We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) change...We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 h.The typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable technique.To investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat test.Based on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation treatment.Further investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.展开更多
Phase transitions, morphology changes, and oxidation mechanism of the ilmenite oxidation process were investigated. FeTi03 transforms to hematite and rutile when oxidation at 700-800 ℃, and pseudobrookite is formed w...Phase transitions, morphology changes, and oxidation mechanism of the ilmenite oxidation process were investigated. FeTi03 transforms to hematite and rutile when oxidation at 700-800 ℃, and pseudobrookite is formed when the oxidation temperature reaches 900 ℃. The initial ilmenite powder exhibits paramagnetism; however, after being oxidized at the intermediate temperature （800-850 ℃）, the oxidation product exhibits weak ferromagnetism. The oxidation mechanism was discussed. The microstructure observations show that a lot of micro-pores emerge on the surfaces of ilmenite particles at the intermediate temperature, which is deemed to be caoable ofenhancin~ the mass transfer ofoxgen during oxidation.展开更多
The effect of grain size reduction on the high temperature oxidation of binary two phase alloys was discussed based on the recent research progress. The results show that for those two phase alloys with coarse grain p...The effect of grain size reduction on the high temperature oxidation of binary two phase alloys was discussed based on the recent research progress. The results show that for those two phase alloys with coarse grain prepared by the conventional methods, complex oxide scales are easily formed after oxidation under high oxygen pressure or under oxygen pressure below the stability limit of the less reactive component oxides. On the contrary, for the nano sized alloys, an exclusive external oxidation of the most reactive component usually occurs during oxidation in air or pure oxygen even for much lower content of the most reactive component. So the gain size reduction is not always beneficial to improve the oxidation resistance of the materials, but exhibits different effects depending mainly on the protective feature of the scales. The transition mechanisms between the different oxidation modes are discussed with respect to the thermodynamic and dynamic aspects.展开更多
Precisely reducing the size of metal-organic frameworks(MOFs)derivatives is an effective strategy to manipulate their phase engineering owing to size-dependent oxidation;however,the underlying relationship between the...Precisely reducing the size of metal-organic frameworks(MOFs)derivatives is an effective strategy to manipulate their phase engineering owing to size-dependent oxidation;however,the underlying relationship between the size of derivatives and phase engineering has not been clarified so far.Herein,a spatial confined growth strategy is proposed to encapsulate small-size MOFs derivatives into hollow carbon nanocages.It realizes that the hollow cavity shows a significant spatial confinement effect on the size of confined MOFs crystals and subsequently affects the dielectric polarization due to the phase hybridization with tunable coherent interfaces and heterojunctions owing to size-dependent oxidation motion,yielding to satisfied microwave attenuation with an optimal reflection loss of-50.6 d B and effective bandwidth of 6.6 GHz.Meanwhile,the effect of phase hybridization on dielectric polarization is deeply visualized,and the simulated calculation and electron holograms demonstrate that dielectric polarization is shown to be dominant dissipation mechanism in determining microwave absorption.This spatial confined growth strategy provides a versatile methodology for manipulating the size of MOFs derivatives and the understanding of size-dependent oxidation-induced phase hybridization offers a precise inspiration in optimizing dielectric polarization and microwave attenuation in theory.展开更多
Based on the new process named "Combination Method" for metallurgy and separation of Baotou mixed rare earth concentrate(BMREC),the aim of this paper is to clearly elucidate the phase change behavior of BMRE...Based on the new process named "Combination Method" for metallurgy and separation of Baotou mixed rare earth concentrate(BMREC),the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450-800℃.The results indicate that the bastnaesite in BMREC is decomposed at 450-550℃,the weight loss is about 10.3 wt%,and the activation energy(E) is 144 kJ/mol.The bastnaesite in BMREC is decomposed into rare earth fluoride,rare earth oxides(La_(2)O_(3),Ce_(7)O_(12),Pr_(6)O_(11) and Nd_(2)O_(3)),and CO_(2),particularly,with the increase of roasting temperature,bastnaesite in BMREC is more completely decomposed into LaF_(3),which causes a decrease in leaching rate of La during the HCI leaching process.Additionally,the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500℃,and the oxidation reaction rate of cerium increases with the increasing roasting temperature.展开更多
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
Titaniferous magnetite ore is a kind of symbiotic complex ore which comprises ilmenite, magnetite, hercynite and magnesio-hercynite spinel minerals. The ore collected from eastern India was characterized by XRD, WDXRF...Titaniferous magnetite ore is a kind of symbiotic complex ore which comprises ilmenite, magnetite, hercynite and magnesio-hercynite spinel minerals. The ore collected from eastern India was characterized by XRD, WDXRF, SEM and M？ssbauer spectroscopy. The oxidation behaviour of fine ore was investigated by TG-DTA analysis under oxygen atmosphere. Subsequent isothermal oxidation experiments were carried out under oxygen and air atmospheres, holding the samples for different periods of time at different temperatures from 873 K to 1473 K. It was observed that ilmenite phase transformed to hematite and titanium dioxide at lower temperature, whereas ferric-pseudobrookite phase was found at higher temperature. Direct reduction of oxidized sample-coke cylindrical briquettes was successfully achieved for phase transition from titaniferous magnetite to iron and titanium dioxide at 1473 K.展开更多
Initial oxidation behavior of NiCoCrAlY coating prepared by arc-ion plating has been studied in air at 900, 1000 and 1100 ℃. The results showed that phase transformation from transient θ-Al_(2)O_(3) to α-Al_(2)O_(3...Initial oxidation behavior of NiCoCrAlY coating prepared by arc-ion plating has been studied in air at 900, 1000 and 1100 ℃. The results showed that phase transformation from transient θ-Al_(2)O_(3) to α-Al_(2)O_(3) was highly related to the temperature and oxidation time. The oxide scale in the initial stage was mainly composed of θ-Al_(2)O_(3) at 900 ℃. Instead, more amount of α-Al_(2)O_(3) emerged out with increasing oxidation temperature. The elemental distribution after oxidation confirmed that faster chromium diffusion to the oxide scale played an important role in the speedy transformation from θ-Al_(2)O_(3) to α-Al_(2)O_(3). Y segregation at scale/coating interface resulted in less cavity formation and hence improved the oxide scale adherence.展开更多
Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic re...Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V+Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No. 4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzaldehyde were higher than those on the undoped catalyst. This was attributed to the disordered structure of V_2O_5 lattice of the K-doped catalyst and a better interracial contact between the particles.展开更多
In this paper,shorter residence time（a few minutes）with high yield in the trickle bed process for per- acetic acid synthesis by acetaldehyde liquid phase oxidation can be realized on the selected packing material SA...In this paper,shorter residence time（a few minutes）with high yield in the trickle bed process for per- acetic acid synthesis by acetaldehyde liquid phase oxidation can be realized on the selected packing material SA-5118.For acetaldehyde in acetone with ferric ion as catalyst,the optimized process conditions were presented. The main factors influencing the yield,selectivity and conversion are residence time,temperature and acetaldehyde concentration,respectively.The temperature range checked is from 30 to 65℃.High yield of 81.53%with high se- lectivity of 91.84%can be obtained at higher temperature of 55℃when the residence time is 5.5min and the acet- aldehyde concentration is 9.85%（by mass）.And there is a critical acetaldehyde concentration point（Cccp）between 18%and 19.5%（by mass）.At temperature less than 55℃,the highest yield to peracetic acid at each temperature level increases with temperature when the acetaldehyde concentration is below Cccp and decreases with temperature when the acetaldehyde concentration is above Cccp.展开更多
The oxidation of two phase Cu Cr alloys containing 25% and 50% Cr prepared by powder metallurgy (PM) with a rather uniform two phase microstructure has been studied at 700～900 ℃ under oxygen pressure below the stabi...The oxidation of two phase Cu Cr alloys containing 25% and 50% Cr prepared by powder metallurgy (PM) with a rather uniform two phase microstructure has been studied at 700～900 ℃ under oxygen pressure below the stability of the copper oxides. The two PM alloys oxidized very slowly and formed only external Cr 2O 3 scales rather than undergoing an internal oxidation of chromium. This result is attributed mainly to a supply of chromium from the small Cr rich particles dispersed within the Cu rich phase. The oxidation kinetics of the two PM Cu Cr alloys approximately followed the parabolic rate law. The scaling rates are of the same order as those measured for pure chromium under the same oxygen pressure, but smaller than those for the alloys of similar composition prepared by normal arc melting techniques, whose compositions were largely non uniform. The results are interpreted in terms of the two phase nature of these alloys.展开更多
High-temperature oxidation is an important property to evaluate thermal protection materials. However, since oxidation is a complex process involving microstructure evolution, its quantitative analysis has always been...High-temperature oxidation is an important property to evaluate thermal protection materials. However, since oxidation is a complex process involving microstructure evolution, its quantitative analysis has always been a challenge. In this work, a phase field method （PFM） based on the thermodynamics theory is developed to simulate the oxidation behavior and oxidation induced growth stress. It involves microstructure evolution and solves the problem of quantitatively computational analysis for the oxidation behavior and growth stress. Employing this method, the diffusion process, oxidation performance, and stress evolution axe predicted for Fe-Cr-A1-Y alloys. The numerical results agree well with the experimental data. The linear relationship between the maximum growth stress and the environment oxygen concentration is found. PFM provides a powerful tool to investigate high-temperature oxidation in complex environments.展开更多
For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified ...For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.展开更多
In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were...In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.展开更多
The cormsion in air of a two-phase Cu-75Cr alloy was studied at 700-900℃. Thealloy cormded nearly parabolically at 700-800℃, but at 900℃ its instantaneousparabolic mte constant decreased with time. The scales were ...The cormsion in air of a two-phase Cu-75Cr alloy was studied at 700-900℃. Thealloy cormded nearly parabolically at 700-800℃, but at 900℃ its instantaneousparabolic mte constant decreased with time. The scales were complex and consistedof an outermost layer of copper oxide generally followed bg a layer of the double ox-ide Cu2 Cr2 O4 sometimes containing particles of unoxidized chromium surmunded bya chromia layer. An innermost layer of chromia was also observed in some cases.Finally metallic copper was al8o frequently mixed with chromia particles. No Cr de-pletion was observed in the alloy close to the inteffoce with the scale. In any case,this alloy was not able to form an exclusive continuous protective chromia layer. Thespecial cormsion behavior Of this alloy is typical of two-phase binary systems with alange solubility gaP in which the outwaof dthesion fiux of the most-reactive componentin the alloy is strongly reduced and may be inswncient to fOrm a protective externallayer of the cormsponding oxide. In paTticular, the presence of particles of Cr withina double oxide layer is very unusual and is allowed only for the kinetic reason.展开更多
In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction tempe...In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.展开更多
A series of Co-based oxide catalysts were prepared by calcining hydrotalcite precursors in different atmospheres and studied for HCHO catalytic oxidation. The N2-calcined catalyst exhibits enhanced HCHO oxidation and ...A series of Co-based oxide catalysts were prepared by calcining hydrotalcite precursors in different atmospheres and studied for HCHO catalytic oxidation. The N2-calcined catalyst exhibits enhanced HCHO oxidation and superior stability. On the basis of H2-TPR, X-ray photoelectron spectroscopy, and Raman characterizations, this can be ascribed to better redox ability, octahedrally coordinated Co2+ ions derived from the CoO phase, and other surface oxygen species, such as O2– or O–. The extra octahedrally coordinated Co2+ ions may reside in a more open framework site than the inactive tetrahedrally coordinated Co2+ ions. This species of Co2+ can easily make contact with oxygen and oxidize. The surface oxygen species, along with the octahedrally coordinated Co2+ ions, and a part of the Co3+ species constitute the Co2+-oxygen species-Co3+ sites, which enhance the catalytic activities. According to DRIFTS, Co2+-oxygen species-Co3+ makes oxidation of HCHO and conversion of DOM to formate easier.展开更多
To understand the formation and growth of plasma electrolytic oxidation(PEO) coatings in presence of different secondary phases in a substrate,PEO treatment was carried out on AlSi9 Cu3 alloy at different treatment ti...To understand the formation and growth of plasma electrolytic oxidation(PEO) coatings in presence of different secondary phases in a substrate,PEO treatment was carried out on AlSi9 Cu3 alloy at different treatment times ranging from 15 s to 480 s.The coating formation and evolution process was traced by surface and cross-sectional observation of the layers on the different phases of the alloy.The results demonstrated a sequential involvement of the different phases in the plasma discharges:firstly,discharges start on the α-Al matrix,then on the intermetallic Al2 Cu and β-Al5 FeSi phases at the same time and finally on the eutectic Si.The presence of intermetallic Al2 Cu remarkably affects the initial dissolution,the deposition of conversion products and the ignition of discharges at the early stages of processing.Eutectic Si in the substrate exhibits the highest electrochemical stability at all stages and contributes in the beginning to a distinct coating morphology eventually.The resultant PEO coating tends to be uniform if processing times are longer and a double-layer structure appears in the coating.展开更多
Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condit...Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condition and/or eco-friendly solvents. The catalysts were characterized by SEM, EDX, XRD, FTIR, TGA/DTA, and surface area and pore size analysis. Experimental data revealed that Fe2O3/AC(KOH) was an efficient catalyst for the oxidation (dehydrogenation) of alcohol while was found to show catalytic activity for both dehydration and dehydrogenation of alcohols. The catalysts were recycled by simple filtration, and used several times without any loss of catalytic activity.展开更多
In this study,Al-30W(wt.%)alloy powder was prepared by Aluminothermic reduction and hightemperature gas atomization.We then studied the phase composition,surface morphology,spatial phase structure,and thermal oxidatio...In this study,Al-30W(wt.%)alloy powder was prepared by Aluminothermic reduction and hightemperature gas atomization.We then studied the phase composition,surface morphology,spatial phase structure,and thermal oxidation process using XRD,SEM/EDS,TEM,DSC,and DTA/TG analysis.The results showed that the Al-30W alloy powder exhibited high sphericity,and the interior presented a special spatial phase structure in which the Al/W amorphous alloy phase and the metastable Al/W intermetallic compound phase were distributed in the pure Al matrix.When the Al-30W alloy powder was stabilized in a vacuum tube furnace,the spatial phase structure of the alloy powder changed,and a small amount of pure Al was embedded in the Al_(12)W matrix.The resulting Al-30W alloy powder products,treated in air at different temperatures,were collected in situ and characterized.The results presented that with an increase in temperature,the types and morphologies of the Al/W intermetallic compounds in the Al-30W alloy powder changed.Furthermore,the Al-30W alloy powder began to undergo intense oxidation reactions at about 900℃,accompanied by a concentrated energy release and rapid weight gain.The volatilization of WO_(3)produced in the oxidation process promoted the complete oxidation of the Al-30W alloy powder,and the Al-30W alloy powder was completely oxidized at 1300℃.At this stage,all W atoms were transformed into gaseous WO_(3),and only a large number of small Al_(2)O_(3)fragments remained in the oxidation product.Thus,the Al-30W alloy powder exhibited excellent thermal reactivity and oxidation integrity,and may offer excellent application prospects in the field of energetic materials.展开更多
基金Funded by Scientific and Technological Innovation Project of Carbon Emission Peak and Carbon Neutrality of Jiangsu Province(No.BE2022028-4)。
文摘We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 h.The typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable technique.To investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat test.Based on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation treatment.Further investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.
基金Project(51074105) supported by the National Natural Science Foundation of ChinaProject(51225401) supported by the China National Funds for Distinguished Young Scientists
文摘Phase transitions, morphology changes, and oxidation mechanism of the ilmenite oxidation process were investigated. FeTi03 transforms to hematite and rutile when oxidation at 700-800 ℃, and pseudobrookite is formed when the oxidation temperature reaches 900 ℃. The initial ilmenite powder exhibits paramagnetism; however, after being oxidized at the intermediate temperature （800-850 ℃）, the oxidation product exhibits weak ferromagnetism. The oxidation mechanism was discussed. The microstructure observations show that a lot of micro-pores emerge on the surfaces of ilmenite particles at the intermediate temperature, which is deemed to be caoable ofenhancin~ the mass transfer ofoxgen during oxidation.
文摘The effect of grain size reduction on the high temperature oxidation of binary two phase alloys was discussed based on the recent research progress. The results show that for those two phase alloys with coarse grain prepared by the conventional methods, complex oxide scales are easily formed after oxidation under high oxygen pressure or under oxygen pressure below the stability limit of the less reactive component oxides. On the contrary, for the nano sized alloys, an exclusive external oxidation of the most reactive component usually occurs during oxidation in air or pure oxygen even for much lower content of the most reactive component. So the gain size reduction is not always beneficial to improve the oxidation resistance of the materials, but exhibits different effects depending mainly on the protective feature of the scales. The transition mechanisms between the different oxidation modes are discussed with respect to the thermodynamic and dynamic aspects.
基金This work was financially supported by the National Natural Science Foundation of China(U21A2093 and 52102370)the Natural Science Foundation of Shaanxi Province(2022JM-260)+2 种基金the Shanghai Key Laboratory of R&D for Metallic Functional Materials(2021-01)and Open Fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province(JBGS014)Open access funding provided by Shanghai Jiao Tong University
文摘Precisely reducing the size of metal-organic frameworks(MOFs)derivatives is an effective strategy to manipulate their phase engineering owing to size-dependent oxidation;however,the underlying relationship between the size of derivatives and phase engineering has not been clarified so far.Herein,a spatial confined growth strategy is proposed to encapsulate small-size MOFs derivatives into hollow carbon nanocages.It realizes that the hollow cavity shows a significant spatial confinement effect on the size of confined MOFs crystals and subsequently affects the dielectric polarization due to the phase hybridization with tunable coherent interfaces and heterojunctions owing to size-dependent oxidation motion,yielding to satisfied microwave attenuation with an optimal reflection loss of-50.6 d B and effective bandwidth of 6.6 GHz.Meanwhile,the effect of phase hybridization on dielectric polarization is deeply visualized,and the simulated calculation and electron holograms demonstrate that dielectric polarization is shown to be dominant dissipation mechanism in determining microwave absorption.This spatial confined growth strategy provides a versatile methodology for manipulating the size of MOFs derivatives and the understanding of size-dependent oxidation-induced phase hybridization offers a precise inspiration in optimizing dielectric polarization and microwave attenuation in theory.
基金Project supported by the National Key Research and Development Program of China(2020YFC1909104)Science and Technology Major Project of Guangxi(GuikeAA18242022)Hebei Province Key Research and Development Plan Project(20374104D)。
文摘Based on the new process named "Combination Method" for metallurgy and separation of Baotou mixed rare earth concentrate(BMREC),the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450-800℃.The results indicate that the bastnaesite in BMREC is decomposed at 450-550℃,the weight loss is about 10.3 wt%,and the activation energy(E) is 144 kJ/mol.The bastnaesite in BMREC is decomposed into rare earth fluoride,rare earth oxides(La_(2)O_(3),Ce_(7)O_(12),Pr_(6)O_(11) and Nd_(2)O_(3)),and CO_(2),particularly,with the increase of roasting temperature,bastnaesite in BMREC is more completely decomposed into LaF_(3),which causes a decrease in leaching rate of La during the HCI leaching process.Additionally,the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500℃,and the oxidation reaction rate of cerium increases with the increasing roasting temperature.
基金supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
基金financial support from Ministry of Steel SDF project, Government of India for funding and providing fellowship
文摘Titaniferous magnetite ore is a kind of symbiotic complex ore which comprises ilmenite, magnetite, hercynite and magnesio-hercynite spinel minerals. The ore collected from eastern India was characterized by XRD, WDXRF, SEM and M？ssbauer spectroscopy. The oxidation behaviour of fine ore was investigated by TG-DTA analysis under oxygen atmosphere. Subsequent isothermal oxidation experiments were carried out under oxygen and air atmospheres, holding the samples for different periods of time at different temperatures from 873 K to 1473 K. It was observed that ilmenite phase transformed to hematite and titanium dioxide at lower temperature, whereas ferric-pseudobrookite phase was found at higher temperature. Direct reduction of oxidized sample-coke cylindrical briquettes was successfully achieved for phase transition from titaniferous magnetite to iron and titanium dioxide at 1473 K.
基金sponsored by the R&D Program in Key Fields of Guangdong Province(No.2019B010936001)the National Natural Science Foundation of China(Grant No.51671202)+1 种基金supported by the National Engineering Laboratory for Marine and Ocean Engineering Power System-Laboratory for Ocean Engineering Gas Turbine。
文摘Initial oxidation behavior of NiCoCrAlY coating prepared by arc-ion plating has been studied in air at 900, 1000 and 1100 ℃. The results showed that phase transformation from transient θ-Al_(2)O_(3) to α-Al_(2)O_(3) was highly related to the temperature and oxidation time. The oxide scale in the initial stage was mainly composed of θ-Al_(2)O_(3) at 900 ℃. Instead, more amount of α-Al_(2)O_(3) emerged out with increasing oxidation temperature. The elemental distribution after oxidation confirmed that faster chromium diffusion to the oxide scale played an important role in the speedy transformation from θ-Al_(2)O_(3) to α-Al_(2)O_(3). Y segregation at scale/coating interface resulted in less cavity formation and hence improved the oxide scale adherence.
文摘Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V+Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No. 4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzaldehyde were higher than those on the undoped catalyst. This was attributed to the disordered structure of V_2O_5 lattice of the K-doped catalyst and a better interracial contact between the particles.
文摘In this paper,shorter residence time（a few minutes）with high yield in the trickle bed process for per- acetic acid synthesis by acetaldehyde liquid phase oxidation can be realized on the selected packing material SA-5118.For acetaldehyde in acetone with ferric ion as catalyst,the optimized process conditions were presented. The main factors influencing the yield,selectivity and conversion are residence time,temperature and acetaldehyde concentration,respectively.The temperature range checked is from 30 to 65℃.High yield of 81.53%with high se- lectivity of 91.84%can be obtained at higher temperature of 55℃when the residence time is 5.5min and the acet- aldehyde concentration is 9.85%（by mass）.And there is a critical acetaldehyde concentration point（Cccp）between 18%and 19.5%（by mass）.At temperature less than 55℃,the highest yield to peracetic acid at each temperature level increases with temperature when the acetaldehyde concentration is below Cccp and decreases with temperature when the acetaldehyde concentration is above Cccp.
文摘The oxidation of two phase Cu Cr alloys containing 25% and 50% Cr prepared by powder metallurgy (PM) with a rather uniform two phase microstructure has been studied at 700～900 ℃ under oxygen pressure below the stability of the copper oxides. The two PM alloys oxidized very slowly and formed only external Cr 2O 3 scales rather than undergoing an internal oxidation of chromium. This result is attributed mainly to a supply of chromium from the small Cr rich particles dispersed within the Cu rich phase. The oxidation kinetics of the two PM Cu Cr alloys approximately followed the parabolic rate law. The scaling rates are of the same order as those measured for pure chromium under the same oxygen pressure, but smaller than those for the alloys of similar composition prepared by normal arc melting techniques, whose compositions were largely non uniform. The results are interpreted in terms of the two phase nature of these alloys.
基金Project supported by the National Natural Science Foundation of China (Nos. 90505015 and10702035)
文摘High-temperature oxidation is an important property to evaluate thermal protection materials. However, since oxidation is a complex process involving microstructure evolution, its quantitative analysis has always been a challenge. In this work, a phase field method （PFM） based on the thermodynamics theory is developed to simulate the oxidation behavior and oxidation induced growth stress. It involves microstructure evolution and solves the problem of quantitatively computational analysis for the oxidation behavior and growth stress. Employing this method, the diffusion process, oxidation performance, and stress evolution axe predicted for Fe-Cr-A1-Y alloys. The numerical results agree well with the experimental data. The linear relationship between the maximum growth stress and the environment oxygen concentration is found. PFM provides a powerful tool to investigate high-temperature oxidation in complex environments.
基金the Natural Science Foundation of Yunnan Province (2001E0011Q)the Science Foundation of The Education Department of Yunnan Province (0142111 and 07Z11402)
文摘For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.
基金supported by the National Natural Science Foundation of China (No. 21376163)
文摘In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.
文摘The cormsion in air of a two-phase Cu-75Cr alloy was studied at 700-900℃. Thealloy cormded nearly parabolically at 700-800℃, but at 900℃ its instantaneousparabolic mte constant decreased with time. The scales were complex and consistedof an outermost layer of copper oxide generally followed bg a layer of the double ox-ide Cu2 Cr2 O4 sometimes containing particles of unoxidized chromium surmunded bya chromia layer. An innermost layer of chromia was also observed in some cases.Finally metallic copper was al8o frequently mixed with chromia particles. No Cr de-pletion was observed in the alloy close to the inteffoce with the scale. In any case,this alloy was not able to form an exclusive continuous protective chromia layer. Thespecial cormsion behavior Of this alloy is typical of two-phase binary systems with alange solubility gaP in which the outwaof dthesion fiux of the most-reactive componentin the alloy is strongly reduced and may be inswncient to fOrm a protective externallayer of the cormsponding oxide. In paTticular, the presence of particles of Cr withina double oxide layer is very unusual and is allowed only for the kinetic reason.
文摘In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.
基金support by the National Natural Science Foundation of China(91544227,21777166)the National Key R&D Program of China(2016YFC0202202)~~
文摘A series of Co-based oxide catalysts were prepared by calcining hydrotalcite precursors in different atmospheres and studied for HCHO catalytic oxidation. The N2-calcined catalyst exhibits enhanced HCHO oxidation and superior stability. On the basis of H2-TPR, X-ray photoelectron spectroscopy, and Raman characterizations, this can be ascribed to better redox ability, octahedrally coordinated Co2+ ions derived from the CoO phase, and other surface oxygen species, such as O2– or O–. The extra octahedrally coordinated Co2+ ions may reside in a more open framework site than the inactive tetrahedrally coordinated Co2+ ions. This species of Co2+ can easily make contact with oxygen and oxidize. The surface oxygen species, along with the octahedrally coordinated Co2+ ions, and a part of the Co3+ species constitute the Co2+-oxygen species-Co3+ sites, which enhance the catalytic activities. According to DRIFTS, Co2+-oxygen species-Co3+ makes oxidation of HCHO and conversion of DOM to formate easier.
基金the financial surpport from China Scholarship Council(CSC)。
文摘To understand the formation and growth of plasma electrolytic oxidation(PEO) coatings in presence of different secondary phases in a substrate,PEO treatment was carried out on AlSi9 Cu3 alloy at different treatment times ranging from 15 s to 480 s.The coating formation and evolution process was traced by surface and cross-sectional observation of the layers on the different phases of the alloy.The results demonstrated a sequential involvement of the different phases in the plasma discharges:firstly,discharges start on the α-Al matrix,then on the intermetallic Al2 Cu and β-Al5 FeSi phases at the same time and finally on the eutectic Si.The presence of intermetallic Al2 Cu remarkably affects the initial dissolution,the deposition of conversion products and the ignition of discharges at the early stages of processing.Eutectic Si in the substrate exhibits the highest electrochemical stability at all stages and contributes in the beginning to a distinct coating morphology eventually.The resultant PEO coating tends to be uniform if processing times are longer and a double-layer structure appears in the coating.
文摘Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condition and/or eco-friendly solvents. The catalysts were characterized by SEM, EDX, XRD, FTIR, TGA/DTA, and surface area and pore size analysis. Experimental data revealed that Fe2O3/AC(KOH) was an efficient catalyst for the oxidation (dehydrogenation) of alcohol while was found to show catalytic activity for both dehydration and dehydrogenation of alcohols. The catalysts were recycled by simple filtration, and used several times without any loss of catalytic activity.
基金supported by the National Natural Science Foundation of China(No.51871106).We express our grat-itude for analyzing and testing of Huazhong University of Science and Technology Analytical&Testing Center.
文摘In this study,Al-30W(wt.%)alloy powder was prepared by Aluminothermic reduction and hightemperature gas atomization.We then studied the phase composition,surface morphology,spatial phase structure,and thermal oxidation process using XRD,SEM/EDS,TEM,DSC,and DTA/TG analysis.The results showed that the Al-30W alloy powder exhibited high sphericity,and the interior presented a special spatial phase structure in which the Al/W amorphous alloy phase and the metastable Al/W intermetallic compound phase were distributed in the pure Al matrix.When the Al-30W alloy powder was stabilized in a vacuum tube furnace,the spatial phase structure of the alloy powder changed,and a small amount of pure Al was embedded in the Al_(12)W matrix.The resulting Al-30W alloy powder products,treated in air at different temperatures,were collected in situ and characterized.The results presented that with an increase in temperature,the types and morphologies of the Al/W intermetallic compounds in the Al-30W alloy powder changed.Furthermore,the Al-30W alloy powder began to undergo intense oxidation reactions at about 900℃,accompanied by a concentrated energy release and rapid weight gain.The volatilization of WO_(3)produced in the oxidation process promoted the complete oxidation of the Al-30W alloy powder,and the Al-30W alloy powder was completely oxidized at 1300℃.At this stage,all W atoms were transformed into gaseous WO_(3),and only a large number of small Al_(2)O_(3)fragments remained in the oxidation product.Thus,the Al-30W alloy powder exhibited excellent thermal reactivity and oxidation integrity,and may offer excellent application prospects in the field of energetic materials.
