The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction （...The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and optical microscopy （OM）. It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150℃ for 80 min. The final phase constituents mainly consist of Fe, M305 solid solution phase （M=Mg, Ti, and Fe）, and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ.mo1-1.展开更多
A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5＋δ （CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y） were synthesized through a sol-gel route and effects of the Ln3＋ catio...A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5＋δ （CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y） were synthesized through a sol-gel route and effects of the Ln3＋ cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3＋ cations （La3＋, Pr3＋ and Nd3＋） successfully stabilized the double-layered perovskite structure of sintered LBCO, while the smaller ones （Sm3＋, Gd3＋, and Y3＋） resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8× 10^-7 mol.s-1.cm-2 at 925 ℃ with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.展开更多
Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ （BRCFT, R = Ca, La or Sr） membranes were synthesized by a solid-state reaction. Metal cation Ca2＋, La3＋ or Sr2＋ doping on A-site partially substituted Ba2＋ in BaCoo.TFe0.225Ta0....Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ （BRCFT, R = Ca, La or Sr） membranes were synthesized by a solid-state reaction. Metal cation Ca2＋, La3＋ or Sr2＋ doping on A-site partially substituted Ba2＋ in BaCoo.TFe0.225Ta0.07503-δ oxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, Hz-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2＋, La3＋ or Sr2＋, whose ionic radii are smaller than that of Ba2＋, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experi- ments showed that BRCFT with A-site fully occupied by Ba2＋ exhibited good oxygen permeation flux under He flow, reaching about 2.3 mL.min-l .cm-2 at 900 with I mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation （Ba2＋〉La3＋〉SrZ＋〉Ca2＋）.展开更多
The total conductivity,oxygen sorption property,oxygen permeability and stability of pure perovskite-type oxide BaCo0.7Fe0.2Nb0.1O3-δ (BCFNO) in real operating conditions were investigated. Its total conductivity was...The total conductivity,oxygen sorption property,oxygen permeability and stability of pure perovskite-type oxide BaCo0.7Fe0.2Nb0.1O3-δ (BCFNO) in real operating conditions were investigated. Its total conductivity was measured to be 3.6 S·cm-1 at 600°C. Though the total conductivity of the BCFNO membrane is much smaller than that of the Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCFO) membrane,the oxygen permeability of the BCFNO membrane is similar to that of the BSCFO membrane. SEM observation and EDX analysis of the BCFN...展开更多
Ba1.0Co0.7Fe0.2Nb0.1O3-γ（BCFN） oxide with perovskite cubic structure was synthesized by solid state reaction method. COa corrosion of BCFN membrane was investigated by X-ray diffraction （XRD）, scanning electron m...Ba1.0Co0.7Fe0.2Nb0.1O3-γ（BCFN） oxide with perovskite cubic structure was synthesized by solid state reaction method. COa corrosion of BCFN membrane was investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, diffuse reflectance infrared Fourier- transformed spectroscopy （DRIFT） and X-ray absorption fine structure spectroscopy （XAFS）. Cobalt （Co） K-edge absorption spectra of BCFN annealed in COa reveal that the oxidation states of Co in all the samples were larger than ＋3 and they decreased with the increase of calcination time. At 800 ℃, 1% CO2 introduced into He could speed up the reduction of Co cations in comparison with pure He. In addition, sulfate ions in the bulk of BCFN membrane preferred to migrate to the surface under CO2 calcination and form monoclinic Ba（CO3）0.9（SO4）0.1 besides orthorhombic witherite. Moreover, SEM results indicate that the nucleation and growth of carbonates grains started at the grain boundary of the membrane.展开更多
The preparation and solidification of metallic droplets attract more and more attention for their signiifcance in both engineering and scientiifc ifelds. In this paper, the preparation and characterization of Sn-based...The preparation and solidification of metallic droplets attract more and more attention for their signiifcance in both engineering and scientiifc ifelds. In this paper, the preparation and characterization of Sn-based al oy droplets using different methods such as atomization and consumable electrode direct current arc （CDCA） technique are reviewed. The morphology and structure of these droplets were determined by optical microscopy, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The solidiifcation behavior of single droplet was systematical y studied by means of scanning calorimetry （DSC）, and the nucleation kinetics was also calculated. In particular, the development of fast scanning calorimetry （FSC） made it possible to investigate the evolution of undercooling under ultrafast but control able heating and cooling conditions. The combination of CDCA technique and FSC measurements opens up a new door for quantitative studies on droplet solidiifcation, which is accessible to demonstrate some theories by experiments.展开更多
Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon...Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.展开更多
Tin nanoparticles with different size distribution were synthesized using chemical reduction method by applying NaBH4 as reduction agent.The Sn nanoparticles smaller than 100 nm were less agglomerated and no obviously...Tin nanoparticles with different size distribution were synthesized using chemical reduction method by applying NaBH4 as reduction agent.The Sn nanoparticles smaller than 100 nm were less agglomerated and no obviously oxidized.The melting properties of these synthesized nanoparticles were studied by differential scanning calorimetry.The melting temperatures of Sn nanoparticles in diameter of 81,40,36 and 34 nm were 226.1,221.8,221.1 and 219.5？欲espectively.The size-dependent melting temperature and size-dependent latent heat of fusion have been observed.The size-dependent melting properties of tin nanoparticles in this study were also comparatively analyzed by employing different size-dependent theoretical melting models and the differences between these models were discussed.The results show that the experimental data are in accordance with the LSM model and SPI model,and the LSM model gives the better understanding for the melting property of the Sn nanoparticles.展开更多
The influence of casting parameters on stray grain formation of a unidirectionally solidified superalloy IN738LC casting with three platforms was investigated by using a 3D cellular automaton-finite element （CAFE） m...The influence of casting parameters on stray grain formation of a unidirectionally solidified superalloy IN738LC casting with three platforms was investigated by using a 3D cellular automaton-finite element （CAFE） model in CALCOSOFT package. The model was first validated by comparison of the reported grain structure of AI-7%Si （mass fraction） alloy. Then, the influence of pouring temperature, heat flux of the lateral surface, convection heat coefficient of the cooled chill and mean undercooling of the bulk nucleation on the stray grain formation was studied during the unidirectional solidification. The predictions show that the stray grain formation is obviously sensitive to the pouring temperature, heat flux and mean undercooling of the bulk nucleation. However, increasing the heat convection coefficient has little influence on the stray grain formation.展开更多
Chou model was used to investigate the dehydriding reaction kinetic mechanism of MgH_2-Nb_2O_5 hydrogen storage materials at 573 K.A new conception,'characteristic absorption/desorption time(t_c)'was introduce...Chou model was used to investigate the dehydriding reaction kinetic mechanism of MgH_2-Nb_2O_5 hydrogen storage materials at 573 K.A new conception,'characteristic absorption/desorption time(t_c)'was introduced to characterize the reaction rate The fitting results show that for the hydrogen desorbing mechanism,the surface penetration is the rate-controlling step.The mechanism remains the same even when the original panicle size of Nb_2O_5 is before ball milling(BM) or when the BM time changes And t_c indicates that the desorption rate of MgH_2-Nb_2O_5 will be faster than that of MgH_2-Nb_2O_5 by BM.The dehydriding reaction rate of MgH_2-Nb_2O_5(micro particle) BMed for 50 h is 4.76 times faster than that of the MgH_2-Nb_2O_5(micro panicle) BMed for 0.25 h,while the dehydriding reaction rate of MgH_2-Nb_2O_5(nano particle) BMed for 50 h is only 1.18 times as that of the MgH2-Nb_2O_5 (nano particle) BMed for 0.25 h.The dehydriding reaction rate of the BMed MgH_2-Nb_2O_5(nano particle) is 1-9 times faster than that of the BMed MgH_2-Nb_2O_5(micro particle).展开更多
In the present work, crystal structure and for- mation mechanism of the secondary phase in Heusler Ni- Mn-Sn-Co materials were investigated using X-ray dif- fraction, scanning/transmission electron microscopy and sele...In the present work, crystal structure and for- mation mechanism of the secondary phase in Heusler Ni- Mn-Sn-Co materials were investigated using X-ray dif- fraction, scanning/transmission electron microscopy and selected-area electron diffraction techniques. Experimental results showed that the secondary phase presented in both Ni44.1Mn35.1Sn10.8Co10 as-cast bulk alloy and melt-spun ribbon, possessing a face-centered cubic （fcc） NilTSn3-type structure. The secondary phase in the as-cast bulk alloy was resulted from a eutectic reaction after the formation of a primary dendritic flphase during cooling. However in the melt-spun rapidly solidified ribbon, the secondary phase was largely suppressed as nano-precipitates distributed along the grain boundaries, which was attributed to a divorced eutectic reaction. The secondary phase exhibited partial amorphous state due to high local cooling rate.展开更多
The performance of LiNi/γ-Al2O3 catalysts modified by rare earth metal oxide （La2O3 or CeO2） packed on BCFNO membrane reactor was discussed for the partial oxidation of methane （POM） in coke oven gas （COG） at 8...The performance of LiNi/γ-Al2O3 catalysts modified by rare earth metal oxide （La2O3 or CeO2） packed on BCFNO membrane reactor was discussed for the partial oxidation of methane （POM） in coke oven gas （COG） at 875 ℃. The NiO/γ-Al2O3 catalysts with different amounts of La2O3 and CeO2 were prepared with the same preparation method and under the same condition in order to compare the reaction performance （oxygen permeation, CH4 conversion, H2 and CO selectivity） on the membrane reactor. The results show that the oxygen permeation flux increased significantly with LiNiREOx/γ-Al2O3 （RE = La or Ce） catalysts by adding the element of rare earth especially the Ce during the POM in COG. Such as, the Li15wt%CeO29wt%NiO/γ-Al2O3 catalyst with an oxygen permeation flux of 24.71 ml·cm^-2·min^-1 and a high CH4 conversion was obtained in 875 ℃. The resulted high oxygen permeation flux may be due to the added Ce that inhibited the strong interaction between Ni and Al2O3 to form the NiAl2O4 phase. In addition, the introduction of Ce leads up to an important property of storing and releasing oxygen.展开更多
Dual-phase membranes of 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Pr Ba Co2exFexO3 d（0 x 2） were prepared by a combined citrate and ethylene diamine tetraacetic acid（EDTA） complexing method. X-ray diffraction（XRD）results re...Dual-phase membranes of 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Pr Ba Co2exFexO3 d（0 x 2） were prepared by a combined citrate and ethylene diamine tetraacetic acid（EDTA） complexing method. X-ray diffraction（XRD）results revealed the good chemical compatibility between ion-conducting phase CGO and electron-conducting phases PBC2 xFxO after sintering in air. The Fe ionic dopant had a significant effect on the phase structure stability and oxygen permeability under CO2 atmosphere, which was confirmed by XRD, thermogravimetrye differential scanning calorimetry（TGeD SC）, scanning electron microscopy（SEM） and oxygen permeation experiments. CGOeP BC0.5F1.5O dual-phase membrane demonstrated a stable oxygen permeation flux of2.71x10-7mol cm 2s 1with 50 mol% He/CO2 as the sweep gas at 925 C, and this value was much higher than that of perovskite-type membranes. The rate-limiting step in the oxygen permeation process changed from the bulk diffusion to the surface oxygen exchange when the CGOeP BC0.5F1.5O membrane thickness decreased to 0.8 mm or less. Due to the high oxygen permeation fluxes and the excellent structural stability under CO2 atmosphere, the CGOeP BC0.5F1.5O membrane is a great potential candidate material for separating oxygen from air in the oxy-fuel combustion techniques.展开更多
The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SC...The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SCFNO with a thickness of 1 mm had a high level of oxygen permeation flux of 1.4 ml.min^(-1).cm^(-2) at 850 ℃ under air/He gradient.The bulk diffusion is the rate-limiting step in overall oxygen permeation mechanism for SCFNO when the thickness is higher than 1.0 mm.The partial substitution of Nb for Co suppresses the transition of oxygen vacancies order/disorder proven by DSC measurement and enhances the phase stability under low oxygen partial pressure.During long-term tests under low oxygen pressure,the SCFNO exhibites structural stability and stable oxygen permeation.It is proved that substitution of Nb for Co is an effective way to improve the properties of SCFO.展开更多
A small amount of Fe3O4 catalyst is known to substantially improve the adsorption and desorption thermodynamics and kinetics of Mg-based materials. Using density functional theory in combination with nudged elastic ba...A small amount of Fe3O4 catalyst is known to substantially improve the adsorption and desorption thermodynamics and kinetics of Mg-based materials. Using density functional theory in combination with nudged elastic band method,the dissociative chemisorptions of hydrogen on both pure and Fe-doped Mg(0001) surfaces were studied. The adsorption energy calculations show that a weakly physisorbed state above pure and Fe-doped Mg surface atoms can serve as a precursor state to dissociative chemisorption. Then,the dissociation pathway of H2 and the relative barrier were investigated. The calculated dissociation barrier(1.08 eV) of hydrogen molecule on a pure Mg(0001) surface is in good agreement with comparable experimental and theoretical studies. For the Fe-doped Mg(0001) surface,the activated barrier decreases to 0.101 eV due to the strong interaction between the s orbital of H and the d orbital of Fe.展开更多
In this paper, the thermodynamics of the reduction of ilmenite using multiple gases (H<sub>2</sub>/CO) was calculated. It is found that the metallization rate of 20.1%–98.8%, H<sub>2</sub> con...In this paper, the thermodynamics of the reduction of ilmenite using multiple gases (H<sub>2</sub>/CO) was calculated. It is found that the metallization rate of 20.1%–98.8%, H<sub>2</sub> consumption rate of 43.0%–99.1%, and carbon deposition amount of 5.7×10<sup>?7</sup>?0.49mol can be obtained based on the conditions of hydrogen volume fraction of 10%–90% and temperature of 450–1200°C. Experimental study was also carried out using synthetic ilmenite as initial materials and reduced in a static bed reactor at 1100°C. The metallization rate reaches 97% when the multiple gas (70% H<sub>2</sub>/10% CO/20% Ar) flow rate is 120ml·min<sup>?1</sup>. A thermogravimetric analyzer was used to measure the variation of sample weight caused by the deposition of solid carbon. The amount of carbon deposited during experiments reaches its maximum while the original hydrogen volume content is 20%. The experimental results are well consistent with the thermodynamic analysis.展开更多
Hydrogen production by catalytic reforming of simulated hot coke oven gas （HCOG） with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg（Al）O catalysts. The catalysts were prepared ...Hydrogen production by catalytic reforming of simulated hot coke oven gas （HCOG） with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg（Al）O catalysts. The catalysts were prepared by a homogeneous precipitation method using urea hydrolysis and characterized by ICE BET, XRD, TPR, TEM and TG. XRD showed that the hydrotalcite type precursor after calcination formed （Ni, Mg）Al2O4 spinel and Ni-Mg-O solid solution structure. TPR results suggested that the increase in Ni/Mg molar ratio gave rise to the decrease in the reduction temperature of Ni^2＋ to Ni^0 on Ni/Mg（Al）O catalysts. The reaction results indicated that toluene and CH4 could completely be converted to H2 and CO in the catalytic reforming of the simulated HCOG under atmospheric pressure and the amount of H2 in the reaction effluent gas was about 4 times more than that in original HCOG. The catalysts with lower Ni/Mg molar ratio showed better catalytic activity and resistance to coking, which may become promising catalysts in the catalytic reforming of HCOG.展开更多
Quenching experiments were performed at different cooling rates under non-directional solidification by differential thermal analysis, and the morphologic variation of primary phase, phase transition temperature and h...Quenching experiments were performed at different cooling rates under non-directional solidification by differential thermal analysis, and the morphologic variation of primary phase, phase transition temperature and hardness change at the same quenching temperature were investigated. The experimental results show that, with the gradual decrease of the cooling rate from 25 K/min, the morphology of ferrite starts to transform experiencing the dendrite, radial pattern, Widmanstatten-like and wire-net. Sample starts to present the Widmanstatten-like microstructure at 10 K/min which does not exist at higher or lower cooling rates, and this microstructure is detrimental to the mechanical property. Except 10 K/min, the hardness decreases with decreasing cooling rate.展开更多
Pulsed magneto-oscillation （PMO） as a new electromagnetic technology to generate the grain refinement in metals and alloys was significantly developed in recent years. The influence of electromagnetic parameters on ...Pulsed magneto-oscillation （PMO） as a new electromagnetic technology to generate the grain refinement in metals and alloys was significantly developed in recent years. The influence of electromagnetic parameters on the grain size reduction in pure AI was investigated under the application of PMO with a constant inputting power. The experimental results show that the grain refinement degree could be improved with the increase in the current intensity in the case of the identical power. Moreover, through analysing the electromagnetic force and resistance force applied on the nucleus, a criterion of the nucleus detached from the mould wall was constructed. Based on the criterion, the detachment of nuclei with finer radius could cause better effect of the grain refinement, when applying a higher current peak. The movement of the detached grains was considered by analysing the influence of electromagnetic force and forced flow.展开更多
A new approach to applying the electric current pulse （ECP） with parallel electrodes to the promotion of the transition from columnar crystal to equiaxed crystal and the improvement of macrosegregation was introduce...A new approach to applying the electric current pulse （ECP） with parallel electrodes to the promotion of the transition from columnar crystal to equiaxed crystal and the improvement of macrosegregation was introduced. The ECP was applied to different stages of the solidification. The results showed that the application of the ECP in both the initial stage （the thickness of solidified shell reached 2 mm approximately） and the late stage （the thickness of solidified shell reached 14 mm approximately） of solidification can promote the columnar to equiaxed transition （CET）. The analysis showed that during solidification, a large number of nuclei around the upper surface fell off due to ECP, which subsequently showered on the melt and impinged the growth front of the columnar crystal. Therefore, the CEToccurred. In addition, this method was also employed to influence the solidification process of bearing steel, and the results showed that the structure was changed from columnar crystal to equiaxed crystal, indicating that ECP can enhance the homogeneity of structure and composition of bearing steel.展开更多
基金supported by the Postgraduate Innovative Foundation of Shanghai University (SHUCX091031)the National Natural Science Foundation of China (No.51074105)the National Basic Research Priorities Program of China (No.2007CB613606)
文摘The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and optical microscopy （OM）. It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150℃ for 80 min. The final phase constituents mainly consist of Fe, M305 solid solution phase （M=Mg, Ti, and Fe）, and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ.mo1-1.
基金supported by the National Natural Science Foundation of China(51004069 and 51474145)the National Science Fund for Distinguished Young Scholars(51225401)
文摘A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5＋δ （CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y） were synthesized through a sol-gel route and effects of the Ln3＋ cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3＋ cations （La3＋, Pr3＋ and Nd3＋） successfully stabilized the double-layered perovskite structure of sintered LBCO, while the smaller ones （Sm3＋, Gd3＋, and Y3＋） resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8× 10^-7 mol.s-1.cm-2 at 925 ℃ with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.
基金supported by the National Natural Science Foundation of China(51004069)the National Science Fund for Distinguished Young Scholars(51225401)+1 种基金China Postdoctoral Science Foundation(201104254)the Innovation Program of Shanghai Municipal Education Commission and Shanghai University(14YZ013 and SDCX2012002)
文摘Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ （BRCFT, R = Ca, La or Sr） membranes were synthesized by a solid-state reaction. Metal cation Ca2＋, La3＋ or Sr2＋ doping on A-site partially substituted Ba2＋ in BaCoo.TFe0.225Ta0.07503-δ oxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, Hz-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2＋, La3＋ or Sr2＋, whose ionic radii are smaller than that of Ba2＋, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experi- ments showed that BRCFT with A-site fully occupied by Ba2＋ exhibited good oxygen permeation flux under He flow, reaching about 2.3 mL.min-l .cm-2 at 900 with I mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation （Ba2＋〉La3＋〉SrZ＋〉Ca2＋）.
基金the National High-Tech Research and Development Program of China (No. 2006AA11A189)the Science and Technology Commission of Shanghai Municipality (No. 07DZ12036)+1 种基金the National Engineering Research Center of Advanced Steel Technology (NERCAST, No. 050209)the Education Commission of Shanghai Municipality.
文摘The total conductivity,oxygen sorption property,oxygen permeability and stability of pure perovskite-type oxide BaCo0.7Fe0.2Nb0.1O3-δ (BCFNO) in real operating conditions were investigated. Its total conductivity was measured to be 3.6 S·cm-1 at 600°C. Though the total conductivity of the BCFNO membrane is much smaller than that of the Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCFO) membrane,the oxygen permeability of the BCFNO membrane is similar to that of the BSCFO membrane. SEM observation and EDX analysis of the BCFN...
基金supported by the National Natural Science Foundation of China(No.51274139,51174133)the Innovation Program of Shanghai Municipal Education Commission(13YZ019)+1 种基金the Doctoral Fund of Ministry of Education of China(20123108120020)the Innovative Foundation of Shanghai University
文摘Ba1.0Co0.7Fe0.2Nb0.1O3-γ（BCFN） oxide with perovskite cubic structure was synthesized by solid state reaction method. COa corrosion of BCFN membrane was investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, diffuse reflectance infrared Fourier- transformed spectroscopy （DRIFT） and X-ray absorption fine structure spectroscopy （XAFS）. Cobalt （Co） K-edge absorption spectra of BCFN annealed in COa reveal that the oxidation states of Co in all the samples were larger than ＋3 and they decreased with the increase of calcination time. At 800 ℃, 1% CO2 introduced into He could speed up the reduction of Co cations in comparison with pure He. In addition, sulfate ions in the bulk of BCFN membrane preferred to migrate to the surface under CO2 calcination and form monoclinic Ba（CO3）0.9（SO4）0.1 besides orthorhombic witherite. Moreover, SEM results indicate that the nucleation and growth of carbonates grains started at the grain boundary of the membrane.
基金supported by the National Natural Science Foundation of China(Grant Nos.51171105 and 50971086)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learningthe 085 project in Shanghai University
文摘The preparation and solidification of metallic droplets attract more and more attention for their signiifcance in both engineering and scientiifc ifelds. In this paper, the preparation and characterization of Sn-based al oy droplets using different methods such as atomization and consumable electrode direct current arc （CDCA） technique are reviewed. The morphology and structure of these droplets were determined by optical microscopy, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The solidiifcation behavior of single droplet was systematical y studied by means of scanning calorimetry （DSC）, and the nucleation kinetics was also calculated. In particular, the development of fast scanning calorimetry （FSC） made it possible to investigate the evolution of undercooling under ultrafast but control able heating and cooling conditions. The combination of CDCA technique and FSC measurements opens up a new door for quantitative studies on droplet solidiifcation, which is accessible to demonstrate some theories by experiments.
基金supported by the National High Technology Research and Development Program of China (Grant No. 2006AA11A189)Science and Technology Commission of Shanghai Municipality (Grant Nos. 0952NM01400 and 07DZ12036)
文摘Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.
基金Project(2006AA03Z339)supported by the National High-tech Research and Development Program of ChinaProject(50571057)supported by the National Natural Science Foundation of ChinaProject(08520740500)supported by Science and Technology Commission of Shanghai Municipality,China
文摘Tin nanoparticles with different size distribution were synthesized using chemical reduction method by applying NaBH4 as reduction agent.The Sn nanoparticles smaller than 100 nm were less agglomerated and no obviously oxidized.The melting properties of these synthesized nanoparticles were studied by differential scanning calorimetry.The melting temperatures of Sn nanoparticles in diameter of 81,40,36 and 34 nm were 226.1,221.8,221.1 and 219.5？欲espectively.The size-dependent melting temperature and size-dependent latent heat of fusion have been observed.The size-dependent melting properties of tin nanoparticles in this study were also comparatively analyzed by employing different size-dependent theoretical melting models and the differences between these models were discussed.The results show that the experimental data are in accordance with the LSM model and SPI model,and the LSM model gives the better understanding for the melting property of the Sn nanoparticles.
基金Project(08BZ1130100) supported by the Science and Technology Committee of Shanghai,ChinaProject(SHUCX102251) supported by the Innovation Fund for Graduate Student of Shanghai University,China
文摘The influence of casting parameters on stray grain formation of a unidirectionally solidified superalloy IN738LC casting with three platforms was investigated by using a 3D cellular automaton-finite element （CAFE） model in CALCOSOFT package. The model was first validated by comparison of the reported grain structure of AI-7%Si （mass fraction） alloy. Then, the influence of pouring temperature, heat flux of the lateral surface, convection heat coefficient of the cooled chill and mean undercooling of the bulk nucleation on the stray grain formation was studied during the unidirectional solidification. The predictions show that the stray grain formation is obviously sensitive to the pouring temperature, heat flux and mean undercooling of the bulk nucleation. However, increasing the heat convection coefficient has little influence on the stray grain formation.
基金Project(2006AZ001)supported by the Shanghai Municipal Education Commission,ChinaProject(06JC14031)supported by the Scienceand Technology Commission of Shanghai Municipality,China+2 种基金Project(06QA14021)supported by the Shanghai Rising-Star Program(Atype),ChinaProject(200746)supported by the Foundation for the Author of National Excellent Doctoral Dissertation of ChinaProjectsupported by the Innovation Fund for Graduate Student of Shanghai University,China
文摘Chou model was used to investigate the dehydriding reaction kinetic mechanism of MgH_2-Nb_2O_5 hydrogen storage materials at 573 K.A new conception,'characteristic absorption/desorption time(t_c)'was introduced to characterize the reaction rate The fitting results show that for the hydrogen desorbing mechanism,the surface penetration is the rate-controlling step.The mechanism remains the same even when the original panicle size of Nb_2O_5 is before ball milling(BM) or when the BM time changes And t_c indicates that the desorption rate of MgH_2-Nb_2O_5 will be faster than that of MgH_2-Nb_2O_5 by BM.The dehydriding reaction rate of MgH_2-Nb_2O_5(micro particle) BMed for 50 h is 4.76 times faster than that of the MgH_2-Nb_2O_5(micro panicle) BMed for 0.25 h,while the dehydriding reaction rate of MgH_2-Nb_2O_5(nano particle) BMed for 50 h is only 1.18 times as that of the MgH2-Nb_2O_5 (nano particle) BMed for 0.25 h.The dehydriding reaction rate of the BMed MgH_2-Nb_2O_5(nano particle) is 1-9 times faster than that of the BMed MgH_2-Nb_2O_5(micro particle).
基金supports from the National Natural Science Foundation of China(Grant Nos.51201096 and 51474144)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No. 20123108120019)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘In the present work, crystal structure and for- mation mechanism of the secondary phase in Heusler Ni- Mn-Sn-Co materials were investigated using X-ray dif- fraction, scanning/transmission electron microscopy and selected-area electron diffraction techniques. Experimental results showed that the secondary phase presented in both Ni44.1Mn35.1Sn10.8Co10 as-cast bulk alloy and melt-spun ribbon, possessing a face-centered cubic （fcc） NilTSn3-type structure. The secondary phase in the as-cast bulk alloy was resulted from a eutectic reaction after the formation of a primary dendritic flphase during cooling. However in the melt-spun rapidly solidified ribbon, the secondary phase was largely suppressed as nano-precipitates distributed along the grain boundaries, which was attributed to a divorced eutectic reaction. The secondary phase exhibited partial amorphous state due to high local cooling rate.
基金supported by the National High Technology Research and Development Program of China (No. 2006AA11A189)Science and Technology Commission of Shanghai Municipality (No. 06DZ12212)+1 种基金National Engineering Research Center of Advanced Steel Technology (NERCAST) (No. 050209)the Innovation Fund for Graduate Studentof Shanghai University (SHUCX0910003)
文摘The performance of LiNi/γ-Al2O3 catalysts modified by rare earth metal oxide （La2O3 or CeO2） packed on BCFNO membrane reactor was discussed for the partial oxidation of methane （POM） in coke oven gas （COG） at 875 ℃. The NiO/γ-Al2O3 catalysts with different amounts of La2O3 and CeO2 were prepared with the same preparation method and under the same condition in order to compare the reaction performance （oxygen permeation, CH4 conversion, H2 and CO selectivity） on the membrane reactor. The results show that the oxygen permeation flux increased significantly with LiNiREOx/γ-Al2O3 （RE = La or Ce） catalysts by adding the element of rare earth especially the Ce during the POM in COG. Such as, the Li15wt%CeO29wt%NiO/γ-Al2O3 catalyst with an oxygen permeation flux of 24.71 ml·cm^-2·min^-1 and a high CH4 conversion was obtained in 875 ℃. The resulted high oxygen permeation flux may be due to the added Ce that inhibited the strong interaction between Ni and Al2O3 to form the NiAl2O4 phase. In addition, the introduction of Ce leads up to an important property of storing and releasing oxygen.
基金supported by the National Natural Science Foundation of China (Nos. 51004069 and 51474145)the National Science Fund for Distinguished Young Scholars (No. 51225401)the Innovation Program of Shanghai Municipal Education Commission and Shanghai University (Nos. 14YZ013 and SDCX2012002)
文摘Dual-phase membranes of 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Pr Ba Co2exFexO3 d（0 x 2） were prepared by a combined citrate and ethylene diamine tetraacetic acid（EDTA） complexing method. X-ray diffraction（XRD）results revealed the good chemical compatibility between ion-conducting phase CGO and electron-conducting phases PBC2 xFxO after sintering in air. The Fe ionic dopant had a significant effect on the phase structure stability and oxygen permeability under CO2 atmosphere, which was confirmed by XRD, thermogravimetrye differential scanning calorimetry（TGeD SC）, scanning electron microscopy（SEM） and oxygen permeation experiments. CGOeP BC0.5F1.5O dual-phase membrane demonstrated a stable oxygen permeation flux of2.71x10-7mol cm 2s 1with 50 mol% He/CO2 as the sweep gas at 925 C, and this value was much higher than that of perovskite-type membranes. The rate-limiting step in the oxygen permeation process changed from the bulk diffusion to the surface oxygen exchange when the CGOeP BC0.5F1.5O membrane thickness decreased to 0.8 mm or less. Due to the high oxygen permeation fluxes and the excellent structural stability under CO2 atmosphere, the CGOeP BC0.5F1.5O membrane is a great potential candidate material for separating oxygen from air in the oxy-fuel combustion techniques.
基金supported by the National Natural Science Foundation of China (No. 51174133)the National High Technology Research and Development Program of China(No. 2006AA11A189)the Science and Technology Commission of Shanghai Municipality (No. 11ZR1412900)
文摘The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SCFNO with a thickness of 1 mm had a high level of oxygen permeation flux of 1.4 ml.min^(-1).cm^(-2) at 850 ℃ under air/He gradient.The bulk diffusion is the rate-limiting step in overall oxygen permeation mechanism for SCFNO when the thickness is higher than 1.0 mm.The partial substitution of Nb for Co suppresses the transition of oxygen vacancies order/disorder proven by DSC measurement and enhances the phase stability under low oxygen partial pressure.During long-term tests under low oxygen pressure,the SCFNO exhibites structural stability and stable oxygen permeation.It is proved that substitution of Nb for Co is an effective way to improve the properties of SCFO.
基金Project(2007AA05Z118) supported by the Hi-tech Research and Development Program of ChinaProject(50804029, 50504010) supported by the National Natural Science Foundation of China+1 种基金Project(200746) supported by Foundation for the Author of National Excellent Doctoral Dissertation of ChinaProject(IRT0739) supported by Program for Changjiang Scholars and Innovative Research Team in University
文摘A small amount of Fe3O4 catalyst is known to substantially improve the adsorption and desorption thermodynamics and kinetics of Mg-based materials. Using density functional theory in combination with nudged elastic band method,the dissociative chemisorptions of hydrogen on both pure and Fe-doped Mg(0001) surfaces were studied. The adsorption energy calculations show that a weakly physisorbed state above pure and Fe-doped Mg surface atoms can serve as a precursor state to dissociative chemisorption. Then,the dissociation pathway of H2 and the relative barrier were investigated. The calculated dissociation barrier(1.08 eV) of hydrogen molecule on a pure Mg(0001) surface is in good agreement with comparable experimental and theoretical studies. For the Fe-doped Mg(0001) surface,the activated barrier decreases to 0.101 eV due to the strong interaction between the s orbital of H and the d orbital of Fe.
基金financially supported by the National Natural Science Foundation of China(No.51074105)China National Funds for Distinguished Young Scientists(No.51225401)
文摘In this paper, the thermodynamics of the reduction of ilmenite using multiple gases (H<sub>2</sub>/CO) was calculated. It is found that the metallization rate of 20.1%–98.8%, H<sub>2</sub> consumption rate of 43.0%–99.1%, and carbon deposition amount of 5.7×10<sup>?7</sup>?0.49mol can be obtained based on the conditions of hydrogen volume fraction of 10%–90% and temperature of 450–1200°C. Experimental study was also carried out using synthetic ilmenite as initial materials and reduced in a static bed reactor at 1100°C. The metallization rate reaches 97% when the multiple gas (70% H<sub>2</sub>/10% CO/20% Ar) flow rate is 120ml·min<sup>?1</sup>. A thermogravimetric analyzer was used to measure the variation of sample weight caused by the deposition of solid carbon. The amount of carbon deposited during experiments reaches its maximum while the original hydrogen volume content is 20%. The experimental results are well consistent with the thermodynamic analysis.
基金The financial support received from the National High Technology Research and Development Program of China (Grant No.2006AA11A189)Science and Technology Commission of Shanghai Municipality (Grant No. 07DZ12036)National Engineering Research Center for Advanced Steel Technology (NERCAST)(Grant No. 050209)
文摘Hydrogen production by catalytic reforming of simulated hot coke oven gas （HCOG） with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg（Al）O catalysts. The catalysts were prepared by a homogeneous precipitation method using urea hydrolysis and characterized by ICE BET, XRD, TPR, TEM and TG. XRD showed that the hydrotalcite type precursor after calcination formed （Ni, Mg）Al2O4 spinel and Ni-Mg-O solid solution structure. TPR results suggested that the increase in Ni/Mg molar ratio gave rise to the decrease in the reduction temperature of Ni^2＋ to Ni^0 on Ni/Mg（Al）O catalysts. The reaction results indicated that toluene and CH4 could completely be converted to H2 and CO in the catalytic reforming of the simulated HCOG under atmospheric pressure and the amount of H2 in the reaction effluent gas was about 4 times more than that in original HCOG. The catalysts with lower Ni/Mg molar ratio showed better catalytic activity and resistance to coking, which may become promising catalysts in the catalytic reforming of HCOG.
基金Funded by the National Natural Science Foundation of China(No.2010DFB70630)
文摘Quenching experiments were performed at different cooling rates under non-directional solidification by differential thermal analysis, and the morphologic variation of primary phase, phase transition temperature and hardness change at the same quenching temperature were investigated. The experimental results show that, with the gradual decrease of the cooling rate from 25 K/min, the morphology of ferrite starts to transform experiencing the dendrite, radial pattern, Widmanstatten-like and wire-net. Sample starts to present the Widmanstatten-like microstructure at 10 K/min which does not exist at higher or lower cooling rates, and this microstructure is detrimental to the mechanical property. Except 10 K/min, the hardness decreases with decreasing cooling rate.
基金Acknowledgements The authors acknowledge the financial support from the National Natural Science Foundation of China （Grant Nos. 51504048, 50574056 and U1760204） and the National Key Research Program of China （Grant No. 2017YFB0701800）.
文摘Pulsed magneto-oscillation （PMO） as a new electromagnetic technology to generate the grain refinement in metals and alloys was significantly developed in recent years. The influence of electromagnetic parameters on the grain size reduction in pure AI was investigated under the application of PMO with a constant inputting power. The experimental results show that the grain refinement degree could be improved with the increase in the current intensity in the case of the identical power. Moreover, through analysing the electromagnetic force and resistance force applied on the nucleus, a criterion of the nucleus detached from the mould wall was constructed. Based on the criterion, the detachment of nuclei with finer radius could cause better effect of the grain refinement, when applying a higher current peak. The movement of the detached grains was considered by analysing the influence of electromagnetic force and forced flow.
基金Item Sponsored by National Natural Science Foundation of China(50674064,50734008)
文摘A new approach to applying the electric current pulse （ECP） with parallel electrodes to the promotion of the transition from columnar crystal to equiaxed crystal and the improvement of macrosegregation was introduced. The ECP was applied to different stages of the solidification. The results showed that the application of the ECP in both the initial stage （the thickness of solidified shell reached 2 mm approximately） and the late stage （the thickness of solidified shell reached 14 mm approximately） of solidification can promote the columnar to equiaxed transition （CET）. The analysis showed that during solidification, a large number of nuclei around the upper surface fell off due to ECP, which subsequently showered on the melt and impinged the growth front of the columnar crystal. Therefore, the CEToccurred. In addition, this method was also employed to influence the solidification process of bearing steel, and the results showed that the structure was changed from columnar crystal to equiaxed crystal, indicating that ECP can enhance the homogeneity of structure and composition of bearing steel.
