Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electr...Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.展开更多
The oxidation of PM Cu 50Cr, MA Cu 40Cr and MS Cu 40Cr alloys at 800 ℃ in 0.1 MPa O 2 was studied. The most important difference of their oxidation behaviors is the formation of an exclusive chromia scale on the surf...The oxidation of PM Cu 50Cr, MA Cu 40Cr and MS Cu 40Cr alloys at 800 ℃ in 0.1 MPa O 2 was studied. The most important difference of their oxidation behaviors is the formation of an exclusive chromia scale on the surface of the MS Cu 40Cr alloy and a continuous chromia layer beneath an outer CuO layer corresponding MA Cu 40Cr alloy, while a complex scale composing of CuO, Cu 2O, Cu 2Cr 2O 4 and Cr 2O 3 formed on the PM Cu 50Cr alloy. This result implies that alloy microstructure affects their oxidation behaviors largely. Microcrystalline structure provides numerous diffusion paths for reactive component chromium, shorter diffusion distance and rapid dissolution of Cr riched second phase. All these favor the exclusive formation of the most stable oxide. [展开更多
Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Thre...Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.展开更多
Three novel multi-microalloying TiAl-based alloys containing high Nb were designed and fabricated Thermogravimetric method was applied to investigate the influence of Cr on the oxidation behavior of high Nb TiAl alloy...Three novel multi-microalloying TiAl-based alloys containing high Nb were designed and fabricated Thermogravimetric method was applied to investigate the influence of Cr on the oxidation behavior of high Nb TiAl alloy at 1,073 K for 200 h in laboratory air. The 2 at.% and 4 at.% Cr were added into the alloy,(respectivel named 2 Cr and 4 Cr compared to the Cr-free ternary alloy, 0 Cr alloy). The alloys' microstructure and compositio as well as the composition distribution of the oxidation scale were analyzed by means of Scanning Electro Microscopy(SEM), Energy Dispersive Spectroscopy(EDS), and X-Ray Diffractometry(XRD). The results show that the addition of Cr decreases the grain size of the Nb-TiAl alloy and leads to a transformation from a full lamellar structure to a nearly fully lamellar structure. When oxidized at 1,073 K for 200 h, the oxidized mass gai of the alloy increases with an increase in Cr addition amount in the first 100 h and decreases in the last 100 h With the increase of Cr content, the oxidation surface turns compact but uneven in morphology, which may affec the oxidation resistance of the alloy by increasing the peeling off risk of the oxidation layer at friction conditions.展开更多
A series of Cr doped TiO2 films were prepared by micro arc oxidation （MAO） using an electrolyte of Na3PO4＋K2Cr2O7. X-ray diffraction and scanning electron microscopy revealed that the films mainly consisted of anat...A series of Cr doped TiO2 films were prepared by micro arc oxidation （MAO） using an electrolyte of Na3PO4＋K2Cr2O7. X-ray diffraction and scanning electron microscopy revealed that the films mainly consisted of anatase phase with a porous surface morphology. The films have an excellent photocatalytic effect for degradation of methylene blue and decomposition of water under visible light illumination. This arises from the formation of Cr3＋/Cr4＋ and oxygen vacancy energy levels owing to Cr doping. The former reduces the electron-hole recombination chance, while the latter generates a new gap between the conduction band （CB） and valence band （VB） of TiO2, which lowers the photo energy of the excited electron in the VB to the oxygen vacancy states. The mechanisms for film synthesis during the MAO process are also presented.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
The oxidation behavior of sputtered Ni-3Cr-20Al coating at 900℃ in air was investigated. A dense Al2O3 layer was formed on the sputtered Ni-3Cr-20AI coating after 200 h oxidation. However, owing to the segregation of...The oxidation behavior of sputtered Ni-3Cr-20Al coating at 900℃ in air was investigated. A dense Al2O3 layer was formed on the sputtered Ni-3Cr-20AI coating after 200 h oxidation. However, owing to the segregation of Ni3Al during oxidation process at high temperature, the spinel NiAI2O4 was also formed in the Al2O3 layer. It was found that the formation of NiAI204 had no detrimental effect on the oxidation resistance of the sputtered N?3O-20AI coating due to the excellent adhesion shown by the Al2O3 and NiAl2O4complex oxide scale.展开更多
In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temper...In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.展开更多
Cr1-xAlxN coatings have been deposited on a Ti3Al based alloy by reactive sputtering method. The results of the isothermal oxidation test at 800-900℃ showed that Cr1-xAlxN coatings could remarkably reduce the oxidati...Cr1-xAlxN coatings have been deposited on a Ti3Al based alloy by reactive sputtering method. The results of the isothermal oxidation test at 800-900℃ showed that Cr1-xAlxN coatings could remarkably reduce the oxidation rate of the alloy owing to the formation of Al2O3＋Cr2O3 mixture oxide scale on the surface of the coatings. No spallation of the coatings or oxide scales took place during the cyclic oxidation at 800℃. Ti was observed to diffuse into the coatings, the diffusion distance of which was very short, and the diffusion ability of it was proportional to the AI content in the coatings. Compared to Ti, Nb can diffuse much more easily through the whole coatings and oxide scales.展开更多
Hydrous magnesium oxide coated fly ash （MFA） has environmental remediation potential by providing a sub- strate for the adsorption of aqueous Cr（Ⅲ）. Aqueous Cr（Ⅲ） adsorption onto MFA was examined as a function...Hydrous magnesium oxide coated fly ash （MFA） has environmental remediation potential by providing a sub- strate for the adsorption of aqueous Cr（Ⅲ）. Aqueous Cr（Ⅲ） adsorption onto MFA was examined as a function of MFA dosage, pH and initial Cr（Ⅲ） concentration with the Box-Behnken approach used for experimental design and optimization using response surface methodology （RSM）. pH and dosage （dosage and concentration） have significant interactive effects on Cr（Ⅲ） adsorption efficiency. Analysis of variance shows that the response surface quadratic model is highly significant and can effectively predict the experimental outcomes. Cr（Ⅲ） removal effi- ciency of 98% was obtained using optimized conditions of MFA dosage, pH and initial Cr（Ⅲ） concentration of 1,5 7 g. L- 1, 4.11 and 126 mg. L- 1, respectively. Cr（Ⅲ） adsorption onto MFA is mainly attributed to the interaction between Or（Ⅲ） and the functional group --OH of the hydrous magnesium oxide, in all probability caused by chemisorptions. The results of this study can conduce to reveal the interactions between Cr（Ⅲ） pollutant and MFA characteristics, posing important implications for the cost-effective alternative adsorption technology in the treatment of heavy metal containing wastewater.展开更多
Test alloys ZG40Cr24 with alloying of 3 wt% aluminium were cast by intermediate frequency induction furnace. The oxidation resistance of test alloys at 1 000 ℃ for 500 hours was examined according to oxidation weight...Test alloys ZG40Cr24 with alloying of 3 wt% aluminium were cast by intermediate frequency induction furnace. The oxidation resistance of test alloys at 1 000 ℃ for 500 hours was examined according to oxidation weight gain method. The scale morphology and composition were studied using scanning electron microscope （SEM） and X-ray diffraction （XRD） respectively. By energy dispersive spectroscopy （EDS） studies, a kind of composite oxide scale compounded highly by Cr2O3, Al2O3 and spinel MCr2O4 in molecule scale came into being at high temperature. With flat and compact structure, fine and even grains, such composite scale granted complete oxidation resistance to alloy ZG40Cr24. The oxidation resistance mechanism was studied deeply in electrochemistry corrosion. The P＋N semiconductor composite scale composed plenty of inner PN junctions, of which the unilateral conductive and the out-of-order arrangement endowed itself insulating in all directions. The positive and negative charges in scale could not move, and the mobile number and transferring rate of them both dropped enormously, as a result, the oxidation rate of the matrix metal was cut down greatly. So the composite scale presented excellent oxidation resistance.展开更多
The oxidation resistance of 5Cr21Mn9Ni4N steel micro-alloying by RE at 700 - 900 ℃ was investigated. The results indicate that oxidation exponent n and oxidation activation energy are increased, and oxidation velocit...The oxidation resistance of 5Cr21Mn9Ni4N steel micro-alloying by RE at 700 - 900 ℃ was investigated. The results indicate that oxidation exponent n and oxidation activation energy are increased, and oxidation velocity constant kp is decreased when 0.2% RE is added in 5Cr21Mn9Ni4N steel. The addition of RE elements does not alter phase constitution of oxidation scale, however it improves the configuration of oxidation scale, and increases thermal stability and adhesivity of oxidation scale, which results in the raise of oxidation resistance of 5Cr21Mn9Ni4N steel at high temperature. The oxidation scale constitutes of refractory steel transfer from manganic oxide mostly to ferric oxide mostly with the increase of temperature, which leads to descend of compactness and desquamation resistance of oxidation scale. The mass increase of ferric oxide in the oxidation scale and the looseness of oxidation scale are the main reason to descend the oxidation resistance of refractory steel.展开更多
The micro-laminated （ZrO2-Y2O3）/（Al2O3-Y2O3） composite films were prepared on the surface of Fe-13Cr alloy by an electrochemical process and a sintering process alternately. High-resolution field emission scanning...The micro-laminated （ZrO2-Y2O3）/（Al2O3-Y2O3） composite films were prepared on the surface of Fe-13Cr alloy by an electrochemical process and a sintering process alternately. High-resolution field emission scanning electron microscopy （FE-SEM） was used to characterize the laminated films, indicating that the micro-laminated （ZrO2-Y2O3）] （Al2O3-Y2O3） films have nano-structures. SEM, EDS and mass gain measurement were adopted to study the oxidation resistance of films on Fe-13Cr alloy. It is proved that such micro-laminated films are more effective than ZrO2-Y2O3 or Al2O3-Y2O3 films to resist the oxidation of the alloy, and the oxidation resistance is increased with increasing layers in micro-laminated films. These beneficial effects can be contributed to the mechanism, by which such micro-laminated （ZrOE- YEO3）/（Al2O3-Y2O3） composite film combines all the beneficial effects and overcomes all the disadvantages of both ZrOE- Y2O3 film and Al2O3-Y2O3 film during oxidation of alloy.展开更多
Glycerol is a by-product of biodiesel production and is an important readily available platform chemical.Valorization of glycerol into value-added chemicals has gained immense attention.Herein,we carried out the conve...Glycerol is a by-product of biodiesel production and is an important readily available platform chemical.Valorization of glycerol into value-added chemicals has gained immense attention.Herein,we carried out the conversion of glycerol to formic acid and glycolic acid using H2O2 as an oxidant and metal(Ⅲ)triflate-based catalytic systems.Aluminum(Ⅲ)triflate was found to be the most efficient catalyst for the selective oxidation of glycerol to formic acid.A correlation between the catalytic activity of the metal cations and their hydrolysis constants(Kh)and water exchange rate constants was observed.At 70 ℃,a formic acid yield of up to 72% could be attained within 12 h.The catalyst could be recycled at least five times with a high conversion rate,and hence can also be used for the selective oxidation of other biomass platform molecules.Reaction kinetics and 1H NMR studies showed that the oxidation of glycerol(to formic acid)involved glycerol hydrolysis pathways with glyceric acid and glycolic acid as the main intermediate products.Both the [Al(OH)x]^n+ Lewis acid species and CF3SO3H Brosted acid,which were generated by the in-situ hydrolysis of Al(OTf)3,were responsible for glycerol conversion.The easy availability,high efficiency,and good recyclability of Al(OTf)3 render it suitable for the selective oxidation of glycerol to high value-added products.展开更多
基金supported by the Science and Technology Foundation of Guizhou Province,China(No.[2020]1Y163)the National Natural Science Foundation of China(No.41827802).
文摘Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.
文摘The oxidation of PM Cu 50Cr, MA Cu 40Cr and MS Cu 40Cr alloys at 800 ℃ in 0.1 MPa O 2 was studied. The most important difference of their oxidation behaviors is the formation of an exclusive chromia scale on the surface of the MS Cu 40Cr alloy and a continuous chromia layer beneath an outer CuO layer corresponding MA Cu 40Cr alloy, while a complex scale composing of CuO, Cu 2O, Cu 2Cr 2O 4 and Cr 2O 3 formed on the PM Cu 50Cr alloy. This result implies that alloy microstructure affects their oxidation behaviors largely. Microcrystalline structure provides numerous diffusion paths for reactive component chromium, shorter diffusion distance and rapid dissolution of Cr riched second phase. All these favor the exclusive formation of the most stable oxide. [
基金the National Natural Science Foundation of China （Nos. 40471070 and 40403009） the Key Project of the Ministry of Education of China （No. 105122） for financial supports to this research.
文摘Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.
基金financially supported by the Fundamental Research Funds for the Central Universities of Ministry of Education of China(Grant Nos.HEUCFP 201731 and 201719)
文摘Three novel multi-microalloying TiAl-based alloys containing high Nb were designed and fabricated Thermogravimetric method was applied to investigate the influence of Cr on the oxidation behavior of high Nb TiAl alloy at 1,073 K for 200 h in laboratory air. The 2 at.% and 4 at.% Cr were added into the alloy,(respectivel named 2 Cr and 4 Cr compared to the Cr-free ternary alloy, 0 Cr alloy). The alloys' microstructure and compositio as well as the composition distribution of the oxidation scale were analyzed by means of Scanning Electro Microscopy(SEM), Energy Dispersive Spectroscopy(EDS), and X-Ray Diffractometry(XRD). The results show that the addition of Cr decreases the grain size of the Nb-TiAl alloy and leads to a transformation from a full lamellar structure to a nearly fully lamellar structure. When oxidized at 1,073 K for 200 h, the oxidized mass gai of the alloy increases with an increase in Cr addition amount in the first 100 h and decreases in the last 100 h With the increase of Cr content, the oxidation surface turns compact but uneven in morphology, which may affec the oxidation resistance of the alloy by increasing the peeling off risk of the oxidation layer at friction conditions.
文摘A series of Cr doped TiO2 films were prepared by micro arc oxidation （MAO） using an electrolyte of Na3PO4＋K2Cr2O7. X-ray diffraction and scanning electron microscopy revealed that the films mainly consisted of anatase phase with a porous surface morphology. The films have an excellent photocatalytic effect for degradation of methylene blue and decomposition of water under visible light illumination. This arises from the formation of Cr3＋/Cr4＋ and oxygen vacancy energy levels owing to Cr doping. The former reduces the electron-hole recombination chance, while the latter generates a new gap between the conduction band （CB） and valence band （VB） of TiO2, which lowers the photo energy of the excited electron in the VB to the oxygen vacancy states. The mechanisms for film synthesis during the MAO process are also presented.
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National Natural Science Foundation of China !under grant 59671060
文摘The oxidation behavior of sputtered Ni-3Cr-20Al coating at 900℃ in air was investigated. A dense Al2O3 layer was formed on the sputtered Ni-3Cr-20AI coating after 200 h oxidation. However, owing to the segregation of Ni3Al during oxidation process at high temperature, the spinel NiAI2O4 was also formed in the Al2O3 layer. It was found that the formation of NiAI204 had no detrimental effect on the oxidation resistance of the sputtered N?3O-20AI coating due to the excellent adhesion shown by the Al2O3 and NiAl2O4complex oxide scale.
基金Supported by the Doctoral Foundation of Education Department of Hebei Province(NoB2004205) Hebei University Re-search Foundation(No2003Z09)
文摘In this study, the kinetics and mechanism of the iridium（ Ⅲ ） -catalyzed oxidation of ethanol amine（EAN） by cerium（Ⅳ） in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298--313 K. It was found that the reaction is of first order with respect to Ce（ Ⅳ ） and It（ Ⅲ ）, and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order （ [EAN ] 〉〉 [ Ce （ Ⅳ） ] ） rate constant koba decreases with the increase of [ H^＋ ] and [ HSO^-4 ]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of koba on the concentration of hydrogen sulfate, Ce（SO4）2 was found to be the kinetically active species. The rate constants of the rote-determining step together with the activation parameters were evaluated.
基金the National Natural Science Foundation of China under grant Nos. 50371095 , 50571106.
文摘Cr1-xAlxN coatings have been deposited on a Ti3Al based alloy by reactive sputtering method. The results of the isothermal oxidation test at 800-900℃ showed that Cr1-xAlxN coatings could remarkably reduce the oxidation rate of the alloy owing to the formation of Al2O3＋Cr2O3 mixture oxide scale on the surface of the coatings. No spallation of the coatings or oxide scales took place during the cyclic oxidation at 800℃. Ti was observed to diffuse into the coatings, the diffusion distance of which was very short, and the diffusion ability of it was proportional to the AI content in the coatings. Compared to Ti, Nb can diffuse much more easily through the whole coatings and oxide scales.
基金Supported by the State Key Development Program for Basic Research of China(2014CB460601)the International S&T Cooperation Program of China(2014DFE70070)
文摘Hydrous magnesium oxide coated fly ash （MFA） has environmental remediation potential by providing a sub- strate for the adsorption of aqueous Cr（Ⅲ）. Aqueous Cr（Ⅲ） adsorption onto MFA was examined as a function of MFA dosage, pH and initial Cr（Ⅲ） concentration with the Box-Behnken approach used for experimental design and optimization using response surface methodology （RSM）. pH and dosage （dosage and concentration） have significant interactive effects on Cr（Ⅲ） adsorption efficiency. Analysis of variance shows that the response surface quadratic model is highly significant and can effectively predict the experimental outcomes. Cr（Ⅲ） removal effi- ciency of 98% was obtained using optimized conditions of MFA dosage, pH and initial Cr（Ⅲ） concentration of 1,5 7 g. L- 1, 4.11 and 126 mg. L- 1, respectively. Cr（Ⅲ） adsorption onto MFA is mainly attributed to the interaction between Or（Ⅲ） and the functional group --OH of the hydrous magnesium oxide, in all probability caused by chemisorptions. The results of this study can conduce to reveal the interactions between Cr（Ⅲ） pollutant and MFA characteristics, posing important implications for the cost-effective alternative adsorption technology in the treatment of heavy metal containing wastewater.
文摘Test alloys ZG40Cr24 with alloying of 3 wt% aluminium were cast by intermediate frequency induction furnace. The oxidation resistance of test alloys at 1 000 ℃ for 500 hours was examined according to oxidation weight gain method. The scale morphology and composition were studied using scanning electron microscope （SEM） and X-ray diffraction （XRD） respectively. By energy dispersive spectroscopy （EDS） studies, a kind of composite oxide scale compounded highly by Cr2O3, Al2O3 and spinel MCr2O4 in molecule scale came into being at high temperature. With flat and compact structure, fine and even grains, such composite scale granted complete oxidation resistance to alloy ZG40Cr24. The oxidation resistance mechanism was studied deeply in electrochemistry corrosion. The P＋N semiconductor composite scale composed plenty of inner PN junctions, of which the unilateral conductive and the out-of-order arrangement endowed itself insulating in all directions. The positive and negative charges in scale could not move, and the mobile number and transferring rate of them both dropped enormously, as a result, the oxidation rate of the matrix metal was cut down greatly. So the composite scale presented excellent oxidation resistance.
文摘The oxidation resistance of 5Cr21Mn9Ni4N steel micro-alloying by RE at 700 - 900 ℃ was investigated. The results indicate that oxidation exponent n and oxidation activation energy are increased, and oxidation velocity constant kp is decreased when 0.2% RE is added in 5Cr21Mn9Ni4N steel. The addition of RE elements does not alter phase constitution of oxidation scale, however it improves the configuration of oxidation scale, and increases thermal stability and adhesivity of oxidation scale, which results in the raise of oxidation resistance of 5Cr21Mn9Ni4N steel at high temperature. The oxidation scale constitutes of refractory steel transfer from manganic oxide mostly to ferric oxide mostly with the increase of temperature, which leads to descend of compactness and desquamation resistance of oxidation scale. The mass increase of ferric oxide in the oxidation scale and the looseness of oxidation scale are the main reason to descend the oxidation resistance of refractory steel.
文摘The micro-laminated （ZrO2-Y2O3）/（Al2O3-Y2O3） composite films were prepared on the surface of Fe-13Cr alloy by an electrochemical process and a sintering process alternately. High-resolution field emission scanning electron microscopy （FE-SEM） was used to characterize the laminated films, indicating that the micro-laminated （ZrO2-Y2O3）] （Al2O3-Y2O3） films have nano-structures. SEM, EDS and mass gain measurement were adopted to study the oxidation resistance of films on Fe-13Cr alloy. It is proved that such micro-laminated films are more effective than ZrO2-Y2O3 or Al2O3-Y2O3 films to resist the oxidation of the alloy, and the oxidation resistance is increased with increasing layers in micro-laminated films. These beneficial effects can be contributed to the mechanism, by which such micro-laminated （ZrOE- YEO3）/（Al2O3-Y2O3） composite film combines all the beneficial effects and overcomes all the disadvantages of both ZrOE- Y2O3 film and Al2O3-Y2O3 film during oxidation of alloy.
基金the National Natural Science Foundation of China(21773061,21373082)the Innovation Program of Shanghai Municipal Education Commission(15ZZ031)~~
文摘Glycerol is a by-product of biodiesel production and is an important readily available platform chemical.Valorization of glycerol into value-added chemicals has gained immense attention.Herein,we carried out the conversion of glycerol to formic acid and glycolic acid using H2O2 as an oxidant and metal(Ⅲ)triflate-based catalytic systems.Aluminum(Ⅲ)triflate was found to be the most efficient catalyst for the selective oxidation of glycerol to formic acid.A correlation between the catalytic activity of the metal cations and their hydrolysis constants(Kh)and water exchange rate constants was observed.At 70 ℃,a formic acid yield of up to 72% could be attained within 12 h.The catalyst could be recycled at least five times with a high conversion rate,and hence can also be used for the selective oxidation of other biomass platform molecules.Reaction kinetics and 1H NMR studies showed that the oxidation of glycerol(to formic acid)involved glycerol hydrolysis pathways with glyceric acid and glycolic acid as the main intermediate products.Both the [Al(OH)x]^n+ Lewis acid species and CF3SO3H Brosted acid,which were generated by the in-situ hydrolysis of Al(OTf)3,were responsible for glycerol conversion.The easy availability,high efficiency,and good recyclability of Al(OTf)3 render it suitable for the selective oxidation of glycerol to high value-added products.
