Fabrication and evaluation of a skutterudite-based thermoelectric module for high-temperature applications

We report a straightforward methodology for the fabrication of high-temperature thermoelectric (TE) modules using commercially available solder alloys and metal barriers. This methodology employs standard and accessible facilities that are simple to implement in any laboratory. A TE module formed by nine n-type Yb x Co4Sb12 and p-type Ce x Fe3CoSb12 state-of-the-art skutterudite material couples was fabricated. The physical properties of the synthesized skutterudites were determined, and the module power output, internal resistance, and thermocycling stability were evaluated in air. At a temperature difference of 365 K, the module provides more than 1.5 W cm−3 volume power density. However, thermocycling showed an increase of the internal module resistance and degradation in performance with the number of cycles when the device is operated at a hot-side temperature higher than 573 K. This may be attributed to oxidation of the skutterudite thermoelements.

Understanding the rapid summer warming and changes in temperature extremes since the mid-1990s over Western Europe

Analysis of observations indicates that there was a rapid increase in summer (June-August, JJA) mean surface air temperature (SAT) since the mid-1990s over Western Europe. Accompanying this rapid warming are significant increases in summer mean daily maximum temperature, daily minimum temperature, annual hottest day temperature and warmest night temperature, and an increase in frequency of summer days and tropical nights, while the change in the diurnal temperature range (DTR) is small. This study focuses on understanding causes of the rapid summer warming and associated temperature extreme changes. A set of experiments using the atmospheric component of the state-of-the-art HadGEM3 global climate model have been carried out to quantify relative roles of changes in sea surface temperature (SST)/sea ice extent (SIE), anthropogenic greenhouse gases (GHGs), and anthropogenic aerosols (AAer). Results indicate that the model forced by changes in all forcings reproduces many of the observed changes since the mid-1990s over Western Europe. Changes in SST/SIE explain 62.2% ± 13.0% of the area averaged seasonal mean warming signal over Western Europe, with the remaining 37.8% ± 13.6% of the warming explained by the direct impact of changes in GHGs and AAer. Results further indicate that the direct impact of the reduction of AAer precursor emissions over Europe, mainly through aerosol-radiation interaction with additional contributions from aerosol-cloud interaction and coupled atmosphere-land surface feedbacks, is a key factor for increases in annual hottest day temperature and in frequency of summer days. It explains 45.5% ± 17.6% and 40.9% ± 18.4% of area averaged signals for these temperature extremes. The direct impact of the reduction of AAer precursor emissions over Europe acts to increase DTR locally, but the change in DTR is countered by the direct impact of GHGs forcing. In the next few decades, greenhouse gas concentrations will continue to rise and AAer precursor emissions over Europe and North America will continue to decline. Our results suggest that the changes in summer seasonal mean SAT and temperature extremes over Western Europe since the mid-1990s are most likely to be sustained or amplified in the near term, unless other factors intervene.

Study of the pozzolanic reaction kinetics in sugar cane bagasse-clay ash/calcium hydroxide system: kinetic parameters and pozzolanic activity

This paper presents a study of the pozzolanic reaction kinetics between calcium hydroxide and a mixture of sugar cane bagasse with 20 and 30% of clay, burned at 800 and 1000 degrees C (SCBCA) by electrical conductivity measurements. A kinetic-diffusive model produced in previous studies by some of the authors was used. The model was fitted to the experimental data, which allowed the computation of the kinetic parameters of the pozzolanic reaction (reaction rate constant and free energy of activation) that rigorously characterised the pozzolanic activity of the materials. The results show that SCBCA demonstrated reactivity and good pozzolanic qualities in the range 800-1000 degrees C.

Interparticle Interactions Effects on the Magnetic Order in Surface of Fe(3)O(4) Nanoparticles

We report interparticle interactions effects on the magnetic structure of the surface region in Fe(3)O(4) nanoparticles. For that, we have studied a desirable system composed by Fe(3)O(4) nanoparticles with (d) = 9.3 nm and a narrow size distribution. These particles present an interesting morphology constituted by a crystalline core and a broad (similar to 50% vol.) disordered superficial shell. Two samples were prepared with distinct concentrations of the particles: weakly-interacting particles dispersed in a polymer and strongly-dipolar-interacting particles in a powder sample. M(H, T) measurements clearly show that strong dipolar interparticle interaction modifies the magnetic structure of the structurally disordered superficial shell. Consequently, we have observed drastically distinct thermal behaviours of magnetization and susceptibility comparing weakly- and strongly-interacting samples for the temperature range 2 K < T < 300 K. We have also observed a temperature-field dependence of the hysteresis loops of the dispersed sample that is not observed in the hysteresis loops of the powder one.

Effect of polyol excess on the electrical property of vegetable-polyurethane film

Freestanding castor oil-based polyurethane (PU) film was obtained using spin-coating method. The effect of polyol content was analysed by means of thermally stimulated depolarisation current and AC dielectric measurements techniques. Two relaxation peaks were observed in the temperature range of -40 to 60 degrees C for PU with different polyol contents. The presence of polyol excess provides a shift to lower temperature of the a relaxation and the decrease in the activation energy of the transition in this region might be attributed to the plasticising effect of the polyol. The peak at higher temperature is due to the Maxwell-Wagner-Sillars relaxation, which also shifts in the low temperature direction as the polyol content is increased.

Damping properties of open cell microcellular pure Al foams

Damping behaviours of the open cell microcellular pure Al foams fabricated by sintering and dissolution process with the relative density of 0·31-0·42 and the pore size of 112-325 μm were investigated. The damping characterisation was conducted on a multifunction internal friction apparatus. The internal friction (IF) was measured at frequencies of 1·0, 3·0 and 6·0 Hz over the temperature range of 298-725 K. The measured IF shows that the open cell pure Al foam has a damping capacity that is enhanced in comparison with pure Al. At a lower temperature (∼400 K), the IF of the open cell pure Al foams increases with decreasing relative density, with decreasing pore size and with increasing frequency. The IF peak was found at the temperature range of 433-593 K in the IF curves. It is clear that the IF peak is relaxational type and the activation energy associated with the IF peak is about 1·60 ± 0·02 eV. Defect effects can be used to interpret the damping mechanisms.

Influence of temperature on evaporative water loss and cutaneous resistance to water vapour diffusion in the orange-thighed frog (Litoria xanthomera)

We evaluated the effect of ambient temperatures between 25 and 43°C on the rate of evaporative water loss (EWL) in eight adult Litoria xanthomera (average body mass = 7.3 ± 0.6 g). Frogs were placed in a cylindrical chamber that permitted them to fully conceal their ventral surfaces using a water-conserving posture. Their EWL was 7.1 ± 0.7 mg g^–1 h^–1 at 25°C and reached 28.0 ± 2.5 mg g^–1 h^–1 at 43°C. Agar replicas of the frogs were used to evaluate boundary-layer resistances associated with the EWL measurements and, thus, to permit evaluation of cutaneous resistance to vapour diffusion (r_c) in live frogs. The r_c of L. xanthomera was stable over the temperature range of 25–35°C, averaging about 28 s cm^–1, and then declined stepwise with ambient temperatures above 37°C. The highest r_c recorded for each individual over the range of temperatures studied averaged 32.0 ± 1.2 s cm^–1. The thermolabile nature of r_c demonstrates a well developed thermoregulatory control of EWL in this species, a trait very similar in pattern and extent to that previously measured in the closely related Litoria chloris.

Secondary emission of nanocrystalline zinc oxide

The Raman and photoluminescence (PL) spectra of nanocrystalline zinc oxide produced by mechanochemical synthesis were measured using a pulsed nitrogen laser (337.1 nm) and xenon lamp (360 nm) as excitation sources in PL measurements and a cw Nd:YAG laser in Raman measurements. PL was observed in the range 400–800 nm. The Raman spectrum of nanocrystalline (90 nm) ZnO was compared to that of coarsegrained ZnO. The Raman bands of nanocrystalline zinc oxide were found to be shifted to lower frequencies and broadened. Laser radiation was shown to cause local heating of zinc oxide up to 1000 K, resulting in photoinduced formation of zinc nanoclusters. Mixtures of zinc oxide and sodium chloride powders are heated to substantially lower temperatures. Under nitrogen laser excitation, the green PL band (535 nm), characteristic of bulk ZnO, is shifted to longer wavelengths by 85 nm. The results are interpreted in terms of light confinement in zinc oxide microclusters consisting of large number of nanocrystallites. The photoinduced processes in question may be a viable approach to producing metal-insulator structures in globular photonic crystals, opals, filled with zinc oxide.

Composite cell components for elevated temperature all-solid-state Li-ion batteries

Application of Li-ion batteries with liquid electrolytes at elevated temperatures (above 60°C) is limited due to the decomposition of the electrolyte. Stable solid state electrolytes can solve this problem, but the conductivity of these electrolytes are relatively low, the interfacial contacts with the electrodes are poor, and the charge transfer kinetics in the electrodes are limited. Solutions for these problems by using composite electrodes and electrolytes have been investigated and the results are described. A new concept for making all-solid-state Li-ion batteries that can be applied in the temperature range between room temperature and about 150°C will be presented.

A new class of proton-conducting ionic plastic crystals based on organic cations and dihydrogen phosphate

Choline dihydrogen phosphate ([N_1.1.1.2OH]DHP) and 1-butyl-3-methylimidazolium dihydrogen phosphate ([C₄mim]DHP) were synthesized as a new class of proton-conducting ionic plastic crystals. Both [N_1.1.1.2OH]DHP and [C₄mim]DHP showed solid–solid phase transition(s) and showed a final entropy of fusion lower than 20 J K⁻¹ mol⁻¹ which is consistent with Timmerman’s criterion for molecular plastic crystals. The ionic conductivity of [N_1.1.1.2OH]DHP was in the range of 10⁻⁶ S cm⁻¹–10⁻³ S cm⁻¹ in the plastic crystalline phase. On the other hand, the ionic conductivity of [C₄mim]DHP showed about 10⁻⁵ S cm⁻¹ in the plastic crystalline phase. [N_1.1.1.2OH]DHP showed one order of magnitude higher ionic conductivity than [C₄mim]DHP in the temperature range where the plastic phase is stable.

Effects of temperature in relation to sheet metal stamping

The demand to reduce the use of lubricants and increase tool life in sheet metal stamping has resulted in increased research on the sliding contact between the tool and the sheet materials. Unlubricated sliding wear tests for soft carbon steel sliding on D2 tool steel were performed using a pin-on-disk tribometer. The results revealed that temperature has an influencing role in the wear of tool steel and that material transfer between tool and sheet can be minimized at a certain temperature range in sheet metal stamping.

Heat tolerance, behavioural temperature selection and temperature-dependent respiration in larval Octopus huttoni

This study reports temperature effects on paralarvae from a benthic octopus species, Octopus huttoni, found throughout New Zealand and temperate Australia. We quantified the thermal tolerance, thermal preference and temperature-dependent respiration rates in 1-5 days old paralarvae. Thermal stress (1°C increase h^-1) and thermal selection (~10-24°C vertical gradient) experiments were conducted with paralarvae reared for 4 days at 16°C. In addition, measurement of oxygen consumption at 10, 15, 20 and 25°C was made for paralarvae aged 1, 4 and 5 days using microrespirometry. Onset of spasms, rigour (CT_max) and mortality (upper lethal limit) occurred for 50% of experimental animals at, respectively, 26.0±0.2°C, 27.8±0.2°C and 31.4±0.1°C. The upper, 23.1±0.2°C, and lower, 15.0±1.7°C, temperatures actively avoided by paralarvae correspond with the temperature range over which normal behaviours were observed in the thermal stress experiments. Over the temperature range of 10°C-25°C, respiration rates, standardized for an individual larva, increased with age, from 54.0 to 165.2nmol larvae^-1h^-1 in one-day old larvae to 40.1-99.4nmol h^-1 at five days. Older larvae showed a lesser response to increased temperature: the effect of increasing temperature from 20 to 25°C (Q₁₀) on 5 days old larvae (Q₁₀=1.35) was lower when compared with the 1 day old larvae (Q₁₀=1.68). The lower Q₁₀ in older larvae may reflect age-related changes in metabolic processes or a greater scope of older larvae to respond to thermal stress such as by reducing activity. Collectively, our data indicate that temperatures >25°C may be a critical temperature. Further studies on the population-level variation in thermal tolerance in this species are warranted to predict how continued increases in ocean temperature will limit O. huttoni at early larval stages across the range of this species.

Effect of compositional gradient on thermal behavior of synthetic graphite-phenolic nanocomposites

Synthetic graphite–phenolic nanocomposites were designed and synthesized with a compositional gradient which is shown to influence transient temperature fields during rapid temperature changes. Such nanocomposites were fabricated using a compression moulding technique, and thermal conductivity and heat capacity of nanocomposites were experimentally determined using a modified transient plane source technique over a wide temperature range from 253.15 to 373.15 K. The effects of four compositional gradient configurations on the transient temperature field across the thickness of a nanocomposite plate, at a high imposed temperature, was investigated. The transient time and temperature fields in nanocomposite structures were highly affected by the compositional gradient configurations.

Gelled ionic liquid sodium ion conductors for sodium batteries

Owing to the unique properties of certain Ionic liquids (ILs) as safe and green solvents, as well as the potential of sodium as an alternative to lithium as charge carriers, we investigate gel sodium electrolytes as safe, low cost and high performance materials with sufficient mechanical properties for application in sodium battery technologies. We investigate the effect of formation of two types of gel electrolytes on the properties of IL electrolytes known to support Na/Na⁺ electrochemistry. The ionic conductivity is only slightly decreased by 0.0005 and 0.0002 S cm^-1 in the case of 0.3 and 0.5 M NaNTf2 systems respectively as the physical properties transition from liquid to gel. We observed facile plating and stripping of Na metal around 0 V vs. Na/Na⁺ through the cyclic voltammetry. A wide-temperature range of the gelled IL state, of more than 100 K around room temperature, is achieved in the case of 0.3 and 0.5 M NaNTf2. We conclude that the formation of a gel does not significantly affect the liquid-like ion dynamics in these materials, as further evidenced by DSC and FTIR analysis.

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2