Production of Functional Nanocrystalline Materials in Hydrogen

On the example of KS25 and KS37 samarium–cobalt-base commercial alloys and LaNi_4.5Al_0.5 alloy, we show the possibility, in principle, of obtaining functional materials in the nanocrystalline state with the help of a planetary mill in hydrogen medium. Milling with a rotational speed of 600 rpm during 24 h leads to the disproportionation of KS25 and KS37 alloys into samarium hydride and iron–cobalt (cobalt) and of LaNi_4.5Al_0.5 into Ni₃Al and amorphous products. After vacuum annealing up to 1181 K, the main phases of samarium–cobalt materials are recombined. The crystallite sizes after annealing are 58–72 and 70 nm for KS25 and KS37, respectively. We established that LaNi_4.5Al_0.5 alloy is not recombined in vacuum, and the nanocrystalline state in it can be reached by milling up to 30 min. The crystallite sizes constitute 45–78 nm.     

To react or not to react? Intrinsic stochasticity of human control in virtual stick balancing

Understanding how humans control unstable systems is central to many research problems, with applications ranging from quiet standing to aircraft landing. Increasingly, much evidence appears in favour of event-driven control hypothesis: human operators only start actively controlling the system when the discrepancy between the current and desired system states becomes large enough. The event-driven models based on the concept of threshold can explain many features of the experimentally observed dynamics. However, much still remains unclear about the dynamics of human-controlled systems, which likely indicates that humans use more intricate control mechanisms. This paper argues that control activation in humans may be not threshold-driven, but instead intrinsically stochastic, noise-driven. Specifically, we suggest that control activation stems from stochastic interplay between the operator''s need to keep the controlled system near the goal state, on the one hand, and the tendency to postpone interrupting the system dynamics, on the other hand. We propose a model capturing this interplay and show that it matches the experimental data on human balancing of virtual overdamped stick. Our results illuminate that the noise-driven activation mechanism plays a crucial role at least in the considered task, and, hypothetically, in a broad range of human-controlled processes.     

Specific features of the interaction of alloys of the didymium-iron-boron system with hydrogen

We study the interaction of alloys of the Dd-Fe-B system [M-82, M-83, M-84, and M-85 alloys with a mass content of 33–40% didymium, up to 0.5% aluminum, and 1–1.25% boron (the rest is iron)] with hydrogen using volumetric, X-ray phase, and differential thermal analysis. If the initial hydrogen pressure is 1.0 MPa, hydrides with 0.4–0.6 mass % of hydrogen are formed. The saturation of these alloys with hydrogen is accompanied by an increase in the spacing a of an elementary cell by 1.2–1.4% and in c by 0.8–1.1% (the general increase in volume is 3.2–3.9%). If the initial pressure is 0.15–0.2 MPa, the time of complete saturation with hydrogen is 15–20 min for most alloys. At 973–1033 K, the alloys under study in hydrogen disproportionate into DdHx didymium hydride (a = 0.5449 – 0.5458 nm), -iron (a = 0.2864 – 0.2866 nm), and Fe2 B iron boride (a = 0.5112 – 0.5117 nm, c = 0.4228 nm). An increase in the initial hydrogen pressure from 0.1 to 5.0 MPa is accompanied by a decrease in the disproportionation temperature to 930 K.Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 40, No. 2, pp. 105–112, March–April, 2004.     

Hydrogen-induced phase transformations in alloys based on Sm Co<Subscript>5</Subscript> under pressures of up to 650 kPA

The interaction of alloys based on SmCo₅ with hydrogen is studied by the methods of differential thermal and X-ray phase diffraction analyses under initial pressures of hydrogen of 200, 300, 400, 500, and 650 kPa at temperatures of up to 1223°K. The hydride of the alloy is formed up to a temperature of 343°K. Within the temperature ranges 388–408°K and 488–523°K, hydrogen is released from the hydrides of phases of the alloy. Within the temperature range 823–863°K, the alloy partially disproportionates into Sm H_x and Co. At 1008–1053°K, SmH_x undergoes partial decomposition and the SmCo₅ and Sm₂Co₁₇ phases are detected. The Co, SmCo₅, and Sm₂Co₁₇ phases exist at temperatures above 1168–1188°K. The compositions of the phases depend on the duration of interaction of the alloy with hydrogen. __________ Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 43, No. 1, pp. 94–98, January–February, 2007.     

Features of the HDDR process in R–Fe–B ferromagnetic alloys (R is a mixture of Nd, Pr, Ce, La, Dy and others)

Features of the conventional hydrogenation, disproportionation, desorption, recombination (HDDR) and solid-HDDR processes in some R–Fe–B (R is a mixture of Nd, Pr, Ce, La, Dy) ferromagnetic alloys were studied in the temperature range 20–990 °C and pressure range from 1×10⁻³ Pa to 0.1 MPa. This was carried out by means of differential thermal analysis (DTA), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) methods. The hydride of the initial phase is formed by heating to 115 °C. The disproportionation of the alloys occurs in the temperature range from 320 to 800 °C. Φ-phase constitutes the base of the initial alloys. Among the disproportionation products, R-hydride, -Fe and two borides (Fe₂B and R_1.1Fe₄B₄) were revealed. The initial phase in all the alloys is recovered after heating in vacuum to a temperature of 990 °C. Full hydrogen desorption occurs in two temperature ranges with the peaks at 200–320 and 630–715 °C.     

Real-time monitoring of benzene, toluene, and p-xylene in a photoreaction chamber with a tunable mid-infrared laser and ultraviolet differential optical absorption spectroscopy

We describe the implementation of a mid-infrared laser-based trace gas sensor with a photoreaction chamber, used for reproducing chemical transformations of benzene, toluene, and p-xylene (BTX) gases that may occur in the atmosphere. The system performance was assessed in the presence of photoreaction products including aerosol particles. A mid-infrared external cavity quantum cascade laser (EC-QCL)-tunable from 9.41-9.88?μm (1012-1063?cm(-1))-was used to monitor gas phase concentrations of BTX simultaneously and in real time during chemical processing of these compounds with hydroxyl radicals in a photoreaction chamber. Results are compared to concurrent measurements using ultraviolet differential optical absorption spectroscopy (UV DOAS). The EC-QCL based system provides quantitation limits of approximately 200, 200, and 600 parts in 10(9) (ppb) for benzene, toluene, and p-xylene, respectively, which represents a significant improvement over our previous work with this laser system. Correspondingly, we observe the best agreement between the EC-QCL measurements and the UV DOAS measurements with benzene, followed by toluene, then p-xylene. Although BTX gas-detection limits are not as low for the EC-QCL system as for UV DOAS, an unidentified by-product of the photoreactions was observed with the EC-QCL, but not with the UV DOAS system.     

Feasibility of high performance in p-type Ge1−xBixTe materials for thermoelectric modules

GeTe is a promising candidate for the fabrication of high-temperature segments for p-type thermoelectric (TE) legs. The main restriction for the widespread use of this material in TE devices is high carrier concentration (up to ∼ 10²¹ cm⁻³), which causes the low Seebeck coefficient and high electronic component of thermal conductivity. In this work, the band structure diagram and phase equilibria data have been effectively used to attune the carrier concentration and to obtain the high TE performance. The Ge_1−xBi_xTe (x = 0.04) material prepared by the Spark plasma sintering (SPS) technique demonstrates a high power factor accompanied by moderate thermal conductivity. As a result, a significantly higher dimensionless TE figure of merit ZT = 2.0 has been obtained at ∼ 800 K. Moreover, we are the first to propose that application of the developed Ge_1−xBi_xTe (x = 0.04) material in the TE unicouple should be accompanied by SnTe and CoGe₂ transition layers. Only such a unique solution for the TE unicouple makes it possible to prevent the negative effects of high contact resistance and chemical diffusion between the segments at high temperatures.