading cannot fall even when its temperature decreases. The fibers bundle model and the spring-block model are also shown to belong to such a class.

Investigation of the effect of the preparation method on the activity and stability of Au/CeZrO4 catalysts for the low temperature water gas shift reaction

The impact of the preparation method on the activity and stability of gold supported on ceria-zirconia low temperature water-gas shift (WGS) catalysts have been investigated. The influence of the gold deposition method, nature of the gold precursor, nature of the washing solution, drying method, Ce: Zr ratio of the support and sulfation of the support have been evaluated. The highest activity catalysts were obtained using a support with a Ce: Zr mole ratio 1: 1, HAuCl4 as the gold precursor deposited via deposition precipitation using sodium carbonate as the precipitation agent and the catalyst washed with water or 0.1 M NH4OH solution. In addition, the drying used was found to be critical with drying under vacuum at room temperature found to be most effective.

Fibre-optic strain sensor system with temperature compensation for arch bridge condition monitoring

This paper presents an innovative sensor system, created specifically for new civil engineering structural monitoring applications, allowing specially packaged fiber grating-based sensors to be used in harsh, in-the-field measurement conditions for accurate strain measurement with full temperature compensation. The sensor consists of two fiber Bragg gratings that are protected within a polypropylene package, with one of the fiber gratings isolated from the influence of strain and thus responding only to temperature variations, while the other is sensitive to both strain and temperature. To achieve this, the temperature-monitoring fiber grating is slightly bent and enclosed in a metal envelope to isolate it effectively from the strain. Through an appropriate calibration process, both the strain and temperature coefficients of each individual grating component when incorporated in the sensor system can be thus obtained. By using these calibrated coefficients in the operation of the sensor, both strain and temperature can be accurately determined. The specific application for which these sensors have been designed is seen when installed on an innovative small-scale flexi-arch bridge where they are used for real-time strain measurements during the critical installation stage (lifting) and loading. These sensors have demonstrated enhanced resilience when embedded in or surface-mounted on such concrete structures, providing accurate and consistent strain measurements not only during installation but subsequently during use. This offers an inexpensive and highly effective monitoring system tailored for the new, rapid method of the installation of small-scale bridges for a variety of civil engineering applications.

Mapping stone surface temperature fluctuations: Implications for lichen distribution and biomodification on historic stone surfaces

The exposure of historic stone to processes of lichen-induced surface biomodification is determined, first and foremost, by the bioreceptivity of those surfaces to lichen colonization. As an important component of surface bioreceptivity, spatiotemporal variation in stone surface temperature plays a critical role in the spatial distribution of saxicolous lichen on historic stone structures, especially within seasonally hot environments. The ornate limestone and tufa stairwell of the Monastery of Cartuja (1516), Granada, Spain, exhibits significant aspect-related differences in lichen distribution. Lichen coverage and
diurnal fluctuations in stone surface temperature on the stairwell were monitored and mapped, under anticyclonic conditions in summer and winter, using an infrared thermometer and Geographical Information Systems approach. This research suggests that it is not extreme high surface temperatures that
determine the presence or absence of lichen coverage on stonework. Instead, average stone surface temperatures
over the course of the year seem to play a critical role in determining whether or not surfaces are receptive to lichen colonization and subsequent biomodification. It is inferred that lichen, capable of surviving extreme surface temperatures during the Mediterranean summer in an ametabolic state, require a respite period of lower temperatures within which they can metabolize, grow and reproduce.
The higher the average annual temperature a surface experiences, the shorter the respite period for any lichen potentially inhabiting that surface. A critical average temperature threshold of approximately 21 ?C has been identified on the stairwell, with average stone surface temperatures greater than this
generally inhibiting lichen colonization. A brief visual condition assessment between lichen-covered and lichen-free surfaces on the limestone sections of the stairwell suggests relative bioprotection induced by lichen coverage, with stonework quality and sharpness remaining more defined beneath lichen-covered surfaces. The methodology employed in this paper may have further applications in the monitoring and mapping of thermal stress fatigue on historic building materials.

Effect of Turbine Inlet Temperature on Rotor Blade Tip Leakage Flow and Heat Transfer

One of the most critical gas turbine engine components, the rotor blade tip and casing, is exposed to high thermal load. It becomes a significant design challenge to protect the turbine materials from this severe situation. The purpose of this paper is to study numerically the effect of turbine inlet temperature on the tip leakage flow structure and heat transfer. In this paper, the effect of turbine inlet temperature on the tip leakage flow structure and heat transfer has been studied numerically. Uniform low (LTIT: 444 K) and high (HTIT: 800 K) turbine inlet temperature, as well as non-uniform inlet temperature have been considered. The results showed the higher turbine inlet temperature yields the higher velocity and temperature variations in the leakage flow aerodynamics and heat transfer. For a given turbine geometry and on-design operating conditions, the turbine power output can be increased by 1.33 times, when the turbine inlet temperature increases 1.80 times. Whereas the averaged heat fluxes on the casing and the blade tip become 2.71 and 2.82 times larger, respectively. Therefore, about 2.8 times larger cooling capacity is required to keep the same turbine material temperature. Furthermore, the maximum heat flux on the blade tip of high turbine inlet temperature case reaches up to 3.348 times larger than that of LTIT case. The effect of the interaction of stator and rotor on heat transfer features is also explored using unsteady simulations. The non-uniform turbine inlet temperature enhances the heat flux fluctuation on the blade tip and casing.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

Studies of the Room-Temperature Multiferroic Pb(Fe0.5Ta0.5)0.4(Zr0.53Ti0.47)0.6O3: Resonant Ultrasound Spectroscopy, Dielectric, and Magnetic Phenomena

Recently, lead iron tantalate/lead zirconium titanate (PZTFT) was demonstrated to possess large, but unreliable, magnetoelectric coupling at room temperature. Such large coupling would be desirable for device applications but reproducibility would also be critical. To better understand the coupling, the properties of all 3 ferroic order parameters, elastic, electric, and magnetic, believed to be present in the material across a range of temperatures, are investigated. In high temperature elastic data, an anomaly is observed at the orthorhombic mm2 to tetragonal 4mm transition, Tot = 475 K, and a softening trend is observed as the temperature is increased toward 1300 K, where the material is known to become cubic. Thermal degradation makes it impos- sible to measure elastic behavior up to this temperature, however. In the low temperature region, there are elastic anomalies near ≈40 K and in the range 160–245 K. The former is interpreted as being due to a magnetic ordering transition and the latter is interpreted as a hysteretic regime of mixed rhom- bohedral and orthorhombic structures. Electrical and magnetic data collected below room temperature show anomalies at remarkably similar temperature ranges to the elastic data. These observations are used to suggest that the three order parameters in PZTFT are strongly coupled.

Monodomain strained ferroelectric PbTiO(3) thin films: Phase transition and critical thickness study

This work demonstrates that instead of paraelectric PbTiO(3), completely c-oriented ferroelectric PbTiO(3) thin films were directly grown on (001)-SrTiO(3) substrates by pulsed-laser deposition with thickness up to 340 nm at a temperature well above the Curie temperature of bulk PbTiO(3). The influence of laser-pulse frequency, substrate-surface termination on growth, and functional properties were studied using x-ray diffraction, transmission electron microscopy, and piezoresponse force microscopy. At low growth rates (frequency 8 Hz) a domains were formed for film thickness above 20-100 nm. Due to coherency strains the Curie temperature (T(c)) of the monodomain films was increased approximately by 350 degrees C with respect to the T(c) of bulk PbTiO(3) even for 280-nm-thick films. Nonetheless, up to now this type of growth mode has been considered unlikely to occur since the Matthews-Blakeslee (MB) model already predicts strain relaxation for films having a thickness of only similar to 10 nm. However, the present work disputes the applicability of the MB model. It clarifies the physical reasons for the large increase in T(c) for thick films, and it is shown that the experimental results are in good agreement with the predictions based on the monodomain model of Pertsev et al. [Phys. Rev. Lett. 80, 1988 (1998)].

A device to investigate the axial strain dependence of the critical current density in superconductors

We have developed an instrument to study the behavior of the critical current density (J(c)) in superconducting wires and tapes as a function of field (mu(0)H), temperature (T), and axial applied strain (epsilon(a)). The apparatus is an improvement of similar devices that have been successfully used in our institute for over a decade. It encompasses specific advantages such as a simple sample layout, a well defined and homogeneous strain application, the possibility of investigating large compressive strains and the option of simple temperature variation, while improving the main drawback in our previous systems by increasing the investigated sample length by approximately a factor of 10. The increase in length is achieved via a design change from a straight beam section to an initially curved beam, placed perpendicular to the applied field axis in the limited diameter of a high field magnet bore. This article describes in detail the mechanical design of the device and its calibrations. Additionally initial J(c)(epsilon(a)) data, measured at liquid helium temperature, are presented for a bronze processed and for a powder-in-tube Nb3Sn superconducting wire. Comparisons are made with earlier characterizations, indicating consistent behavior of the instrument. The improved voltage resolution, resulting from the increased sample length, enables J(c) determinations at an electric field criterion E-c=10 muV/m, which is substantially lower than a criterion of E-c=100 muV/m which was possible in our previous systems. (C) 2004 American Institute of Physics.

Effect of turbine inlet temperature on blade tip leakage flow and heat transfer

One of the most critical gas turbine engine components, rotor blade tip and casing, are exposed to high thermal load. It becomes a significant design challenge to protect the turbine materials from this severe situation. As a result of geometric complexity and experimental limitations, Computational Fluid Dynamics (CFD) tools have been used to predict blade tip leakage flow aerodynamics and heat transfer at typical engine operating conditions. In this paper, the effect of turbine inlet temperature on the tip leakage flow structure and heat transfer has been studied numerically. Uniform low (LTIT: 444 K) and high (HTIT: 800 K) turbine inlet temperature have been considered. The results showed the higher turbine inlet temperature yields the higher velocity and temperature variations in the leakage flow aerodynamics and heat transfer. For a given turbine geometry and on-design operating conditions, the turbine power output can be increased by 1.48 times, when the turbine inlet temperature increases 1.80 times. Whereas the averaged heat fluxes on the casing and the blade tip become 2.71 and 2.82 times larger, respectively. Therefore, about 2.8 times larger cooling capacity is required to keep the same turbine material temperature. Furthermore, the maximum heat flux on the blade tip of high turbine inlet temperature case reaches up to 3.348 times larger than that of LTIT case. The effect of the interaction of stator and rotor on heat transfer features is also explored using unsteady simulations.