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In recent years, skutterudite filled with electronegative elements (S, Se, Cl, Br) has attracted the extensive attention of researchers. By doping electron donors (Pb, Ni, or Te, S, Se) at the Co or Sb sites, the electronegative elements can form thermodynamically stable compounds in the intrinsic pores of the skutterudite, substantially expanding the research scope of skutterudite. In this study, S0.05Co4Sb11.3Te0.6Se0.1 skutterudite was synthesized at high pressure and high temperature, with a pressure range of 2.0-3.5 GPa. The phase composition, micro-morphology, and electrical and thermal transport properties were systematically characterized. The micromorphology analysis shows that the introduction of S element and substituting Te and Se at the Sb sites inhibit the grain growth in a suitable high-pressure environment. Substantial differences are observed in the directions of the lattice stripes in the samples, and rich grain boundaries and many lattice distortions and dislocation defects occur. The carrier concentration can be optimized by filling the voids of the skutterudite with a few S atoms, and the thermoelectric properties can be optimized by scattering phonons through resonance scattering and defect scattering. The samples synthesized at a pressure of 3.0 GPa and a temperature of 900 K have a maximum power factor of 23.85 × 10-4 W m-1 K-2 and a maximum zT value of 1.30 at a test temperature of 773 K.
RESUMO
The thermoelectric (TE) properties of n-type polycrystalline Yb0.5Ba7.5Ga16Ge30 bulks can be optimized by high-pressure and high-temperature (HPHT) sintering. After HPHT sintering, abundant nanograins are randomly distributed in the sample. Grains are refined by HPHT, with the grains being smaller with higher pressure. In comparison with the arc-melted sample, the samples obtained by quenching under high pressure possess a great number of nanograins and lattice structural disorders. Lower thermal conductivity is benefited by our deliberately engineered microstructures via HPHT, and the minimum thermal conductivity is 0.86 W m-1 K-1 at 773 K. The thermal conductivity and electrical properties are optimized simultaneously by raising the reactive sintering pressure. In comparison with the arc-melted sample (0.56), a maximum zT value of 1.13 at 773 K is obtained for the Yb0.5Ba7.5Ga16Ge30 sample fabricated at 5 GPa. This demonstrates that HPHT provides an effective strategy to improve TE performance through simultaneously enhancing electrical and thermal transport properties and should be applicable to other thermoelectric materials.
RESUMO
We developed suitable high-pressure and high-temperature (HPHT) conditions for improvement of the thermoelectric properties of nonstoichiometric TiO1.80. X-ray diffraction, scanning transmission microscopy, transmission electron microscopy, and ultraviolet spectral measurements demonstrate that the crystal structures and microstructures are strongly modulated by our HPHT. The electrical properties and thermal conductivity are improved simultaneously by raising the reactive sintering pressure. The band gap was narrowed, contributing to the increase of the electrical properties with the pressure. In addition, relatively low thermal conductivities were obtained here as a result of a full spectrum of phonon scattering, benefiting from our deliberately engineered microstructures via HPHT. As a consequence, a high dimensionless figure of merit (zT) of 0.36 was obtained at 700 °C in the sample fabricated at 5 GPa. As far as we know, this is higher than all of the results of nonstoichiometric titanium oxide by other means and an enhancement of 57% of the best ever result. HPHT offers us a promising alternative for optimization of the thermoelectric properties, and it is worthwhile to popularize it.
RESUMO
With the continuous development of the diamond industry, the China-type cubic press (CCP) has gradually become larger. As a result, the volume of the tungsten carbide (WC) anvil has been increased. Considering that the WC anvil is sintered, a larger volume will deteriorate sintering quality, which could facilitate the formation of cracks during its operation. One feasible way to reduce the volume of the WC anvil is to decrease its diameter and height. Along these lines, in this work, by performing finite element simulations, it was found that a reduction in the diameter of the WC anvil would increase the von Mises stress (VMS) during the synthesis process, as well as reduce the service life of the WC anvil and the ultimate pressure of the CCP. At the same time, a smaller diameter of the WC anvil would cause a significant increase in the VMS of the base steel block, exceeding its yield limit. In addition, a reduction in the height of the WC anvil would lessen the VMS during the synthesis process, and the VMS of the base steel block will also decrease. A reduction in the height of the WC anvil will decrease the pretightening force on the WC anvil, thereby reducing its lateral support effect. When the interference fit was increased from 0.6 to 0.8 mm and the steel ring angle was changed from 1.5° to 1.1°, the pretightening force on the low WC anvil was similar to the pretightening force on the original WC anvil. Our work provides valuable insights for effectively reducing the volume of the WC anvil.
RESUMO
Experiments have been carried out in a constant volume chamber to investigate the effects of Chlorella oil addition on the laminar burning velocity and Markstein length of Chlorella oil/RP-3 kerosene blends at an initial pressure of 0.1 MPa and temperature of 450 K over a wide equivalence ratio range from 0.8 to 1.4. The result shows that at equivalence ratios of 0.9 and 1.1, with the increase of Chlorella oil addition, no cellular structure is observed in the flame propagation images. It means that the Chlorella oil addition has little effect on the flame stability under these experimental conditions; however, at an equivalence ratio of 1.3, with the increase of Chlorella oil addition from 0 to 0.5, the flame tends to be stable. It is found that the Markstein length of Chlorella oil/RP-3 blend decreases with the increase of the equivalence ratio. The blend with 0.5 Chlorella oil addition has a more rapid decrease in Markstein length compared with that of the RP-3 between the equivalence ratio from 1.1 to 1.3. The peak laminar burning velocity of Chlorella oil/RP-3 kerosene blend is obtained at the equivalence ratio of 1.1, and with the increase of Chlorella oil addition from 0 to 0.5, the laminar burning velocity increases about 20%.
RESUMO
Type-I clathrate compounds Yb x Ba8-x Ga16Ge30 have been synthesized by the high-pressure and high-temperature (HPHT) method rapidly. The effects of the synergy of atom filling and pressure regulation on the microstructure and thermal and electrical properties have been investigated. With the content of Yb atom increasing, the carrier concentration is improved, the electrical resistivity and the absolute Seebeck coefficient are decreased, while the thermal conductivity is reduced significantly. A series of extremely low lattice thermal conductivities are achieved, attributed to the enhancement of multiscale phonon scattering for the "rattling" of the filled guest atoms, the heterogeneous distribution of nano- and microstructures, grain boundaries, abundant lattice distortions, lattice deformations, and dislocations. As a result, a maximum ZT of about 1.07 at 873 K has achieved for the Yb0.5Ba7.5Ga16Ge30 sample.
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In this work, we presented the influence of catalyst geometric construction on temperature distribution, flow structure, the transport processes of the carbon atoms, and the resulting diamond growth in the process of HPHT diamond synthesis. Several catalyst geometry models were tested, and the experimental results of growth rates were compared with numerical simulations. We revealed that increasing the protrusion diameter of the convex-shaped catalysts could significantly improve the growth rate of diamonds. The diamond growth rate was improved from 1.6 mg h-1 to 4 mg h-1 when the protrusion diameter was enlarged by 2 mm. These results will be discussed through the characteristic distributions of the temperature and convection fields in the process of diamond growth.
RESUMO
A double bevel anvil of the cubic high pressure apparatus (CHPA) was developed, adopting tungsten carbide as the anvil material. We have performed finite element analyses of conventional single bevel anvil and double bevel anvil. The results indicate that the double bevel anvil has two advantages. Firstly, to gain the same chamber pressure, the oil pressure of CHPA using double bevel anvil decreases about 10.8% than that using single bevel anvil. Secondly, double beveling can maintain the pressurized seal stability of the sample chamber, which is often sacrificed with improve the pressure of sample chamber. The results of finite element analyses are well consistent with the experimental results at CHPA (SPD-6x1200 type).
RESUMO
Materials combining the hardness and strength of diamond with the higher thermal stability of cubic boron nitride (cBN) have broad potential value in science and engineering. Reacting nanodiamond with cBN at moderate pressures and high temperatures provides a pathway to such materials. Here we report the fabrication of Cx-BN nanocomposites, measuring up to 10 mm in longest dimension, by reacting nanodiamond with pre-synthesized cBN in a large-volume press. The nanocomposites consist of randomly-oriented diamond and cBN domains stitched together by sp(3)-hybridized C-B and C-N bonds, leading to p-type semiconductivity. Dislocations near the sutures accommodate lattice mismatch between diamond and cBN. Nanotwinning within both diamond and cBN domains further contributes to a bulk hardness ~50% higher than sintered cBN. The nanocomposite of C2-BN exhibits p-type semiconductivity with low activation energy and high thermal stability, making it a functional, ultrahard substance.
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The ignition delay times of methane/air mixture diluted by N2 and CO2 were experimentally measured in a chemical shock tube. The experiments were performed over the temperature range of 1300-2100 K, pressure range of 0.1-1.0 MPa, equivalence ratio range of 0.5-2.0 and for the dilution coefficients of 0%, 20% and 50%. The results suggest that a linear relationship exists between the reciprocal of temperature and the logarithm of the ignition delay times. Meanwhile, with ignition temperature and pressure increasing, the measured ignition delay times of methane/air mixture are decreasing. Furthermore, an increase in the dilution coefficient of N2 or CO2 results in increasing ignition delays and the inhibition effect of CO2 on methane/air mixture ignition is stronger than that of N2. Simulated ignition delays of methane/air mixture using three kinetic models were compared to the experimental data. Results show that GRI_3.0 mechanism gives the best prediction on ignition delays of methane/air mixture and it was selected to identify the effects of N2 and CO2 on ignition delays and the key elementary reactions in the ignition chemistry of methane/air mixture. Comparisons of the calculated ignition delays with the experimental data of methane/air mixture diluted by N2 and CO2 show excellent agreement, and sensitivity coefficients of chain branching reactions which promote mixture ignition decrease with increasing dilution coefficient of N2 or CO2.
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The use of detailed chemical reaction mechanisms of kerosene is still very limited in analyzing the combustion process in the combustion chamber of the aircraft engine. In this work, a new reduced chemical kinetic mechanism for fuel n-decane, which selected as a surrogate fuel for kerosene, containing 210 elemental reactions (including 92 reversible reactions and 26 irreversible reactions) and 50 species was developed, and the ignition and combustion characteristics of this fuel in both shock tube and flat-flame burner were kinetic simulated using this reduced reaction mechanism. Moreover, the computed results were validated by experimental data. The calculated values of ignition delay times at pressures of 12, 50 bar and equivalence ratio is 1.0, 2.0, respectively, and the main reactants and main products mole fractions using this reduced reaction mechanism agree well with experimental data. The combustion processes in the individual flame tube of a heavy duty gas turbine combustor were simulated by coupling this reduced reaction mechanism of surrogate fuel n-decane and one step reaction mechanism of surrogate fuel C12H23 into the computational fluid dynamics software. It was found that this reduced reaction mechanism is shown clear advantages in simulating the ignition and combustion processes in the individual flame tube over the one step reaction mechanism.
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This article theoretically investigates the lateral support on cubic high-pressure anvil using finite element analysis. The results show that to gain the same chamber pressure, the value of system oil pressure can be decreased by reducing the lateral support area and the anvils' lifetime is extended when the lateral support area grows. The optimal lateral support area to maximize anvils' lifetime is 27.96 cm(2). Furthermore, the chamber pressure will increase by about 6.99% when the value of lateral support area reduces from 33.16 to 27.96 cm(2) under same hydraulic rams. Our simulation results have been verified by many high-pressure synthesis experiments and illustrated by breakage of anvils.
RESUMO
A hybrid-anvil used in cubic high pressure apparatus is presented, which makes it possible to pressurize samples of 36 mm(3) volume up to 5.5 GPa and to heat simultaneously up to 1350-1400 degrees C for routine operation. The hybrid-anvil has been designed based on the theory of multilayered pressure vessels and massive support, which can save weight about 60.00% compared to the traditional anvil. We note from 10 000 times of experiments that the rate of failure crack decreases about 16.67% and the cost of anvil saves about 66.40% after the modification of the anvil. This represents a relatively simple and inexpensive anvil for material synthesis and research.