In-situ oriented oxygen-defect-rich Mn-N-O via nitridation and electrochemical oxidation based on industrial-scale Mn_(2)O_(3) to achieve high-performance aqueous zinc ion battery

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.

Effect of Ferric Nitrate Loading Mode on Properties of Si_(3)N_(4) Composite MgO-C Refractories Prepared by Nitridation

In order to investigate the effect of the catalyst loading mode on the mechanical properties of Si_(3)N_(4) composite MgO-C refractories prepared by nitridation,fused magnesia,flake graphite,silicon powder,and phenolic resin were used as the main raw materials,and ferric nitrate as the catalyst to prepare refractories by nitriding at 1350℃.The effects of different catalyst supports(silicon powder,silicon powder+phenolic resin)on the formation of Si_(3)N_(4) in MgO-C refractories and the properties of refractories were studied.The results show that the silicon powder+resin catalyst support promotes the participation ofα-Si_(3)N_(4) in the reaction to generateβ-Si_(3)N_(4) and MgSiN_(2),and generates more SiC.However,this loading mode causes more gas to escape from the refractories and loosens the material structure,which reduces the mechanical properties.On the contrary,MgO-C refractories prepared by nitridation with silicon powder-supported catalysts under the same conditions show higher density and better mechanical properties.

Hydrogen peroxide and applications in green hydrocarbon nitridation and oxidation

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.

Nitridation of chromium powder in ammonia atmosphere

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）.

Synthesis of titanium oxycarbonitride by carbothermal reduction and nitridation of ilmenite with recycling of polyethylene terephthalate (PET)

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.

Kinetic study on the direct nitridation of silicon powders diluted with α-Si_3N_4 at normal pressure

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.

A SIMULATIONAL STUDY OF PRECIPITATION KINETICS AND MORPHOLOGY IN NITRIDATION OF ALLOY STEELS

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.

Preparation of Si3N4 Porous Ceramics via Combined Foam-gelcasting and Catalytic Nitridation with Fe Powder as Catalyst

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.

Review on Enhancement of Nitridation of Si Powder

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.

Modification of pillared MFI zeolite nanosheets by nitridation with tailored activity in benzylation of mesitylene and benzyl alcohol

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.

Nitridation of Ni-based alloys:thermodynamics,kinetics,and deformation phenomena accompanying internal precipitation

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.

Study on the nitridation of β-Ga2O3 films

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.

Nitridation Kinetics of Silicon Monocrystal and Morphology of Nitride Film

Basing on TGA (thermal gravimetric analysis) of thermal nitridation at l200, l250, l300℃, respectively, analysis of high temperature kinetics for nitridation of silicon monocrystal has been carried out. According to the theory for kinetics of reaction of vapour with solid phase a nitridation kinetic model, from which it can be shown thal the rate of nitridation reaction of silicon crystal should be controlled by three stage limiting factors, was proposed. These limiting factors are chemical reaction, chemical reaction mixed with diffusion and diffu- sion. Using this model to treat our experimental data, satisfactory correlation coefficient and apparent activation energy of nitridation of p-type (lll) silicon crystal have been obtained. The nitride film was identi' fied to be a-Si_3N_4 (Hexagonal, a=0.7758nm,c_o=0.5623nm) by X-ray diffraction analysis. Morphology of the nitride films formed in different nitridation duration was observed in both planar andcross-sectional views by SEM (scanning electron microscope).

Phase Composition Analysis of TiN-AI_2O_3Synthesized from Aluminum-containing Dross and Rutile by Aluminothermic Reductionnitridation Method

TiN- Al2O3 composite powder was prepared by aluminothermic reduction- nitridation method with starting materials of aluminum-containing dross and rutile,and metallic aluminum in the aluminum-containing dross as reducer. The influences of synthesis temperature（600-1 400 ℃） and aluminum-containing dross addition（20% lower than theoretical value,theoretical value,20% higher than theoretical value,and 50% higher than theoretical value） on phase compositions and microstructure of the composites were investigated,and the reaction mechanism was analyzed. The results show that（1） TiN- Al2O3 composite powder can be synthesized under the experimental conditions; the main phases are TiN,α-Al2O3,a little bytownite,and MgAl2O4;（2）enhancing synthesis temperature or increasing aluminumcontaining dross addition favors the reaction of aluminothermic reduction- nitridation;（3） in the synthesized products,α-Al2O3 is platy or columnar; TiN is sub-micron granular,which reinforces and toughens the composite.

Aluminum Reduction and Nitridation of Bauxite

The application of bauxite with low Al2O3 content has been studied in this paper and β-SiAlON has been obtained from two kinds of bauxites （Al2O3 content 68.08 mass% and 46.30 mass% respectively） by aluminum reduction and nitridation method. The sequence of reactions has been studied using thermal analysis （TG-DTA）, X-ray diffraction （XRD） analysis and scanning electron microscopy （SEM） with EDS. Compared with carbon thermal reduction and nitridation of aluminosilicates employed presently, the reaction in the system of bauxite-Al-N2 occurs at lower temperature. β-SiAlON appears as one of the main products from 1573K and exists stably in the range of the present experimental temperature. The microstructure of β-SiAlON obtained at 1773 K is short column with 5-10μm observed by SEM.

Synthesis of ZrN-Si_3N_4 Composite by Carbothermal Reduction and Nitridation of Zircon

Zircon （ ≤44 μm） and carbon black （≤30μm） were used as starting materials and mixed for 24 h using anhydrous ethanol as medium with the mass ratio of 100：40, dried fully at 60 ℃ and then dry mixed for 10 h. Specimens with size of Ф20 mm × 5 mm were pressed under 60 MPa, then dried fully at 120 ℃ , put into a furnace with 1. 0 L ·min^-1 nitrogen gas and fired at 1 400, 1 450, 1 480 and 1 500℃ for 6, 9 and 12 h, respectively. The phase composition and microstructure of the specimens were studied by XRD and SEM, and the carbothermal reduction and nitridation reaction process was thermodynamically analyzed. The results show that using zircon and carbon black as starting materials, ZrN - Si3N4 composite is synthesized by carbothermal reduction and nitridation reaction in nitrogen atmosphere. The composites with different compositions are obtained by controlling the firing temperature and partial pressure of CO gas. The proper firing temperature and holding time to synthesize ZrN - Si3N4 composite are 1 500 ℃ for 12 h.

Influences of Technological Parameters on Carbothermal Reduction and Nitridation of Titanium Dioxide

The particle size of starting materials, the homogeneity of the carbon/oxide mixtures, and the carbon content are important parameters for a rapid reaction. The influences of technological parameters（carbon particle size, oxide particle size, mixing method, carbon content） on the reaction rate of carbothermal reduction and nitridation of titanium dioxide （TiO2 ） were investigated by a continuous thermo-gravimetric analyzer for large size specimen. The carbon particle size is the most impor tant parameter for a rapid reaction, but carbon particle may have no influence on the morphology of titanium nitride （TiN） powder. Oxide particles are the precursors of TiN powder, but the TiO2 particles size has very little influence on the reaction rate. The carbon content not only influences the reaction rate to some degree, but also influences the purity of TiN powder. The mixing method of the specimen has very little influence on the reaction rate. These results are suitable for other nitrides and carbides prepared by carbothermal reduction method.

Thermodynamic Analysis for Carbothermal Reduction and Nitridation of TiO_2

The diagrams of stability relations（namely,Predominance area phase diagram,PAPD）of nitride,carbide and oxides in Ti-C-N-O system were plotted by thermodynamic calculation.The optimum conditions and main influence factors for the synthesis of titanium nitride and titanium carbide by carbothermal reduction in nitrogen atmosphere were discussed.

FORMATION OF Fe-N COMPOUNDS BY LASER NITRIDATION IN AN ATMOSPHERIC AMBIENT

The formation of Fe-N compounds by laser nitriding in an atmospheric ambient was reported. By CW-CO2 laser irradiation on pure ferrite iron in the atmospheric ambient, Fe-N compounds (including Fe2N, .Fe3AT and Fe4N) are formed as a result of a laser-enhanced and temperature-enhanced reactions. The samples were analyzed with X-ray diffraction. It is found that the laser power density, scanning speed and nitrogen temperature are the main factors influencing the formation of Fe-N compounds. Nitrogen can be activated by pre-heating at some temperature. Nitrogen activation and sample surface melting by CW-CO2 laser greatly enhance the reaction between the sample surface and nitrogen beam. After annealing at 500℃for 3h, some Fe2N and Fe3N converted into more stable Fe4N.