Nitriding of Aluminium Alloy in Nitrogen and Nitrogen-Helium Mixture Using 100 Hz-Pulsed DC Glow Discharge

Nitriding of aluminium alloy （AlFel.sZn0.8） in nitrogen and nitrogen-helium mixture was carried out by using 100 Hz-pulsed DC glow discharge. Samples are treated for different durations, namely 4 h, 8 h and 12 h, in nitrogen plasma as well as in a mixture of nitrogen- helium plasma for the same processing duration of 4 h. All nitriding treatments are carried out at an input power of 100 W, filling pressure of 1 mbar and substrates temperature of 250~C. X-ray diffraction （XRD） results show an expansion in lattice spacing and consequently shift of diffraction peaks towards lower angle with the addition of helium in nitrogen plasma. Surface morphology of the treated sample is investigated by scanning electron microscopy （SEM） and energy dispersive X-ray analysis （EDX）. Vickers micro-hardness testing results show increases in surface hardness with processing duration as well as with the addition of helium in nitrogen plasmas. This increase of surface hardness may be attributed to the diffusion of nitrogen content in the surface layer generating internal stresses. It is observed that the addition of helium positively affects the nitriding of samples.

High Nitrogen Austenitic Stainless Steels Manufactured by Nitrogen Gas Alloying and Adding Nitrided Ferroalloys

A simple and feasible method for the production of high nitrogen austenitic stainless steels involves nitrogen gas alloying and adding nitrided ferroalloys under normal atmospheric conditions. Alloying by nitrogen gas bubbling in Fe-Cr-Mn-Mo series alloys was carried out in MoSi2 resistance furnace and air induction furnace under normal atmospheric conditions. The results showed that nitrogen alloying could be accelerated by increasing nitrogen gas flow rate, prolonging residence time of bubbles, increasing gas/molten steel interfaces, and decreasing the sulphur and oxygen contents in molten steel. Nitrogen content of 0.69% in 18Crl8Mn was obtained using air induction furnace by bubbling of nitrogen gas from porous plug. In addition, the nickel-free, high nitrogen austenitic stainless steels with sound and compact macrostructure had been produced in the laboratory using vacuum induction furnace and electroslag remelting furnace under nitrogen atmosphere by the addition of nitrided alloy with the maximum nitrogen content of 0.81%. Pores were observed in the ingots obtained by melting and casting in vacuum induction furnace with the addition of nitrided ferroalloys and under nitrogen atmosphere. After electroslag remelting of the cast ingots, they were all sound and were free of pores. The yield of nitrogen increased with the decrease of melting rate in the ESR process. Due to electroslag remelting under nitrogen atmosphere and the consequential addition of aluminum as deoxidizer to the slag, the loss of manganese decreased obviously. There existed mainly irregular Al2O3 inclusions and MnS inclusions in ESR ingots, and the size of most of the inclusions was less than 5 um. After homogenization of the hot rolled plate at 1 150℃ × 1 h followed by water quenching, the microstructure consisted of homogeneous austenite.

MATHEMATICAL MODELS OF NITROGEN CONCENTRATION PROFILE OF ION NITRIDED LAYERS AND COMPUTER SIMULATION

The mathematical models of the kinetics of the layer growth at different ion nitriding condi- tions of armco iron.steels 45,40Cr,42CrMo and 38CrMoAl have been established.Based on these models the expression of nitrogen concentration profile of ion nitrided layers have been deduced with profile simulating method.They are C_=C_(min)^+(P_4)/(ξ_1-x)+(P_5)/(ξ_(10)~2)(ξ_1-x)~2 C_(γ′)=C_(min)^(γ′)+(P_1)/(ξ_(21))(ξ_2-x)+(P_2)/(ξ_(21)~2)(ξ_2-x)~2 C_α=C_(min)~α+(C_(33))/(C_(33))/(ξ_(32))(ξ_3-x)~3 Using these models,the kinetics of layer growth and the nitrogen concentration profile of ion nitrided layers were sinulated on Apple-Ⅱ computer.Results show that the simulated curves coincide quite well with the experimental data.

Promotion of activation ability of N vacancies to N2 molecules on sulfur-doped graphitic carbon nitride with outstanding photocatalytic nitrogen fixation ability

Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and temperature-programmed desorption were used to characterize the as-prepared catalyst. The results showed that plasma treatment cannot change the morphology of the as-prepared catalyst but introduces nitrogen vacancies and sulfur into g-C3N4 lattice simultaneously. The as-prepared co-doped g-C3N4 displays an ammonium ion production rate as high as 6.2 mg·L^-1·h^-1·gcat^-1, which is 2.3 and 25.8 times higher than that of individual N-vacancy-doped g-C3N4 and neat g-C3N4, respectively, as well as showing good catalytic stability. Experimental and density functional theory calculation results indicate that, compared with individual N vacancy doping, the introduction of sulfur can promote the activation ability of N vacancies to N2 molecules, leading to promoted N2 photofixation performance.

Microstructures and properties of the nitrided layers fabricated on titanium substrate by direct current nitrogen arc melting technique

The nitrided layers mainly containing TiN dendrites were fabricated by direct current nitrogen arc melting method. The test results show that the layers are harder and more resistant to wear than the titanium substrate. Arc traveling speeds and arc currents have an effect on both the microstructures and the properties of the layers. Decreasing the arc traveling speed or increasing the arc current can obviously enhance the hardness and the wear resistance of the nitrided layers.

Mathematical Models and Computer Simulation of Nitrogen Concentration Profiles in Pulse Plasma Nitrided Layers

Two materials, pure Fe and pure Al, were nitrided in a pulse plasma nitriding facility. The nitrogen profiles in surface layers and the surface phase structures of specimens nitrided at 500℃ for 8 h for Fe and for 6 h for Al were measured using the glow discharge spectrometry and an X-ray diffractometer, respectively. XRD results indicate that the compound layer with hcp crystal structure (AIN) was formed on the top of Al substrate. During nitriding of Fe, the compound layer growth conforms to parabolic law and the surface nitrogen concentration change little with increasing the nitriding time. The surface nitrogen content of nitrided Al specimens is less than theoretical value 34.17 wt pct of AIN. The mathematical models of nitrogen concentration profiles in the surface layer of nitrided Al specimen have been established based on the research of the kinetics of pulse plasma nitriding of Fe and the nitrogen concentration profiles were also simulated. Results show that the predicted curves agree basically with the experimental data.

Enhancing anchoring and catalytic conversion of polysulfides by nitrogen deficient cobalt nitride for advanced lithium-sulfur batteries

While lithium-sulfur(Li-S)battery has attracted remarkable attention owing to the high theoretical capacity,its practical application is still hindered by the shuttle and sluggish conversion kinetics of intermediate lithium polysulfides(Li PSs).Defect engineering,which can regulate the electronic structure and in turn influence the surface adsorption and catalytic capability,has been regarded as a feasible strategy to deal with the above challenges.However,few studies on nitrogen vacancies and their mechanisms are reported.Herein,cobalt nitride with nitrogen vacancies grown on multi-walled carbon nanotube(CNTCo N-VN)is designed and applied as the separator modification material to investigate the enhancing mechanism of nitrogen vacancies on Li-S batteries.The experimental evidence and theoretical calculation indicate that the introduction of nitrogen vacancies into cobalt nitride can enhance the chemical affinity to Li PSs and effectively hamper the shuttle effect.Meanwhile the reduced band gap of the d-band center of Co and p-band center of N for CNT-Co N-VNand the promoted diffusion of Li^(+) can expedite the solid-liquid and liquid-liquid conversions of sulfur species.Due to these superiorities,the cell with CNT-Co NVNmodified separator delivers a favorable initial capacity of 901 m Ah g^(-1)and a capacity of 660 m Ah g^(-1)can be achieved after 250 cycles at 2 C.This work explores the application of metal nitride with nitrogen vacancies and sheds light on the development of functional separators for high-efficient Li-S batteries.

Mathematical Models and Computer Simulation of Nitrogen Concentration Profiles in Pulse Ion Nitrided Layers

The nitrogen concentration profiles in surface layers and surface phase structures were accurately measured respectively using the glow discharge spectrometry and X-ray Diffractometer after the specimens had been pulse ion nitrided at 500℃ for 0.2-8h The results show that the compound layer growth, which is different from that of conventional DC nitriding, conforms to parabolic law At the same time the surface nitrogen concentration change little with increasing the nitriding time, at least it is so when the treating time is longer than 0.2h In addition, the mathematical models of nitrogen concentration profiles in ε -Fe2~3N,γ-Fe4N and α -Fe phases have been established. Using them the nitrogen concentration profiles in nitrided layers were simulated. Results show that the simulated curves coincide quite well with the experimental data.

Boron Nitride Quantum Dots/Ti_(3)C_(2)T_(x)-MXene Heterostructure For Efficient Electrocatalytic Nitrogen Fixation

Electrocatalytic N_(2) fixation through N_(2) reduction reaction(NRR)has been regarded as a promising route for sustainable NH_(3) synthesis,while exploring high-performing NRR catalysts is pivotal yet challenging.Herein,BN quantum dots/Ti_(3)C_(2)T_(x)-MXene(BNQDs/Ti_(3)C_(2)T_(x))heterostructure is demonstrated as an efficient and durable NRR catalyst,exhibiting a high NH_(3) yield of 52.8±3.3μg h^(-1) mg^(-1) with an FE of 19.1±1.6%at0.4 V(vs.RHE),which stand at the high level among all reported BN-and MXene-based NRR catalysts.Theoretical computations reveal that the electronic interactions between BNQDs and Ti_(3)C_(2)T_(x) enrich the electron density of B atoms at the heterointerface and endow them with enhanced electron-donating capability for N_(2) activation and protonation.Meanwhile,the decorated BNQDs can block the active sites of Ti_(3)C_(2)T_(x) for hydrogen evolution,rendering a high N_(2)-to-NH_(3) selectivity.

Effect of Treatment Temperature on Iron Nitride Foils Irradiated with Nitrogen Plasma

We investigated the effect of treatment temperature on the magnetic property of iron nitride foils irradiated with nitrogen plasma. The iron nitride foils irradiated with nitrogen plasma were composed of ε-Fe2/3N, γ'-Fe4N and γ nitrogen austenite in α-Fe of the matrix. The saturation magnetization of the iron nitride foils decreased with increasing the surface temperature. The coercive force of the iron nitride foils increased with increasing the surface temperature.

The microstructural characterization of the nitrided layers prepared by direct current nitrogen arc

The characteristics of nitrided layers prepared on commercially pure titanium substrates by direct current nitrogen arc are presented by scanning electron microscopy （SEM） and transmission electron microscopy （TEM） micrographs as well as X-ray diffraction （ XRD ）. The titanium nitride （ TiN ） dendrites were fully developed with interconnected cellular morphologies at the top surface but grew almost perpendicular to the integrace with coarser arms in the middle area. Also less TiN was found near the interface. The energy inputs had an obvious effect on the microstructures and the hardness of the nitrided layers. The maximum micro-hardness was 2 500 HV at the top surface which was over 9 times higher than that of the substrate.

A new trick on an old support: Zr in situ defects-created carbon nitride for efficient electrochemical nitrogen fixation

Electrochemical nitrogen reduction reaction(NRR) to produce ammonia under ambient conditions is considered as a promising approach to tackle the energy-intensive Haber-Bosch process,but the low Faradaic efficiency and yield of NH_3 are still a challenge.Herein,a carbon-vacancies enriched mesoporous g-C_3 N_4 is developed by an in situ Zr doping strategy.The in situ mesoporous-forming mechanism is deeply understood by TPSR to reveal the functions of Zr dopant that pulls C from the precursor of C_3 N_4,resulting the formation of homogeneous mesopores with about 57% of the one C-defective s-triazine ring in C_3 N_4.Due to the defect sites obtained in metal doping synthesis,the RuAu bimetallic supported catalyst(RuAu_3/0.3 Zr-C_3 N_4) exhibits effective NRR performance with a Faraday efficiency of 11.54% and an NH_3 yield of 5.28 μg h^(-1) mg_(cat) ^(-1).at-0.1 V(RHE),which is nearly 10 times higher than that of RuAu_3/C_3 N_4 catalyst.This work proposes a simple and template-free preparation method for the high defect density mesoporous C_3 N_4,and provides new possibilities of a wide application of mesopore g-C3 N4.

Smart Interfacing between Co-Fe Layered Double Hydroxide and Graphitic Carbon Nitride for High-efficiency Electrocatalytic Nitrogen Reduction

Bimetallic compounds such as hydrotalcite-type layered double hydroxides(LDHs)are promising electrocatalysts owing to their unique electronic structures.However,their abilities toward nitrogen adsorption and reduction are undermined since the surface-mantled,electronegative-OH groups hinder the charge transfer between transition metal atoms and nitrogen molecules.Herein,a smart interfacing strategy is proposed to construct a coupled heterointerface between LDH and 2D g-C_(3)N_(4),which is proven by density functional theory(DFT)investigations to be favorable for nitrogen adsorption and ammonia desorption compared with neat LDH surface.The interfaced LDH and g-C_(3)N_(4) is further hybridized with a self-standing TiO_(2) nanofibrous membrane(NM)to maximize the interfacial effect owing to its high porosity and large surface area.Profited from the synergistic superiorities of the three components,the LDH@C_(3)N_(4)@TiO_(2) NM delivers superior ammonia yield(2.07×10^(−9) mol s^(−1) cm^(−2))and Faradaic efficiency(25.3%),making it a high-efficiency,noble-metal-free catalyst system toward electrocatalytic nitrogen reduction.

Improvement of the Corrosion Resistance of High Alloyed Austenitic Cr-Ni-Mo Stainless Steels by Solution Nitriding

Characteristic features of austenitic steel grades combine a good corrosion resistance with a low hardness, wear resistance and scratch resistance. An interesting possibility for improving the wear behaviour of these steels without loss of their corrosion resistance lies in enriching the near surface region with nitrogen. The process of a solution nitriding allows the rise of the solution of nitrogen in the solid phase. On this state nitrogen increases the corrosion resistance and the tribilogical load-bearing capacity. The aim of the study was, to investigate the improvement of the pitting corrosion behaviour by solution nitriding. A special topic was to observe the effect of nitrogen by different molybdenum content. So austenitic stainless steels (18% Cr, 12% Ni, Mo gradation between 0.06 to 3.6%) had been solution nitrided. The samples could be prepared with various surface content of nitrogen from 0.04 to 0.45% with a step-by-step grinding. The susceptibility against pitting corrosion of these samples had been tested by determination of the stable pitting potential in 0.5M and 1M NaCl at 25°C. For the investigated steel composition and the used corrosion system there is no influence of molybdenum on the effectiveness of nitrogen. The influence of nitrogen to all of the determined parameters can be described well by PRE = Cr + 3,3 * Mo + 25 *N. XPS analysis of the sample surfaces support the results of the pitting corrosion tests.Additionally surface investigations with an acid elektolyte (0,1M HC1 + 0,4M NaCl) were performed. In this case the passivation effective nitrogen content increases markedly with rising molybdenum concentration of the steel. Obviously an interaction of Mo and N is connected with a strongly acid electrolyte.

Interfacial engineering of graphitic carbon nitride(g-C_3N_4)-based metal sulfide heterojunction photocatalysts for energy conversion: A review

As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemical, graphitic carbon nitride (g-C3N4) has become research hotspots in the community. However, g-C3N4 photocatalyst still suffers from many problems, resulting in unsatisfactory photocatalytic activity such as low specific surface area, high charge recombination and insufficient visible light utilization. Since 2009, g-C3N4-based heterostructures have attracted the attention of scientists worldwide for their greatly enhanced photocatalytic performance. Overall, this review summarizes the recent advances of g-C3N4-based nanocomposites modified with transition metal sulfide (TMS), including (1) preparation of pristine g-C3N4,(2) modification strategies of g-C3N4,(3) design principles of TMS-modified g-C3N4 heterostructured photocatalysts, and (4) applications in energy conversion. What is more, the characteristics and transfer mechanisms of each classification of the metal sulfide heterojunction system will be critically reviewed, spanning from the following categories:(1) Type I heterojunction,(2) Type II heterojunction,(3) p-n heterojunction,(4) Schottky junction and (5) Z-scheme heterojunction. Apart from that, the application of g-C3N4-based heterostructured photocatalysts in H2 evolution, CO2 reduction, N2 fixation and pollutant degradation will also be systematically presented. Last but not least, this review will conclude with invigorating perspectives, limitations and prospects for further advancing g-C3N4-based heterostructured photocatalysts toward practical benefits for a sustainable future.

Nitrogen vacancies enriched Ce-doped Ni_(3)N hierarchical nanosheets triggering highly-efficient urea oxidation reaction in urea-assisted energy-saving electrolysis

Urea oxidation reaction (UOR),which has favorable thermodynamic energy barriers compared with oxygen evolution reaction (OER),can provide more cost-effective electrons for the renewable energy systems,but is trapped by its sluggish UOR kinetics and intricate reaction intermediates formation/desorption process.Herein,we report a novel and effective electrocatalyst consisting of carbon cloth supported nitrogen vacancies-enriched Ce-doped Ni_(3)N hierarchical nanosheets (Ce-Ni_(3)N @CC) to optimize the flat-footed UOR kinetics,especially the stiff rate-determine CO_(2)desorption step of UOR.Upon the introduction of valance state variable Ce,the resultant nitrogen vacancies enriched Ce-Ni_(3)N @CC exhibits an enhanced UOR performance where the operation voltage requires only 1.31 V to deliver the current density of 10 mA cm^(-2),which is superior to that of Ni_(3)N @CC catalyst (1.36 V) and other counterparts.Density functional theory (DFT) results demonstrate that the incorporation of Ce in Ni_(3)N lowers the formation energy of nitrogen vacancies,resulting in rich nitrogen vacancies in Ce-Ni_(3)N @CC.Moreover,the nitrogen vacancies together with Ce doping optimize the local charge distribution around Ni sites,and balance the adsorption energy of CO_(2)in the rate-determining step (RDS),as well as affect the initial adsorption structure of urea,leading to the superior UOR catalytic performance of Ce-Ni_(3)N @CC.When integrating the Ce-Ni_(3)N catalyst in UOR//HER and UOR//CO_(2)R flow electrolyzer,both of them perform well with low operation voltage and robust long-term stability,proofing that the thermodynamically favorable UOR can act as a suitable substitute anodic reaction compared with that of OER.Our findings here not only provide a novel UOR catalyst but also offer a promising design strategy for the future development of energy-related devices.

Effects of alloying elements on nitrogen diffusion behavior around TiN/Ti interface α region in as-cast titanium alloys

To characterize the effects of alloying elements on inclusion dissolution of titanium nitride, the content profiles of elements around TiN/Ti boundary α phase regions in liquid titanium alloys have been experimentally carried out. Four kinds of commercial alloys of CpTi, Ti64, Ti17 and Ti6242 containing different α stabilizing or β stabilizing elements are examined through artificially embedding the TiN sponge particle into liquid alloys in VAR conditions. The content profiles of nitrogen and alloying elements around TiN/Ti boundary were measured by WDX and microprobe for as cast samples. The content profiles of nitrogen and alloying elements around N containing solid in α Ti region of these alloys show a common features of a steep change. In particular, the content profiles of elements for Ti6242 demonstrate unique change of a more gentle change tendency and further deeper into the alloy matrix. The experiment results show that, the differences among composite effects of alloying elements in different alloys within nitrogen induced diffusion α region result in different dissolution and diffusion behaviors to overcome the α phase region barriers.

Transition‐metal‐atom‐pairs deposited on g‐CN monolayer for nitrogen reduction reaction:Density functional theory calculations

The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fabricated using transition‐metal(TM)atoms(TM=Sc−Zn)doped into g‐CN monolayers.The electrochemical mechanism of APCs for an NRR has been reported by well‐defined density functional theory calculations.The calculated limiting potentials were−0.47 and−0.78 V for the Fe_(2)@CN and Co_(2)@CN catalysts,respectively.Owing to its high suppression of hydrogen evolution reactions,Co_(2)@CN is a superior electrocatalytic material for a N_(2)fixation.Stable Fe_(2)@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity.The two‐way charge transfer affirmed the donation‐acceptance procedure between N_(2)and Fe_(2)@CN or Co_(2)@CN,which play a crucial role in the activation of inert N≡N bonds.This study provides an in‐depth investigation into atom‐pair catalysts and will open up new avenues for highly efficient g‐CN‐based nanostructures for an NRR.

Research on the Fe-silicon nitride material self-producing N_2 at high temperature

The Fe silicon nitride synthesized by flashing combustion process was studied to determine the reaction temperature between Fe and silicon nitride, the account of N2 given out in the course of the reaction, and the change of the microstructure during calcination. The results showed that at 1127.2℃ the Fe-silicon nitride self-reacts and releases N2 and under 101.3 kPa the volume of N2 given out in the course of the reaction is 20 times more than that of the starting material. N2 is produced quickly, and completes in several decade seconds. With the producing of N2, the structure of Silicon Nitride around Fe becomes loose and porous, or cracks are formed by the reaction between Fe and silicon nitride. So if it is made use of that Fe-silicon nitride self-producing N2 at the high temperature, the performance of the material on a base of Fe-silicon nitride could be greatly improved.

1+1>2: Learning from the interfacial modulation on single-atom electrocatalysts to design dual-atom electrocatalysts for dinitrogen reduction

Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene(hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction(NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dualatom catalysts for NRR.