Strong metal–support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Tuning the crystallinity of titanium nitride on copper-embedded carbon nanofiber interlayers for accelerated electrochemical kinetics in lithium-sulfur batteries

The development of lithium-sulfur(Li-S)batteries is hindered by the disadvantages of shuttling of polysulfides and the sluggish redox kinetics of the conversion of sulfur species during discharge and charge.Herein,the crystallinities of a titanium nitride(TiN)film on copper-embedded carbon nanofibers(Cu-CNFs)are regulated and the nanofibers are used as interlayers to resolve the aforementioned crucial issues.A low-crystalline TiN-coated Cu-CNF(L-TiN-Cu-CNF)interlayer is compared with its highly crystalline counterpart(H-TiN-Cu-CNFs).It is demonstrated that the L-TiN coating not only strengthens the chemical adsorption toward polysulfides but also greatly accelerates the electrochemical conversion of polysulfides.Due to robust carbon frameworks and enhanced kinetics,impressive highrate performance at 2 C(913 mAh g^(-1)based on sulfur)as well as remarkable cyclic stability up to 300 cycles(626 mAh g^(-1))with capacity retention of 46.5%is realized for L-TiN-Cu-CNF interlayer-configured Li-S batteries.Even under high loading(3.8 mg cm^(-2))of sulfur and relatively lean electrolyte(10μL electrolyte per milligram sulfur)conditions,the Li-S battery equipped with L-TiN-Cu-CNF interlayers delivers a high capacity of 1144 mAh g^(-1)with cathodic capacity of 4.25 mAh cm^(-2)at 0.1 C,providing a potential pathway toward the design of multifunctional interlayers for highly efficient Li-S batteries.

Preparation and Properties of Cu-Containing High-entropy Alloy Nitride Films by Magnetron Sputtering on Titanium Alloy

Magnetron sputtering deposition with regulated Cu target power was used for depositing Cu-containing high-entropy alloy nitride(Cu-(HEA)N)films on TC4 titanium alloy substrates.The microscopic morphologies,surface compositions,and thicknesses of the films were characterized using SEM+EDS;the anti-corrosion,wear resistance and antibacterial properties of the films in simulated seawater were investigated.The experimental results show that all four Cu-(HEA)N films are uniformly dense and contained nanoparticles.The film with Cu doping come into contact with oxygen in the air to form cuprous oxide.The corrosion resistance of the(HEA)N film without Cu doping on titanium alloy is better than the films with Cu doping.The Cu-(HEA)N film with Cu target power of 16 W shows the best wear resistance and antibacterial performance,which is attributed to the fact that Cu can reduce the coefficient of friction and exacerbate corrosion,and the formation of cuprous oxide has antibacterial properties.The findings of this study provide insights for engineering applications of TC4 in the marine field.

Reaction between Ti and boron nitride based investment shell molds used for casting titanium alloys

The aim of this paper was to study the reaction between a Ti-6Al-4V alloy and boron nitride based investment shell molds used for investment casting titanium. In BN based investment shell molds, the face coatings are made of pretreated hexagonal boron nitride （hBN） with a few yttria （Y2O3） and colloidal yttria as binder. The Ti-6Al-4V alloy was melted in a controlled atmosphere induction furnace with a segment water-cooled copper crucible. The cross-section of reaction interface between Ti alloys and shell mold was investigated by electron probe micro-analyzer （EPMA） and microhardness tester. The results show that the reaction is not serious, the thickness of the reacting layer is about 30-50 μm, and the thickness of α-case is about 180-200 pro. Moreover the α-case formation mechanism was also discussed.

COMPARISON OF SURFACE PROPERTIES OF Ti-6Al-4V COATED WITH TITANIUM NITRIDE, TiN+TiC+Ti(C,N)/DLC, TiN/DLC AND TiC/DLC FILMS BY PLASMA-BASED ION IMPLANTATION

The surface properties of Ti-6Al-4V alloy coated with titanium nitride, TiN+TiC+Ti(C,N)/DLC (diamond like carbon), TiN/DLC and TiC/DLC films by plasma-based ion implantation (PBII) with nitrogen, PBII with nitrogen then acetylene, PBII with nitrogen then glow discharge deposition with acetylene plus hydrogen and PBII with acetylene then glow discharge deposition with acetylene plus hydrogen respectively were studied. The corresponding films are found getting dimmer, showing light gold or gold, smoky color (uneven), light red in black (uneven), and graphite black separately. The corresponding film resistivities are given. Antioxidation ability of the titanium nitride film is poor, while the existence of carbon (or carbide) improves the antioxidation ability of the films. Having undergone excellent intermediate transitional region of nitrogen and carbon implantation, the top DLC layer of the TiN+TiC+Ti(C,N)/DLC multilayer are formed after the carbon implantation has the best adhesion with the substrate among all the multilayers. Although microhardness of the samples increases in the order of coatings of titanium nitride, TiN/DLC, TiN+TiC+Ti(C,N)/DLC and TiC/DLC, the TiN/DLC and TiC/DLC multilayers have greater brittleness as compared with other films.

Palladium nanoparticles assembled on titanium nitride for enhanced electrochemical hydrodechlorination of 2,4-dichlorophenol in water

We report a one‐pot surfactant‐free wet‐chemical reduction approach to the synthesis of palladium/titanium nitride(Pd/TiN)and Pd/carbon(Pd/C)composites,in which^5 nm Pd NPs were uniformly dispersed on TiN or C.In terms of catalytic performance,Pd/TiN showed enhanced efficiency and stability compared with those of Pd/C and bare TiN in the electrocatalytic hydrodechlorination(EHDC)reaction of 2,4‐dichlorophenol(2,4‐DCP)in aqueous solution.The superior performance of Pd/TiN arises from the promotion effect of TiN.Strong metal‐support interactions modified the electronic structure of Pd,which optimized generation of H*ads and 2,4‐DCP adsorption/activation.The cathode potential plays a vital role in controlling the EHDC efficiency and the product distribution.A working potential of?0.80 V was shown to be optimal for achieving the highest EHDC efficiency and maximizing conversion of 2,4‐DCP to phenol(P).Our studies of the reaction pathway show that EHDC of 2,4‐DCP on Pd/TiN proceeded by 2,4‐DCP→p‐chlorophenol(p‐CP),o‐chlorophenol(o‐CP)→P;however,Pd/TiN presented little selectivity for cleavage of p‐C‐Cl vs o‐C‐Cl.This work presents a new approach to enhancing Pd performance towards EHDC through the effects of a support.The strategy demonstrated here could also be extended to design highly efficient catalysts for other hydrogenation reactions.

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.

Effect of frequency and pulse-on time of high power impulse magnetron sputtering on deposition rate and morphology of titanium nitride using response surface methodology

Titanium nitride thin films were deposited on silicon by high power impulse magnetron sputtering(HiPIMS)method at different frequencies(162-637 Hz)and pulse-on time(60-322μs).Response surface methodology(RSM)was employed to study the simultaneous effect of frequency and pulse-on time on the current waveforms and the crystallographic orientation,microstructure,and in particular,the deposition rate of titanium nitride at constant time and average power equal to 250 W.The crystallographic structure and morphology of deposited films were analyzed using XRD and FESEM,respectively.It is found that the deposition rate of HiPIMS samples is tremendously dependent on pulse-on time and frequency of pulses where the deposition rate changes from 4.5 to 14.5 nm/min.The regression equations and analyses of variance(ANOVA)reveal that the maximum deposition rate(equal to(17±0.8)nm/min)occurs when the frequency is 537 Hz and pulse-on time is 212μs.The experimental measurement of the deposition rate under this condition gives rise to the deposition rate of 16.7 nm/min that is in good agreement with the predicted value.

Evaluation of 1031 primary titanium nitride coated mobile bearing total knee arthroplasties in an orthopedic clinic

AIM To evaluate the influence of the titanium nitride(TiN) coating on the results of a total knee arthroplasty(TKA). METHODS A total of 910 patients(338 men; 572 woman), with a mean age of 65(range 36-94) undergoing 1031 primary TKAs were assessed. Clinical evaluation and patientreported outcomes were gathered one year after surgery. The questionnaires included the Knee injury and Osteoarthritis Outcome Score(KOOS)-Dutch version, Visual Analogue Scale(VAS) pain scores in rest and during active knee movement, VAS-satisfaction scores, and EQ-5 D-3 L health scores. This was aimed to assess the overall knee function and patient satisfaction, and to enable us to make a gross comparison to other TKAs.RESULTS At a mean follow-up of 46 mo(range 1-92) the overall implant survival was 97.7% and 95.1% for any operative reason related to the implant. Twenty-three knees(2.2%) required revision surgery. Arthrofibrosis was the most common indication for a re-operation. The clinical evaluation and patient-reported outcomes revealed good to excellent patient satisfaction and function of the arthroplasty. The median postoperative VAS-pain scores on a scale of 0-100, at one year after surgery were 1 in rest and 2 during movement.CONCLUSION The Ti N coated, mobile bearing TKA results are excellent and similar to those of other widely used TKA designs. Residual pain of the knee remains a concern and the Ti N coating in combination with the mobile bearing does not seem to be the simple solution to this problem. Future research will have to show that the coating gives a better survival than the cobalt chrome version.

Theoretical study of the elastic properties of titanium nitride

The equilibrium lattice parameter, relative volume V/V0, elastic constants Cij, and bulk modulus of titanium nitride are successfully obtained using the ab initio planewave pseudopotential （PW-PP） method within the framework of density functional theory. The quasi-harmonic Debye model, using a set of total energy vs molar volume obtained with the PW-PP method, is applied to the study of the elastic properties and vibrational effects. We analyze the relationship between the bulk modulus and temperature up to 2000 K and obtain the relationship between bulk modulus B and pressure at different temperatures. It is found that the bulk modulus B increases monotonously with increasing pressure and decreases with increasing temperature. Moreover, the Debye temperature is determined from the non-equilibrium Gibbs functions.

Preparation of Titanium Nitride Nanoparticles from a Novel Refluxing Derived Precursor

Titanium nitride （TiN） nanoparticles were prepared from a novel refluxing-derived precursor.The organic/inorganic hybrid precursor was prepared by a two-stage refluxing method using hydrous TiO2 as titania source and n-dodecane as carbon source.The precursor was heat-treated to 1 200 °C in flowing ammonia （NH3） to get TiN nanoparticles.The phase and chemical compositions were investigated by means of XRD,Raman spectroscopy and XPS.Samples microstructure was studied by means of SEM,TEM and SEAD.XRD pattern indicated that the product was face-centered cubic TiN with a lattice constant a = 4.236 · and average crystallite sizes of 35.2 nm.Raman spectra indicated that long time refluxing results in Alkane dehydrogenation and the formation of coke on TiO2 nanoparticles.Oxygen presence in TiN lattice was confirmed by XPS investigation.The particle size that was showed by Electron microscopy photographs ranged from 20 to 60 nm.

High performance corrosion and wear resistant composite titanium nitride layers produced on the AZ91D magnesium alloy by a hybrid method

Composite,diffusive titanium nitride layers formed on a titanium and aluminum sub-layer were produced on the AZ91D magnesium alloy.The layers were obtained using a hybrid method which combined the PVD processes with the final sealing by a hydrothermal treatment.The microstructure,resistance to corrosion,mechanical damage,and frictional wear of the layers were examined.The properties of the AZ91D alloy covered with these layers were compared with those of the untreated alloy and of some engineering materials such as 316L stainless steel,100Cr6 bearing steel,and the AZ91D alloy subjected to commercial anodizing.It has been found that the composite diffusive nitride layer produced on the AZ91D alloy and then sealed by the hydrothermal treatment ensures the corrosion resistance comparable with that of 316L stainless steel.The layers are characterized by higher electrochemical durability which is due to the surface being overbuilt with the titanium oxides formed,as shown by the XPS examinations,from titanium nitride during the hydrothermal treatment.The composite titanium nitride layers exhibit high resistance to mechanical damage and wear,including frictional wear which is comparable with that of 100Cr6 bearing steel.The performance properties of the AZ91D magnesium alloy covered with the composite titanium nitride coating are substantially superior to those of the alloy subjected to commercial anodizing which is the dominant technique employed in industrial practice.

Structure and properties of diffusive titanium nitride layers produced by hybrid method on AZ91D magnesium alloy

A diffusive titanium nitride layers were produced on AZ91 D magnesium alloy by a hybrid method which combines the titanium coating physical vapor deposition（PVD） with subsequent nitriding. The layers are composed of a thin surface zone of titanium nitrides and oxides, an intermediate titanium zone and Ti-Al-Mg type diffusive zone. Since the layers improve the corrosion resistance, the best corrosion resistance is obtained when the layers are produced on aluminum base sub-layer by oxynitriding.

Pt Supported on Plasma-Chemical Titanium Nitride for Efficient Room-Temperature CO Oxidation

Catalysts of carbon monoxide oxidation were synthesized by deposition of platinum on titanium nitride (TiN). Two substrates with an average particle size of 18 and 36 nm were obtained by hydrogen reduction of titanium tetrachloride in a stream of microwave plasma of nitrogen. The surface of the catalysts was studied by X-ray photoelectron spectroscopy (XPS). The data obtained by us in the present work indicate the presence of oxynitride as a transition layer between nitride and oxide. It was found that the CO oxidation rate on the 9 - 15 wt.% Pt loaded TiN catalysts is 120 times higher than that on the platinum black with a specific surface of 30 m2/g. Increase in the reaction rate of CO oxidation on Pt/TiN catalysts as compared to platinum black can be associated with both an increase in the concentration of CO molecules adsorbed and a decrease in the activation energy of the reaction. Catalysts are promising for use in catalytic air purification systems.

Study on Titanium Nitride Film Modified for Intraocular Lens

Objective:To study the characteristics of the intraocular lens using ion beam sputtering depositing titanium nitride thin film on the intraocular lens(IOLs).Methods:To deposite titanium nitride thin film on the top of intraocular lens by ion beam sputtering depositing.We analyzed the surface morphology of intraocular lens through SEM and AFM.We detected intraocular lens resolution through the measurement of intraocular lens.Biocompatibility of intraocular lens is preliminary evaluated in this test.Results:The surface morphology of intraocular lens material was not changed,and was in line with the requirements of smoothness.Resolution was in line with national requirements.Unmodified and modified IOLs's cytotoxicity were 1 and 0.6 grade respectively.Hemolytic rates of modified and unmodified were both less than 5%.Conclusion:Ion beam sputtering deposition of objects didn't only affect the surface morphology and the basic optical performance,but also can enhance the biocompatibility of intraocular lens.Ion beam sputtering deposition technique has provided new methods for the surface modification of IOLs and PMMA materials.

Flexible regulation engineering of titanium nitride nanofibrous membranes for efficient electromagnetic microwave absorption in wide temperature spectrum

Simultaneous development of well impedance matching and strong loss capability has become a mainstream method for achieving outstanding electromagnetic microwave absorption(EMWA)performances over wide temperature range.However,it is difficult to pursue both due to the mutual restraint of relationship between impedance matching and loss capability about temperature.Here,we propose a flexible regulation engineering of titanium nitride(TiN)nanofibrous membranes(NMs,TNMs),which could be distributed uniformly in the polydimethylsiloxane(PDMS)matrix and contributed to the formation of abundant local conductive networks,generating the local conductive loss and enhancing the loss ability of EMWs.Moreover,when the TNMs are used as functional units and dispersed in the matrix,the corresponding composites exhibit an outstanding anti-reflection effect on microwaves.As hoped,under the precondition of good impedance matching,local conductive loss and polarization loss together improve the loss capacity at room temperature,and polarization loss can compensate the local conductive loss to acquire effective dielectric response at elevated temperature.Benefiting from the reasonably synergistic loss ability caused by flexible regulation engineering,the corresponding composites exhibit the perfect EMWA performances in a wide temperature range from 298 to 573 K.This work not only elaborates the ponderable insights of independent membrane in the composition-structure-function connection,but also provides a feasible tactic for resolving coexistence of well impedance matching and strong loss capability issues in wide temperature spectrum.

Effect of nitriding-sulfurizing composite treatment on the tribological behavior of titanium alloys

A composite layer was prepared on the surface of Ti-6Al-4V alloy by nitriding-sulfurizing composite treatment,and its microstructure and phase structure were examined by scanning electron microscopy（SEM） and X-ray diffraction（XRD）,respectively.The tribological performance was measured to investigate its dependence on the nitriding-sulfurizing composite treatment process.The results indicated that the composite layer was mainly comprised of Ti2N,TiN,and TiS2.It was found that the composite layer exhibited superior tribological properties under dry friction and absolute sliding conditions due to the formation of sulfides with self-lubricating function.

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.

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.

汽轮机末级叶片用SP-700钛合金气体渗氮层结构和性能的研究

采用真空气体渗氮工艺在不同温度下对SP-700钛合金表面进行了渗氮强化。利用扫描电子显微镜、光学显微镜、显微维氏硬度仪、往复摩擦磨损试验仪、白光干涉三维表面轮廓仪和电化学工作站,分别测试了强化层的表面和截面形貌、硬度、耐磨性能和电化学腐蚀性能;通过浸泡腐蚀方法测定了涂层在HF溶液中的腐蚀行为。结果表明:渗氮温度对SP-700钛合金的微观形貌影响较大,随着温度的升高,试样表面氮化物数量增加,氮化物层更加致密;高温渗氮试样的硬度较基体提高了约1.9倍,相对耐磨性可达51.34;所有试样在3.5%NaCl溶液中均能自发钝化,有较好的耐电化学腐蚀性能;渗氮试样在HF腐蚀液中表现更优,渗氮温度越高,试样的耐腐蚀性能越好。