A thermal nitridation route for the assembly and polymerization of molecular triazine units to heptazine-based covalent frameworks has been successfully established. The obtained conjugated carbon nitride polymers fea...A thermal nitridation route for the assembly and polymerization of molecular triazine units to heptazine-based covalent frameworks has been successfully established. The obtained conjugated carbon nitride polymers feature nanostructures that show enhanced photocatalytic reactivity for hydrogen production under visible light irradiation.展开更多
Homogenization heat treatment is a key process to remove the micro-segregation and re-dissolve the undesired phases for wrought superalloy.The oxidation behavior of the wrought superalloy during the high-temperature h...Homogenization heat treatment is a key process to remove the micro-segregation and re-dissolve the undesired phases for wrought superalloy.The oxidation behavior of the wrought superalloy during the high-temperature homogenization process,however,was rarely studied.The oxidation film evolution and growth kinetics of an as-cast superalloy Rene 65 during the homogenization were systematically studied.The oxide film consists of Cr_(2)O_(3) external oxidation layer and dendritic TiO_(2) and Al_(2)O_(3) internal oxidation layer.And the growth kinetics of the oxide film followed a parabolic law.Internal nitridation occurs during the oxidation process,and TiN is apparently formed at the tip of internal oxidation layer.The originally formed TiN can be transformed into TiO_(2) or retained with the progress of oxidation.Meanwhile,the TiN is newly formed in the deeper matrix at the new oxidation-layer tip.Thermodynamic analyses revealed that there is a competition between the oxidation and nitridation.Nitridation can occur when the partial pressure of nitrogen exceeds the threshold of nitridation and the critical partial pressure ratio of nitrogen and oxygen.展开更多
β-Sialon/ZrN bonded corundum composites were synthesized using fused white corundum,alumina micro powder,zircon and carbon black by nitridation reaction sintering process. Phase composition and microstructure of the ...β-Sialon/ZrN bonded corundum composites were synthesized using fused white corundum,alumina micro powder,zircon and carbon black by nitridation reaction sintering process. Phase composition and microstructure of the synthesized composites were investigated by X-ray powder diffraction and scanning electronic microscope,and the formation process of the composites was discussed. The results show that the composites with different compositions can be obtained by controlling the heating temperature and contents of zircon and carbon black. The proper temperature to synthesize the composites is 1773 K.展开更多
The effect of nitridation process, i.e. temperature and time, on crystal structure and magnetic properties of SmFe9Nx inter- stitial compounds was systematically investigated. After nitridation treatment, nitrogen ato...The effect of nitridation process, i.e. temperature and time, on crystal structure and magnetic properties of SmFe9Nx inter- stitial compounds was systematically investigated. After nitridation treatment, nitrogen atoms were incorporated into SmFe9 alloys to form SnaFe9Nx interstitial compounds, which increased the distance of Fe-Fe and enhanced Fe-Fe interaction. As a result, SmFe9Nx interstitial compounds had a higher Curie temperature and more excellent magnetic properties than SmFe9 alloys. The relationships between nitridation temperature, nitridation time, nitriding efficiency, magnetic properties and phase transition were researched. It could be concluded that nitriding efficiency was strongly associated with magnetic properties and phase transition at different tem- peratures. The nitriding efficiency also had a connection with magnetic properties under different time, while no obvious phase transi- tion was found during that process. By studying nitridation process under a series of temperatures and time in this experiment, a suit- able nitridation temperature （713 K） and an ideal length of nitridation time （8 h） was decided, which would produce the optimal mag- netic behavior of SmFegNx interstitial compounds.展开更多
Basic organic chemicals and high value–added products are mainly produced by hydrocarbon nitridation and oxidation.However,several drawbacks limit the application of the traditional oxidation and nitridation technolo...Basic organic chemicals and high value–added products are mainly produced by hydrocarbon nitridation and oxidation.However,several drawbacks limit the application of the traditional oxidation and nitridation technologies in the future,such as complex processes,poor intrinsic safety,low atom utilization,and serious environmental pollution.The green nitridation and oxidation technologies are urgently needed.Hydrogen peroxide,a well–known green oxidant,is widely used in green hydrocarbon oxidation and nitridation.But its industrial production in China adopts fixed–bed technology,which is fall behind slurry–bed technology adopted by advanced foreign chemical companies,limiting the development of hydrogen peroxide industry and green hydrocarbon nitridation or oxidation industry.This article reviews the industrial production technologies of hydrogen peroxide and basic organic chemicals such as caprolactam,aniline,propene oxide,epichlorohydrin,phenol,and benzenediol,especially introduces the green production technologies of basic organic chemicals related with H_(2)O_(2).The article also emphasis on the efforts of Chinese researchers in developing its own slurry–bed technology of hydrogen peroxide production,and corresponding green hydrocarbon nitridation or oxidation technologies with hydrogen peroxide.Compared with traditional nitridation or oxidation technologies,green production technologies of caprolactam,propene oxide,epichlorohydrin,and benzenediol with hydrogen peroxide promote the nitrogen atom utilization from 60%to near 100%and the carbon atom utilization from 80%to near 100%.The waste emissions and environmental investments are reduced dramatically.Technological blockade against the green chemical industry of China are partially broken down,and technological upgrade in the chemical industry of China is guaranteed.展开更多
Nitrided hierarchical porous ZSM-5 was synthesized by nitridation of hierarchical porous ZSM-5 with flowing ammonia at elevated temperature.The samples were characterized by XRD,SEM,Nitrogen sorption isotherms,NH3-TPD...Nitrided hierarchical porous ZSM-5 was synthesized by nitridation of hierarchical porous ZSM-5 with flowing ammonia at elevated temperature.The samples were characterized by XRD,SEM,Nitrogen sorption isotherms,NH3-TPD and Py-IR,and evaluated in alkylation of benzene and methanol.The result indicated that the high specific surface area of parent ZSM-5 was maintained,while the Bronsted acidity was effectively adjusted by nitridation.Moreover,the high suppression of ethylbenzene was observed on nitrided catalyst and this could be attributed to the decrease of Bronsted acidity which suppressed the methanol to olefins reactions.展开更多
CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were...CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different tempera- tures. Chromium nitride formed at 700-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction （XRD）, and the Cr2N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr2N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy （HRTEM）. After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope （SEM）.展开更多
An innovative and sustainable carbothermal reduction and nitridation(CTRN) process of ilmenite(FeTiO_3) using a mixture of polyethylene terephthalate(PET) and coal as the primary reductant under an H_2–N_2 atmosphere...An innovative and sustainable carbothermal reduction and nitridation(CTRN) process of ilmenite(FeTiO_3) using a mixture of polyethylene terephthalate(PET) and coal as the primary reductant under an H_2–N_2 atmosphere was proposed. The use of PET as an alternative source of carbon not only enhances the porosity of the pellets but also results in the separation of Fe from titanium oxycarbonitride(TiOxCyNz) particles because of the differences in surface tension. The experiments were carried out at 1250°C for 3 h using four different PET contents ranging from 25wt% to 100wt% in the reductant. X-ray diffraction(XRD),scanning electron microscopy(SEM) in conjunction with energy-dispersive X-ray spectroscopy(EDX),and LECO elemental analysis were used to study the phases and microstructures of the reduced samples. In the case of 75wt% PET,iron distinctly separated from the synthesized Ti OxCyNz phase. With increasing PET content in the sample,the reduction and nitridation rates substantially increased. The synthesis of an oxycarbonitride with stoichiometry of TiO_(0.02)C_(0.13)N_(0.85) with minimal intermediate titanium sub-oxides was achieved. The results also showed that the iron particles formed from CTRN of FeTiO_3 exhibited a spherical morphology,which is conducive for Fe removal via the Becher process.展开更多
Silicon nitride （Si3N4） powders were prepared by the direct nitridation of silicon powders diluted with a- Si3N4 at normal pressure. Silicon powders of 2.2 μm in average diameter were used as the raw materials. The...Silicon nitride （Si3N4） powders were prepared by the direct nitridation of silicon powders diluted with a- Si3N4 at normal pressure. Silicon powders of 2.2 μm in average diameter were used as the raw materials. The nitriding temperature was from 1623 to 1823 K, and the reaction time ranged from 0 to 20 min. The phase compositions and morphologies of the products were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The effects of nitriding temperature and reaction time on the conversion rate of silicon were determined. Based on the shrinking core model as well as the relationship between the conversion rate of silicon and the reaction time at different temperatures, a simple model was derived to describe the reaction between silicon and nitrogen. The model revealed an asymptotic exponential trend of the silicon conversion rate with time. Three kinetic parameters of silicon nitridation at atmospheric pressure were calculated, including the pre-exponential factor （2.27 cm.s^-1） in the Arrhenius equation, activation energy （114 kJ·mol^-1）, and effective diffusion coefficient （6.2×10-s cm2.s^-1）. A formula was also derived to calculate the reaction rate constant.展开更多
The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary c...The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.展开更多
Prenitridation of the TiBx coating surface of the Sigma SM1240 SiC fiber can form more stable compounds at the surface and obstruct the release of boron atoms into the Ti-based alloy matrix. The effect of nitridation ...Prenitridation of the TiBx coating surface of the Sigma SM1240 SiC fiber can form more stable compounds at the surface and obstruct the release of boron atoms into the Ti-based alloy matrix. The effect of nitridation on the tensile strength of the fiber was investigated in this work. Nitridation could degrade the tensile strength of the SiC fiber if the treating temperature and time are not optimized. The chemical reaction between the W core and SiC and the modification of fiber microstructure during the nitridation are responsible for the degradation in strength. The strength can be maintained by further optimization of the treating temperature and time. Therefore, stabilizing the surface of TiBx coating and hence the interface of the SiCf/Ti composite by the nitridation of the SiC fiber is a feasible technique for practical applications.展开更多
Isothermal thermo-gravimetric analysis was applied to investigate the nitridation kinetics of manganese powder with different particle sizes at 800, 900 and 1000 ℃. The apparent activation energy and nitridation kine...Isothermal thermo-gravimetric analysis was applied to investigate the nitridation kinetics of manganese powder with different particle sizes at 800, 900 and 1000 ℃. The apparent activation energy and nitridation kinetics equations of manganese powder with different particle sizes were obtained from unreacted shrinking core model and Arrhenius formula. It was found that the nitridation mechanism was controlied by interracial chemical reaction. The apparent activation energy and the apparent rate constant of nitridation reaction were affected by particle sizes. With the decrease of particle size, the apparent activation energy decreased whilst the apparent rate constant increased. It was suggested that the refinement of the manganese powder contributed to the increase of molar surface energy, which accounted for the lower apparent activation energy.展开更多
An atomic model of compound precipitation in alloys, which couples cellular automaton growth/dissociation of precipitates and randomwalk diffusion, has been developed and programmed for 2 dimensional computer simulati...An atomic model of compound precipitation in alloys, which couples cellular automaton growth/dissociation of precipitates and randomwalk diffusion, has been developed and programmed for 2 dimensional computer simulation. With boundary condition parameters and diffusion parameters variable, a series of simulation experiments were carried out for a qualitative study of nitride precipitation behavior in nitridation of alloy steels. Effects of nitrogen potential and alloy composition on kinetics and microstructure of the precipitation were addressed, and the so called "iso-activity aging" phenomenon was examined.展开更多
As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batter...As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs.展开更多
Single-crystal GaN layers have been obtained by nitridingβ-Ga2O3 films in NH3 atmosphere.The effect of the temperature and time on the nitridation and conversion of Ga2O3 films have been investigated.The nitridation ...Single-crystal GaN layers have been obtained by nitridingβ-Ga2O3 films in NH3 atmosphere.The effect of the temperature and time on the nitridation and conversion of Ga2O3 films have been investigated.The nitridation process results in lots of holes in the surface of films.The higher nitridation temperature and longer time can promote the nitridation and improve the crystal quality of GaN films.The converted Ga N porous films show the single-crystal structures and lowstress,which can be used as templates for the epitaxial growth of high-quality GaN.展开更多
Si3N4 porous ceramics were fabricated by a combined foam-gelcasting and catalytic nitridation method at 1473-1623 K using silicon powder as the starting material,hexadecyl trimethyl ammonium bromide(CTAB)as the foamin...Si3N4 porous ceramics were fabricated by a combined foam-gelcasting and catalytic nitridation method at 1473-1623 K using silicon powder as the starting material,hexadecyl trimethyl ammonium bromide(CTAB)as the foaming agent,and different amounts of micron Fe powder as the catalyst.The effects of the nitridation temperature and the Fe powder addition on the phase composition,the mechanical properties,and the microstructure of the samples were researched.The results show that when nitriding at 1573 K for 5 h and adding 1 mass%Fe powder(with respect to the Si powder),the sample has a high porosity and suitable mechanical properties:the porosity of 76.5%,the compressive strength of 16.2 MPa,and the specific strength of 22.7 MPa•cm3•g^-1.展开更多
This paper reviewed the effect of powder characteristics and additives including metals,rare earth oxides,and ZrO2 on nitridation of Si powder.The decrease of particle size of Si powder increased nitridation.Most of m...This paper reviewed the effect of powder characteristics and additives including metals,rare earth oxides,and ZrO2 on nitridation of Si powder.The decrease of particle size of Si powder increased nitridation.Most of metal additives inhibited nitridation,while some metal additives such as Fe,Cu,Cr,and Ca increased nitrida—tion.Otherwise,the addition of metals might lead to the degradation of physical and mechanical properties of Si3N4.All the rare earth oxides,especially CeO2 and Eu2O3,showed nitridation enhancing effect.In addition,ZrO2 with small particle size showed a stronger enhancing effect.展开更多
L1_(0)-ordered FeNi alloy with a high uniaxial magnetic anisotropy and large magnetic moment is a promising candidate for rare-earth-free permanent magnets applications.However,the synthesis of this chemically ordered...L1_(0)-ordered FeNi alloy with a high uniaxial magnetic anisotropy and large magnetic moment is a promising candidate for rare-earth-free permanent magnets applications.However,the synthesis of this chemically ordered phase remains a longstanding challenge because of its low chemical order-disorder transition temperature(200-320℃).Although a non-equilibrium synthetic route based on a nitrogen topotactic reaction has been proposed as a valid approach,the volume fraction and degree of chemical ordering of the product phase are limited.Herein,we propose a promising approach that promotes the efficient formation of L1_(0)-ordered nitride phase in FeNi nanopowders by introducing a quenching treatment during a low-oxygen induction thermal plasma process.The quenched FeNi nanopowders possessed much smaller powder sizes(40.4 vs 74.0 nm),exhibited higher number densities of nanotwins(39.8%vs 24.1%)and formed much larger volume fraction(33.6 wt.%vs 0.6 wt.%)of ordered phase than the unquenched nanopowders.Notably,quenching-induced high-density nanotwins led to the dominant coverage of serrated{001}crystal facets over the surfaces of the FeNi nanopowders.Such unique features substantially accelerated the formation of the L1_(0)-ordered nitride phase in the FeNi nanopowders because the{001}crystallographic orientation had the highest nitrogen diffusivity.This work provides not only a valid synthetic approach for mass production of the L10-ordered nitride phase in FeNi nanopowders but also novel insights into the crystal-defect-assisted nitridation of nanomaterials.展开更多
When a moderately stable phase is precipitated out during an intemal reaction, the behaviour of the penetrating atoms within the diffusion zone can be interpreted based on thermodynamic considerations. Evidence for “...When a moderately stable phase is precipitated out during an intemal reaction, the behaviour of the penetrating atoms within the diffusion zone can be interpreted based on thermodynamic considerations. Evidence for “up-hill” diffusion of the penetrating species through the matrix towards the precipitation front during the intemal nitridation of Ni-Cr alloys at 1125℃ and 6000 bar of N2-pressure was predicted. Such behaviour of nitrogen is opposite to the boundary conditions in Wagner＇s description of internal reactions. A volume change associated with the precipitation reaction resulted in a stress gradient between the alloys surface and the intemal nitridation front. Stress relief occurred mainly by transport of nickel to the gas/metal interface. Pipe diffusion-controlled creep is the dominant stress accommodation mechanism during nitriding of dilute Ni-Cr alloys at 700℃ under a flowing NH3 ＋ H2 gas mixture.展开更多
High-quality ferrovanadium nitride(FeV45N,FeV55N and Fe65N)was fabricated using the raw materials of Fe_(3)O_(4),V_(2)O_(5) and graphite via carbothermal reduction nitridation method.Compared with the traditional meth...High-quality ferrovanadium nitride(FeV45N,FeV55N and Fe65N)was fabricated using the raw materials of Fe_(3)O_(4),V_(2)O_(5) and graphite via carbothermal reduction nitridation method.Compared with the traditional methods,it shortens the production process of ferrovanadium nitride by avoiding the preparation of ferrovanadium.The effects of C/O molar ratio and reaction temperature on phase transition,density,carbon,oxygen and nitrogen contents and microstructure were investigated.The appropriate C/O molar ratio is crucial to obtain the products with high nitrogen content.It is also found that a higher temperature is beneficial for the densification,and the density of the products obtained at 1550℃ is much higher than that at 1500℃.Moreover,a higher temperature contributes to the increase in nitrogen content owing to the higher reaction kinetics.The carbothermal reduction nitridation method is proved to be a facile route to fabricate cost-effective ferrovanadium nitride and is possible to be applied for industrial production.展开更多
基金supported by the National Basic Research Program of China(973 Program2013CB632405)+3 种基金the National Natural Science Foundation of China(2142530921033003)the Specialized Research Fund for the Doctoral Program of Higher Education(20133514110003)the Department of Education of Fujian Province in China~~
文摘A thermal nitridation route for the assembly and polymerization of molecular triazine units to heptazine-based covalent frameworks has been successfully established. The obtained conjugated carbon nitride polymers feature nanostructures that show enhanced photocatalytic reactivity for hydrogen production under visible light irradiation.
基金supported by the Beijing Municipal Natural Science Foundation(No.2212041)National Natural Science Foundation of China(No.51804232)supported by the Interdisciplinary Research Project for Young Teachers of USTB(Fundamental Research Funds for the Central Universities)(FRF-IDRY-20-020).
文摘Homogenization heat treatment is a key process to remove the micro-segregation and re-dissolve the undesired phases for wrought superalloy.The oxidation behavior of the wrought superalloy during the high-temperature homogenization process,however,was rarely studied.The oxidation film evolution and growth kinetics of an as-cast superalloy Rene 65 during the homogenization were systematically studied.The oxide film consists of Cr_(2)O_(3) external oxidation layer and dendritic TiO_(2) and Al_(2)O_(3) internal oxidation layer.And the growth kinetics of the oxide film followed a parabolic law.Internal nitridation occurs during the oxidation process,and TiN is apparently formed at the tip of internal oxidation layer.The originally formed TiN can be transformed into TiO_(2) or retained with the progress of oxidation.Meanwhile,the TiN is newly formed in the deeper matrix at the new oxidation-layer tip.Thermodynamic analyses revealed that there is a competition between the oxidation and nitridation.Nitridation can occur when the partial pressure of nitrogen exceeds the threshold of nitridation and the critical partial pressure ratio of nitrogen and oxygen.
基金Project(50274021) supported by the National Natural Science Foundation of China and Baoshan Iron and Steel Co., Ltd.
文摘β-Sialon/ZrN bonded corundum composites were synthesized using fused white corundum,alumina micro powder,zircon and carbon black by nitridation reaction sintering process. Phase composition and microstructure of the synthesized composites were investigated by X-ray powder diffraction and scanning electronic microscope,and the formation process of the composites was discussed. The results show that the composites with different compositions can be obtained by controlling the heating temperature and contents of zircon and carbon black. The proper temperature to synthesize the composites is 1773 K.
基金Project supported by National High Technology Research and Development Program of China （863 Program） （2011AA03A402） and the International Scientific and Technological Cooperation Project （2010DFB53520）
文摘The effect of nitridation process, i.e. temperature and time, on crystal structure and magnetic properties of SmFe9Nx inter- stitial compounds was systematically investigated. After nitridation treatment, nitrogen atoms were incorporated into SmFe9 alloys to form SnaFe9Nx interstitial compounds, which increased the distance of Fe-Fe and enhanced Fe-Fe interaction. As a result, SmFe9Nx interstitial compounds had a higher Curie temperature and more excellent magnetic properties than SmFe9 alloys. The relationships between nitridation temperature, nitridation time, nitriding efficiency, magnetic properties and phase transition were researched. It could be concluded that nitriding efficiency was strongly associated with magnetic properties and phase transition at different tem- peratures. The nitriding efficiency also had a connection with magnetic properties under different time, while no obvious phase transi- tion was found during that process. By studying nitridation process under a series of temperatures and time in this experiment, a suit- able nitridation temperature （713 K） and an ideal length of nitridation time （8 h） was decided, which would produce the optimal mag- netic behavior of SmFegNx interstitial compounds.
基金support from the National Natural Science Foundation of China(U19B6002)National Key Research and Development Program of China(2016YFB0301600).
文摘Basic organic chemicals and high value–added products are mainly produced by hydrocarbon nitridation and oxidation.However,several drawbacks limit the application of the traditional oxidation and nitridation technologies in the future,such as complex processes,poor intrinsic safety,low atom utilization,and serious environmental pollution.The green nitridation and oxidation technologies are urgently needed.Hydrogen peroxide,a well–known green oxidant,is widely used in green hydrocarbon oxidation and nitridation.But its industrial production in China adopts fixed–bed technology,which is fall behind slurry–bed technology adopted by advanced foreign chemical companies,limiting the development of hydrogen peroxide industry and green hydrocarbon nitridation or oxidation industry.This article reviews the industrial production technologies of hydrogen peroxide and basic organic chemicals such as caprolactam,aniline,propene oxide,epichlorohydrin,phenol,and benzenediol,especially introduces the green production technologies of basic organic chemicals related with H_(2)O_(2).The article also emphasis on the efforts of Chinese researchers in developing its own slurry–bed technology of hydrogen peroxide production,and corresponding green hydrocarbon nitridation or oxidation technologies with hydrogen peroxide.Compared with traditional nitridation or oxidation technologies,green production technologies of caprolactam,propene oxide,epichlorohydrin,and benzenediol with hydrogen peroxide promote the nitrogen atom utilization from 60%to near 100%and the carbon atom utilization from 80%to near 100%.The waste emissions and environmental investments are reduced dramatically.Technological blockade against the green chemical industry of China are partially broken down,and technological upgrade in the chemical industry of China is guaranteed.
基金the National Natural Science Foundation of China (Nos. 21476207 and 21506189)Zhejiang Postdoctoral Research Funded Projects (No. BSH1502147)National Basic Research Program of China (973 Program, No. 2011CB710800)
文摘Nitrided hierarchical porous ZSM-5 was synthesized by nitridation of hierarchical porous ZSM-5 with flowing ammonia at elevated temperature.The samples were characterized by XRD,SEM,Nitrogen sorption isotherms,NH3-TPD and Py-IR,and evaluated in alkylation of benzene and methanol.The result indicated that the high specific surface area of parent ZSM-5 was maintained,while the Bronsted acidity was effectively adjusted by nitridation.Moreover,the high suppression of ethylbenzene was observed on nitrided catalyst and this could be attributed to the decrease of Bronsted acidity which suppressed the methanol to olefins reactions.
基金financially supported by the Innovation Foundation of Shanghai University (Nos. sdcx2012033 and sdcx2012062)the Special Research Foundation for Training and Selecting Outstanding Young Teachers of Universities in Shanghai (No. B.37-0407-12-008)+1 种基金the National Natural Science Foundation of China (Nos. 51072112 and 51272154)the Projects of International Cooperation and Exchanges NSFC (No. 51311130110)
文摘CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different tempera- tures. Chromium nitride formed at 700-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction （XRD）, and the Cr2N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr2N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy （HRTEM）. After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope （SEM）.
基金financial support from Universiti Sains Malaysia(USM)Fellowship(APEX 1002/JHEA/ATSG4001)financially supported by USM and Ministry of Higher Education(MOHE)of Malaysia through Fundamental Research Grant Scheme(FRGS)(Nos.203/PBAHAN/6071230 and 203/PBAHAN/607126)Research University Grant for Individual(RUI)from USM(No.1001/PBAHAN/814273)
文摘An innovative and sustainable carbothermal reduction and nitridation(CTRN) process of ilmenite(FeTiO_3) using a mixture of polyethylene terephthalate(PET) and coal as the primary reductant under an H_2–N_2 atmosphere was proposed. The use of PET as an alternative source of carbon not only enhances the porosity of the pellets but also results in the separation of Fe from titanium oxycarbonitride(TiOxCyNz) particles because of the differences in surface tension. The experiments were carried out at 1250°C for 3 h using four different PET contents ranging from 25wt% to 100wt% in the reductant. X-ray diffraction(XRD),scanning electron microscopy(SEM) in conjunction with energy-dispersive X-ray spectroscopy(EDX),and LECO elemental analysis were used to study the phases and microstructures of the reduced samples. In the case of 75wt% PET,iron distinctly separated from the synthesized Ti OxCyNz phase. With increasing PET content in the sample,the reduction and nitridation rates substantially increased. The synthesis of an oxycarbonitride with stoichiometry of TiO_(0.02)C_(0.13)N_(0.85) with minimal intermediate titanium sub-oxides was achieved. The results also showed that the iron particles formed from CTRN of FeTiO_3 exhibited a spherical morphology,which is conducive for Fe removal via the Becher process.
基金supported by the Natural Science Foundation of China(No.51106008)the Major State Basic Research and Development Program of China(No.2012CB720406)
文摘Silicon nitride （Si3N4） powders were prepared by the direct nitridation of silicon powders diluted with a- Si3N4 at normal pressure. Silicon powders of 2.2 μm in average diameter were used as the raw materials. The nitriding temperature was from 1623 to 1823 K, and the reaction time ranged from 0 to 20 min. The phase compositions and morphologies of the products were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The effects of nitriding temperature and reaction time on the conversion rate of silicon were determined. Based on the shrinking core model as well as the relationship between the conversion rate of silicon and the reaction time at different temperatures, a simple model was derived to describe the reaction between silicon and nitrogen. The model revealed an asymptotic exponential trend of the silicon conversion rate with time. Three kinetic parameters of silicon nitridation at atmospheric pressure were calculated, including the pre-exponential factor （2.27 cm.s^-1） in the Arrhenius equation, activation energy （114 kJ·mol^-1）, and effective diffusion coefficient （6.2×10-s cm2.s^-1）. A formula was also derived to calculate the reaction rate constant.
基金Supported by the Science and Technology Program of Guangzhou,China(201804010172)National Natural Science Foundation of China(21808040,21706031,21276052,21776049)Science and Technology Planning Project of Guangdong Province,China(2012A090300006)
文摘The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.
基金The authors wish to thank the Royal Society, UK, and the Chinese Academy of Sciences for sponsoring a joint project-Grant No.761. The nitridation of the SiC fiber (Sigma SM1240) was carried out at QM, University of London, UK. Supply of the SiC fiber by
文摘Prenitridation of the TiBx coating surface of the Sigma SM1240 SiC fiber can form more stable compounds at the surface and obstruct the release of boron atoms into the Ti-based alloy matrix. The effect of nitridation on the tensile strength of the fiber was investigated in this work. Nitridation could degrade the tensile strength of the SiC fiber if the treating temperature and time are not optimized. The chemical reaction between the W core and SiC and the modification of fiber microstructure during the nitridation are responsible for the degradation in strength. The strength can be maintained by further optimization of the treating temperature and time. Therefore, stabilizing the surface of TiBx coating and hence the interface of the SiCf/Ti composite by the nitridation of the SiC fiber is a feasible technique for practical applications.
基金Sponsored by National Natural Science Foundation of China(51374023)
文摘Isothermal thermo-gravimetric analysis was applied to investigate the nitridation kinetics of manganese powder with different particle sizes at 800, 900 and 1000 ℃. The apparent activation energy and nitridation kinetics equations of manganese powder with different particle sizes were obtained from unreacted shrinking core model and Arrhenius formula. It was found that the nitridation mechanism was controlied by interracial chemical reaction. The apparent activation energy and the apparent rate constant of nitridation reaction were affected by particle sizes. With the decrease of particle size, the apparent activation energy decreased whilst the apparent rate constant increased. It was suggested that the refinement of the manganese powder contributed to the increase of molar surface energy, which accounted for the lower apparent activation energy.
基金We gratefully acknowledge the sponsorship of the present work by Natural Science Fundation of China under the project numbered
文摘An atomic model of compound precipitation in alloys, which couples cellular automaton growth/dissociation of precipitates and randomwalk diffusion, has been developed and programmed for 2 dimensional computer simulation. With boundary condition parameters and diffusion parameters variable, a series of simulation experiments were carried out for a qualitative study of nitride precipitation behavior in nitridation of alloy steels. Effects of nitrogen potential and alloy composition on kinetics and microstructure of the precipitation were addressed, and the so called "iso-activity aging" phenomenon was examined.
基金supports from the National Natural Science Foundation of China(No.21805063)the Natural Science Foundation of Guangdong Province for Distinguished Young Scholars(No.2018B030306022)+2 种基金the Project of International Science and Technology Cooperation in Guangdong Province(No.2020A0505100016)the Shenzhen Sauvage Nobel Laureate Laboratory for Smart Materialsthe Shenzhen Science and Technology Program(Nos.KQTD20200820113045083,ZDSYS20190902093220279)。
文摘As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs.
基金Project supported by the National Key Research and Development Program of China(Grant No.2017YFB0404201)the Six-Talent Peaks Project in Jiangsu Province,China(Grant No.XCL-107)+2 种基金the State Key Research and Development Program of Jiangsu Province,China(Grant No.BE2018115)the Fund from the Solid-state Lighting and Energy-saving Electronics Collaborative Innovation Center,PAPDthe Fund from the State Grid Shandong Electric Power Company
文摘Single-crystal GaN layers have been obtained by nitridingβ-Ga2O3 films in NH3 atmosphere.The effect of the temperature and time on the nitridation and conversion of Ga2O3 films have been investigated.The nitridation process results in lots of holes in the surface of films.The higher nitridation temperature and longer time can promote the nitridation and improve the crystal quality of GaN films.The converted Ga N porous films show the single-crystal structures and lowstress,which can be used as templates for the epitaxial growth of high-quality GaN.
基金National Natural Science Foundation of China(Grant No.51672194 and 51872210)Program for Innovative Teams of Outstanding Young and Middle-aged Researchers in the Higher Education Institutions of Hubei Province(T201602)+1 种基金Key Program of Natural Science Foundation of Hubei Province,China(Contract No.2017CFA004)the China Scholarship Council(CSC)(No.201808420278).
文摘Si3N4 porous ceramics were fabricated by a combined foam-gelcasting and catalytic nitridation method at 1473-1623 K using silicon powder as the starting material,hexadecyl trimethyl ammonium bromide(CTAB)as the foaming agent,and different amounts of micron Fe powder as the catalyst.The effects of the nitridation temperature and the Fe powder addition on the phase composition,the mechanical properties,and the microstructure of the samples were researched.The results show that when nitriding at 1573 K for 5 h and adding 1 mass%Fe powder(with respect to the Si powder),the sample has a high porosity and suitable mechanical properties:the porosity of 76.5%,the compressive strength of 16.2 MPa,and the specific strength of 22.7 MPa•cm3•g^-1.
基金financially supported by Guangdong Innovative and Entrepreneurial Research Team Program ( No. 2013G061)the National Natural Science Foundation of China ( No. 51402055)
文摘This paper reviewed the effect of powder characteristics and additives including metals,rare earth oxides,and ZrO2 on nitridation of Si powder.The decrease of particle size of Si powder increased nitridation.Most of metal additives inhibited nitridation,while some metal additives such as Fe,Cu,Cr,and Ca increased nitrida—tion.Otherwise,the addition of metals might lead to the degradation of physical and mechanical properties of Si3N4.All the rare earth oxides,especially CeO2 and Eu2O3,showed nitridation enhancing effect.In addition,ZrO2 with small particle size showed a stronger enhancing effect.
文摘L1_(0)-ordered FeNi alloy with a high uniaxial magnetic anisotropy and large magnetic moment is a promising candidate for rare-earth-free permanent magnets applications.However,the synthesis of this chemically ordered phase remains a longstanding challenge because of its low chemical order-disorder transition temperature(200-320℃).Although a non-equilibrium synthetic route based on a nitrogen topotactic reaction has been proposed as a valid approach,the volume fraction and degree of chemical ordering of the product phase are limited.Herein,we propose a promising approach that promotes the efficient formation of L1_(0)-ordered nitride phase in FeNi nanopowders by introducing a quenching treatment during a low-oxygen induction thermal plasma process.The quenched FeNi nanopowders possessed much smaller powder sizes(40.4 vs 74.0 nm),exhibited higher number densities of nanotwins(39.8%vs 24.1%)and formed much larger volume fraction(33.6 wt.%vs 0.6 wt.%)of ordered phase than the unquenched nanopowders.Notably,quenching-induced high-density nanotwins led to the dominant coverage of serrated{001}crystal facets over the surfaces of the FeNi nanopowders.Such unique features substantially accelerated the formation of the L1_(0)-ordered nitride phase in the FeNi nanopowders because the{001}crystallographic orientation had the highest nitrogen diffusivity.This work provides not only a valid synthetic approach for mass production of the L10-ordered nitride phase in FeNi nanopowders but also novel insights into the crystal-defect-assisted nitridation of nanomaterials.
文摘When a moderately stable phase is precipitated out during an intemal reaction, the behaviour of the penetrating atoms within the diffusion zone can be interpreted based on thermodynamic considerations. Evidence for “up-hill” diffusion of the penetrating species through the matrix towards the precipitation front during the intemal nitridation of Ni-Cr alloys at 1125℃ and 6000 bar of N2-pressure was predicted. Such behaviour of nitrogen is opposite to the boundary conditions in Wagner＇s description of internal reactions. A volume change associated with the precipitation reaction resulted in a stress gradient between the alloys surface and the intemal nitridation front. Stress relief occurred mainly by transport of nickel to the gas/metal interface. Pipe diffusion-controlled creep is the dominant stress accommodation mechanism during nitriding of dilute Ni-Cr alloys at 700℃ under a flowing NH3 ＋ H2 gas mixture.
基金The authors gratefully acknowledge financial support from the National Natural Science Foundation of China(Grant No.51734002).
文摘High-quality ferrovanadium nitride(FeV45N,FeV55N and Fe65N)was fabricated using the raw materials of Fe_(3)O_(4),V_(2)O_(5) and graphite via carbothermal reduction nitridation method.Compared with the traditional methods,it shortens the production process of ferrovanadium nitride by avoiding the preparation of ferrovanadium.The effects of C/O molar ratio and reaction temperature on phase transition,density,carbon,oxygen and nitrogen contents and microstructure were investigated.The appropriate C/O molar ratio is crucial to obtain the products with high nitrogen content.It is also found that a higher temperature is beneficial for the densification,and the density of the products obtained at 1550℃ is much higher than that at 1500℃.Moreover,a higher temperature contributes to the increase in nitrogen content owing to the higher reaction kinetics.The carbothermal reduction nitridation method is proved to be a facile route to fabricate cost-effective ferrovanadium nitride and is possible to be applied for industrial production.
