An Efficient Boron Source Activation Strategy for the Low‑Temperature Synthesis of Boron Nitride Nanotubes

Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid boron.In this study,we developed a novel approach for efficiently activating boron by introducing alkali metal compounds into the conventional MgO–B system.This approach can be adopted to form various low-melting-point AM–Mg–B–O growth systems.These growth systems have improved catalytic capability and reactivity even under low-temperature conditions,facilitating the synthesis of BNNTs at temperatures as low as 850℃.In addition,molecular dynamics simulations based on density functional theory theoretically demonstrate that the systems maintain a liquid state at low temperatures and interact with N atoms to form BN chains.These findings offer novel insights into the design of boron activation and are expected to facilitate research on the low-temperature synthesis of BNNTs.

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.

Microstructure evolution and nitrides precipitation in in-situ Ti_2 AlN/TiAl composites during isothermal aging at 900°C

Microstructures of Ti2AlN/TiAl composites prepared by in-situ method were characterized in in-situ and aging treatment conditions and the nitride precipitation was investigated in Ti2AlN/TiAl composites aged at 900 ℃ for 24 h after being heat treated at 1400 ℃ for 0.5 h. The in-situ composites consist of γ＋α2 lamellar colonies, equiaxed y grains and Ti2AlN reinforcements. Matrix with nearly fully lamellar structure formed after solution and subsequently aging treatment. With the increase of Ti2AlN content, the nearly fully lamellar structure becomes instable for the aged composites. According to TEM study, fine Ti2AlN precipitates are found to distribute at the grain boundaries of lamellar colony. Needle-like Ti3AlN precipitates arrange in line with growing axis parallel to [001] direction of the γ-TiAl matrix and another needle-like Ti3AlN precipitates with lager size distribute at the dislocations. Key words：

Thermal nitridation of triazine motifs to heptazine-based carbon nitride frameworks for use in visible light photocatalysis

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.

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）.

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.

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.

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.

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.

Effects of Nitridation on Properties of SiC Fiber and Interface of Ti Matrix Composite

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.

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.

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.

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.

Preparation of β-Sialon/ZrN bonded corundum composites from zircon by nitridation reaction sintering process

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.

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.

In-situ multi-information measurement system for preparing gallium nitride photocathode

We introduce the first domestic in-situ multi-information measurement system for a gallium nitride （GaN） photo- cathode. This system can successfully fulfill heat cleaning and activation for GaN in an ultrahigh vacuum environment and produce a GaN photocathode with a negative electron affinity （NEA） status. Information including the heat clean- ing temperature, vacuum degree, photocurrent, electric current of cesium source, oxygen source, and the most important information about the spectral response, or equivalently, the quantum efficiency （QE） can be obtained during prepa- ration. The preparation of a GaN photocathode with this system indicates that the optimal heating temperature in a vacuum is about 700 ~C. We also develop a method of quickly evaluating the atomically clean surface with the vacuum degree versus wavelength curve to prevent possible secondary contamination when the atomic level cleaning surface is tested with X-ray photoelectron spectroscopy. The photocurrent shows a quick enhancement when the current ratio between the cesium source and oxygen source is 1.025. The spectral response of the GaN photocathode is flat in a wavelength range from 240 nm to 365 nm, and an abrupt decline is observed at 365 nm, which demonstrates that with the in-si$u multi-information measurement system the NEA GaN photocathode can be successfully prepared.

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.

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).

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.