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High-entropy nanoparticles have received notable attention due to their tunable properties and broad material space. However, these nanoparticles are not suitable for certain applications (e.g., battery electrodes), where their microparticle (submicron to micron) counterparts are more preferred. Conventional methods used for synthesizing high-entropy nanoparticles often involve various ultrafast shock processes. To increase the size thereby achieving high-entropy microparticles, longer reaction time (e.g., heating duration) is usually used, which may also lead to undesired particle overgrowth or even densified microstructures. In this work, an approach based on Joule heating for synthesizing high-entropy oxide (HEO) microparticles with uniform elemental distribution is reported. In particular, two key synthesis conditions are identified to achieve high-quality HEO microparticles: 1) the precursors need to be loosely packed to avoid densification; 2) the heating time needs to be accurately controlled to tens of seconds instead of using milliseconds (thermal shock) that leads to nanoparticles or longer heating duration that forms bulk structures. The utility of the synthesized HEO microparticles for a range of applications, including high-performance Li-ion battery anode and water oxidation catalyst. This study opens up a new door toward synthesizing high-entropy microparticles with high quality and broad material space.
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The exsolution of nanoparticles (NPs) on material surfaces exhibits good performance with great potential in the field of catalysis. In this study, a method with twice lasers treatment (TLT) is proposed for the first time to rapidly promote the exsolution of Co NPs to the surface of (La0.7Sr0.3)0.93Ti0.93Co0.07O3(LSTC) by laser rapid heating to enhance the electrochemical performance of the LSTC. The entire process from precursor powder-stable perovskite crystal structure-Co NPs exsolution on the LSTC surface takes only ≈36 s by TLT. The Co NPs exsolution was confirmed by x-ray diffractometer, scanning electron microscopy and high-resolution transmission electron microscopy. After TLT, a large number of Co NPs reached 75 particlesµm-2appeared on the surface of LSTC with the onset potential of 1.38 V, the overpotential of 214 mV, and the Tafel slope of 81.14 mV dec-1, showing good catalytic activity and long-term stability. The novel process of using TLT to rapidly induce exsolution of NPs enables the rapid preparation of nanoparticle-decorated perovskite materials with better electrochemical properties, thus enriching exsolution technology and opening a new avenue for surface science research.
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Fast charging is a key enabler of mainstream adoption of electric vehicles (EVs). None of today's EVs can withstand fast charging in cold or even cool temperatures due to the risk of lithium plating. Efforts to enable fast charging are hampered by the trade-off nature of a lithium-ion battery: Improving low-temperature fast charging capability usually comes with sacrificing cell durability. Here, we present a controllable cell structure to break this trade-off and enable lithium plating-free (LPF) fast charging. Further, the LPF cell gives rise to a unified charging practice independent of ambient temperature, offering a platform for the development of battery materials without temperature restrictions. We demonstrate a 9.5 Ah 170 Wh/kg LPF cell that can be charged to 80% state of charge in 15 min even at -50 °C (beyond cell operation limit). Further, the LPF cell sustains 4,500 cycles of 3.5-C charging in 0 °C with <20% capacity loss, which is a 90× boost of life compared with a baseline conventional cell, and equivalent to >12 y and >280,000 miles of EV lifetime under this extreme usage condition, i.e., 3.5-C or 15-min fast charging at freezing temperatures.
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High Li+ conductivity, good interfacial compatibility, and nano-scale particle size have always been essential conditions for selecting inorganic fillers in high-performance composite solid electrolytes. In this study, non-milled in situ LLZO fillers with nanosize was synthesized via the sol-gel method by rapid heating sintering, which resulted in more surface defects and fewer impurities in LLZO. Compared with milled LLZO fillers, these non-milled LLZO fillers with more surface defects and fewer impurities can effectively reduce the crystallinity of PEO and agglomeration in PEO, which can form composite electrolytes with high Li+ conductivity. Most importantly, the discharge capacity of the 7.5% non-milled LLZO-PEO-based LiFePO4/Li battery is about 135.5 mA h g-1 at 1C and 60 °C. After 100 cycles, the discharge specific capacity remains at 99%. It is worth noting that nano-sized non-milled LLZO will improve the discharge capacity of LiFePO4/Li batteries to 122.1 mA h g-1 at 0.2C and 30 °C.
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Interactions between energetic material relevant nanoscale metal oxides (SiO2, TiO2, MgO, Al2O3, CuO, Bi2O3) and poly(vinylidene fluoride) (PVDF) at high temperature were investigated by temperature-jump/time-of-flight mass spectrometry (T-jump/TOFMS) and thermogravimetric-differential scanning calorimetry (TGA-DSC). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology of the compositions, while X-ray diffraction (XRD) was utilized to analyze the condensed phase crystalline species at temperatures of interest. The exergonicity and exothermicity of HF gas with hydroxyl-terminated metal oxide surfaces make HF the likely fluorine-bearing moiety and primary mode of the fluorinating reactions, where terminal OH- configurations are replaced by F- in the formation of a stronger metal-fluorine bond. However, not all compositions produce corresponding stable metal fluoride. The results show that while some of the investigated metal oxide-PVDF compositions enhance PVDF decomposition and release HF in larger quantities than PVDF, others release HF in smaller quantities than PVDF and even retard PVDF decomposition. The former compositions demonstrate exothermic, multistep mass loss modes prior to neat PVDF mass loss, and the relative intensity of HF gas increases as the temperature of the release point decreases, implying a correlation between HF release and the progression of exothermic behavior. An interplay dynamic where surface interactions both lower the onset of HF release and engage exothermically with HF gas subsequently is proposed.
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Al alloy parts fabricated by powder bed fusion (PBF) have attracted much attention because of the degrees of freedom in both shapes and mechanical properties. We previously reported that the Si regions in Al-Si alloy that remain after the rapid remelting process in PBF act as intrinsic heterogeneous nucleation sites during the subsequent resolidification. This suggests that the Si particles are crucial for a novel grain refinement strategy. To provide guidelines for grain refinement, the effects of solidification, remelting, and resolidification conditions on microstructures were investigated by multiphase-field simulation. We revealed that the resolidification microstructure is determined by the size and number of Si regions in the initial solidification microstructures and by the threshold size for the nucleation site, depending on the remelting and resolidification conditions. Furthermore, the most refined microstructure with the average grain size of 4.8 µm is predicted to be formed under conditions with a large temperature gradient of Gsol = 106 K/m in the initial solidification, a high heating rate of HR = 105 K/s in the remelting process, and a fast solidification rate of Rresol = 10-1 m/s in the resolidification process. Each of these conditions is necessary to be considered to control the microstructures of Al-Si alloys fabricated via PBF.
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Concerning the emissions of hydrogen cyanide (HCN) and other N-bearing air pollutants from the fluid catalytic cracking (FCC) regeneration units, this paper has conducted a comprehensive testing and surface characterisation of four industrial spent catalysts, aged catalysts and hard coke sample in three different schemes, Ar-TPD, O2 -TPO and rapid heating to elaborate the transformation of N upon the influence of the heterogeneity of coke and N speciation. In the Ar-TPD scheme, the surface N is responsive for the emission of gaseous NH3 from pyrrolic N-5 and HCN from both pyridinic N-6 and quaternary N-Q. The removal of soft coke is beneficial in promoting the surface exposure of hard coke, thereby increasing the HCN emission dramatically. In the O2-TPO scheme, the oxygen accessibility is the principal factor governing the emission of HCN. The external soft coke is able to access the bulk O2 firstly, the combustion of which in turn provides heat back to promote the cracking of internal hard coke from the same and neighbouring particles to release more HCN. The induction effect of bulk O2 is also superior over the spent catalyst properties in formulating a nearly identical trend of HCN emission for all the four spent catalysts tested. Finally, for the use of rapid heating scheme that is typical in a commercial FCC regenerator, it is effective in accelerating the volatilisation of soft coke quickly, thereby promoting the oxygen accessibility to hard coke and the internal N-bearing precursors so as to mitigate the emission of HCN effectively. The use of a large superficial velocity of gas is further effective in sweeping the volatiles including HCN away from the catalyst, promoting their oxidation extent accordingly.
Assuntos
Poluentes Atmosféricos , Coque , Catálise , Gases , OxigênioRESUMO
Surface rapid heating process is an efficient and green method for large-volume production of polymer optics by adopting 3D graphene network coated silicon molds with high thermal conductivity. Nevertheless, the heat transfer mechanism including the interface thermal resistance evolution between 3D graphene network coating and polymer has not been thoroughly revealed. In this study, the interface thermal resistance model was established by simplifying the contact situation between the coating and polymethylmethacrylate (PMMA), and then embedding into the finite element method (FEM) model to study the temperature variations of PMMA in surface rapid heating process. Heating experiments for graphene network were then carried out under different currents to provide the initial heat for heat transfer model. In addition, residual stress of the PMMA lens undergoing the non-uniform thermal history during molding was presented by the simulation model together. Finally, the optimal molding parameters including heating time and pressure will be determined according to calculation results of the interface thermal resistance model and microlens array molding experiment was conducted to illustrate that the interface thermal resistance model can predict the temperature of the polymer to achieve a better filling of microlens array with smooth surface and satisfactory optical performance.
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When hot forging 7075 aluminum alloy, as a military material durable enough for most of its applications, it needs to be heat-treated to ensure the target material property achieves the application requirements. However, the material properties change because of heat throughout usage. In this study, a new approach was devised to heat treat the alloy to prevent material property changes. The study further clarified the effect of rapid heat treatment on the high-temperature resistance of a hot forging 7075 aluminum alloy. Infrared (IR) heat treatment was used as a rapid heating technique to effectively replace the conventional resistance heat (RH) treatment method. Our experimental result showed that IR heat treatment resulted in better age hardening at the initial aging stage, where its tensile strength and elongation appeared like that of a resistance heat treatment. More so, based on hardness and tensile test results, the IR-heated treatment process inhibited the phase transformation of precipitations at a higher temperature, improving high-temperature softening resistance and enhancing the thermal stability of the hot forging 7075 aluminum alloy.
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Thermal nanoimprint lithography is playing a vital role in fabricating micro/nanostructures on polymer materials by the advantages of low cost, high throughput, and high resolution. However, a typical thermal nanoimprint process usually takes tens of minutes due to the relatively low heating and cooling rate in the thermal imprint cycle. In this study, we developed an induction heating apparatus for the thermal imprint with a mold made of ferromagnetic material, nickel. By applying an external high-frequency alternating magnetic field, heat was generated by the eddy currents and magnetic hysteresis losses of the ferromagnetic nickel mold at high speed. Once the external alternating magnetic field was cut off, the system would cool down fast owe to the small thermal capacity of the nickel mold; thus, providing a high heating and cooling rate for the thermal nanoimprint process. In this paper, nanostructures were successfully replicated onto polymer sheets with the scale of 4-inch diameter within 5 min.
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The invasive brown marmorated stink bug, Halyomorpha halys, is causing economic and ecological damage in invaded areas. Its overwintering behavior warrants mitigation practices in warehouses and shipping operations. The aim of this study was to characterize the mortality response curves of H. halys adults to short high-temperature exposure. Here we compared field-collected individuals entering (ENA) and exiting diapause (EXA). EXA adults displayed increased susceptibility to high temperatures compared to ENA individuals. Complete mortality of all tested individuals was obtained after 10 min exposure at 50.0 °C, and after 15 (EXA) or 20 min (ENA) at 47.5 °C. The nutritional status of these insects had no effect on high-temperature tolerance. The mortality curves obtained here may be used for the definition of cost-effective heat treatments aimed at the H. halys control.
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Micro process engineering as a process synthesis and intensification tool enables an ultra-short thermal treatment of foods within milliseconds (ms) using very high surface-area-to-volume ratios. The innovative application of ultra-short pasteurization and sterilization at high temperatures, but with holding times within the range of ms would allow the preservation of liquid foods with higher qualities, thereby avoiding many unwanted reactions with different temperature-time characteristics. Process challenges, such as fouling, clogging, and potential temperature gradients during such conditions need to be assessed on a case by case basis and optimized accordingly. Owing to the modularity, flexibility, and continuous operation of micro process engineering, thermal processes from the lab to the pilot and industrial scales can be more effectively upscaled. A case study on thermal inactivation demonstrated the feasibility of transferring lab results to the pilot scale. It was shown that micro process engineering applications in thermal food treatment may be relevant to both research and industrial operations. Scaling of micro structured devices is made possible through the use of numbering-up approaches; however, reduced investment costs and a hygienic design must be assured.
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Amorphous Fe73B7Si16Nb3Cu1 ribbon was crystallized rapidly by electric current heating under simultaneously applied tensile stress along the ribbon axis. As a result, strong transverse magnetic anisotropy was induced in the ribbon. Dynamic magnetic properties of the ribbons rapidly heated either under the tensile stress or without tensile stress were measured using toroidal cores. Optimal electric current heating regime that provides maximum improvement of the initial magnetic permeability and core loss was determined. Tensile stress increase from 0 to 180 MPa was shown to result in the decrease of the initial magnetic permeability down to 400 and core loss at frequencies from 0.4 to 200 kHz. Comparative analysis of magnetic properties of the cut core (with non-magnetic gap) and the cores heated under tensile stress was carried out. The magnetic properties of the latter cores are advantageous for manufacturing the reactors and linear chokes of switch-mode power supplies.