[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significant...[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.展开更多
The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly effici...The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.展开更多
At present,the most common preparation method of amorphous boron powder is magnesium thermal reduction method,but the amorphous boron powder obtained by this method mostly contains impurities such as magnesium and oxy...At present,the most common preparation method of amorphous boron powder is magnesium thermal reduction method,but the amorphous boron powder obtained by this method mostly contains impurities such as magnesium and oxygen which are difficult to remove,and these impurities will seriously affect the application of amorphous boron powder and need to be strictly removed.In this research,the acid-insoluble impurities were modified through sintering and quenching,while the magnesium impurities were optimized via ultrasonic acid leaching.We observed that the quenching temperature played a crucial role in determining the efficiency of magnesium impurity removal.The results show that the magnesium content in amorphous boron powder can be reduced from 5.67%to 2.40%by quenching the amorphous boron powder at 800°C and using ultrasonic assisted acid leaching.Furthermore,the oxidation reaction of boron is influenced by the powder's particle size and specific surface area,with the effective activation energy being intimately tied to both these factors.Post-quenching and acid leaching,we observed an increase in the specific surface area of the boron powder samples,leading to enhanced activity.In conclusion,our study presents an effective strategy to mitigate magnesium impurities and elevate the performance of amorphous boron powder,offering promising avenues for advancing its utilization across diverse industries.展开更多
Interfacial adhesion between carbon fibers(CF)and polyetherketoneketone(PEKK)is a key factor that affects the mechanical performances of their composites.It is therefore of great importance to impregnate the CF bundle...Interfacial adhesion between carbon fibers(CF)and polyetherketoneketone(PEKK)is a key factor that affects the mechanical performances of their composites.It is therefore of great importance to impregnate the CF bundles with PEKK as effi-ciently as possible.We report that PEKK with a good dispersion in a mixed solution of 4-chlorophenol and 1,2-dichloroethane can be introduced onto CF surfaces by solution impregnation and curing at 280,320,340 and 360℃.The excellent wettability or infiltra-tion of the PEKK solution guarantees a full covering and its tight binding to CFs,making it possible to evaluate the interfacial shear strength(IFSS)with the microdroplet method.The interior of the CF bundles is completely and uniformly filled with PEKK by solu-tion impregnation,leading to a high interlaminar shear strength(ILSS).The maximum IFSS and ILSS reached 107.8 and 99.3 MPa,respectively.Such superior shear properties are ascribed to the formation of amorphous PEKK in the small spaces between CFs.展开更多
Flow based Erosion e corrosion problems are very common in fluid handling equipments such as propellers, impellers, pumps in warships, submarine. Though there are many coating materials available to combat erosionecor...Flow based Erosion e corrosion problems are very common in fluid handling equipments such as propellers, impellers, pumps in warships, submarine. Though there are many coating materials available to combat erosionecorrosion damage in the above components, iron based amorphous coatings are considered to be more effective to combat erosionecorrosion problems. High velocity oxy-fuel(HVOF)spray process is considered to be a better process to coat the iron based amorphous powders. In this investigation, iron based amorphous metallic coating was developed on 316 stainless steel substrate using HVOF spray technique. Empirical relationships were developed to predict the porosity and micro hardness of iron based amorphous coating incorporating HVOF spray parameters such as oxygen flow rate, fuel flow rate, powder feed rate, carrier gas flow rate, and spray distance. Response surface methodology(RSM) was used to identify the optimal HVOF spray parameters to attain coating with minimum porosity and maximum hardness.展开更多
The preparation process of amorphous nanometer boron powders through combustion synthesis was investigated, and the effects of the reactant ratio, the heating agent and the milling rate on the activity and particle si...The preparation process of amorphous nanometer boron powders through combustion synthesis was investigated, and the effects of the reactant ratio, the heating agent and the milling rate on the activity and particle size of amorphous boron powders were studied. The results show that the boron powders exist in the form of an amorphous phase which has the crystallinity lower than 30.4%, and the panicle size of boron powder decreases with an increase of the high-energy ball milling rate. The purity of amorphous boron powder is 94.8% and panicle sizes are much smaller than 100 nm when the mass ratio of B2O3/Mg/KClO3 is 100：105：17 and the ball milling time is 20 min with the milling rate of 300 r/min. At the same time, the amorphous boron nano-fibers appear in the boron powders.展开更多
Rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy was prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter in a continuous or isothermal heating mode. ...Rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy was prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter in a continuous or isothermal heating mode. phase transformation was investigated, with a special interest in primary crystallization, by using an in-situ examination of X-ray diffractometry （XRD） and high resolution transmission electron microscopy （HRTEM）. The results show that, the whole devitrification of rapidly solidified Al87NiyCu3Nd3 amorphous alloy involves two main processes of primary crystallization and secondary crystallization that consist mainly of two reactions. For primary crystallization, the apparent activation energies, EIso and EKis and growth activation energies Eg are about 153, 166 and 288 kJ/mol, respectively. The interdiffusion of Al atoms is a rate-controlled step of formation of the a（Al） particles, but slow diffusion of Ni and Nd atoms plays a significant role in retarding growth of the α （Al） particles. For secondary crystallization, EIso, EKis and Eg of the first reaction are about 291,208 and 290 kJ/mol, and those of the second reaction are about 367, 269 and 372 kJ/mol. The two reactions of secondary crystallization are controlled mainly in an interface-controlled three-dimensional mode, depending mainly on slow diffusion of Ni and Nd atoms.展开更多
Ti/Cr (atomic ratio 3:4) amorphous alloy was prepared by ball milling the rapidly quenched Ti/Cr ribbons for 30h, and then milled with MgH_2 for 50 h under Ar atmosphere to obtain MgH_2-30wt. % Ti/Cr composite. The XR...Ti/Cr (atomic ratio 3:4) amorphous alloy was prepared by ball milling the rapidly quenched Ti/Cr ribbons for 30h, and then milled with MgH_2 for 50 h under Ar atmosphere to obtain MgH_2-30wt. % Ti/Cr composite. The XRD results indicate that MgH_2 decomposed partly during ball milling process. The brittle MgH_2 and the mechanical driving force resulted in a highly dispersive distribution of the Ti/Cr amorphous phase in the Mg matrix. The favorable hydrogenation performance is mainly attributed to the com...展开更多
Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous h...Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous hydrogen storage characteristics were investigated. The XRD, TEM and SEM linked with EDS detections reveal that the as-spun Nd-free alloy holds an entire nanocrystalline structure but a nanocrystalline and amorphous structure for the as-spun Nd-added alloy, implying that the addition of Nd facilitates the glass forming in the Mg_2Ni-type alloy. Furthermore, the degree of amorphization of the as-spun Nd-added alloy and thermal stability of the amorphous structure clearly increase with the spinning rate rising. The melt spinning ameliorates the hydriding and dehydriding kinetics of the alloys dramatically. Specially, the rising of the spinning rate from 0(the as-cast was defined as the spinning rate of 0 m/s) to 40 m/s brings on the hydrogen absorption saturation ratio(R_5~a)(a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increasing from 36.9% to 91.5% and the hydrogen desorption ratio(R_(1 0)~d)(a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) rising from 16.4% to 47.7% for the(x=10) alloy, respectively.展开更多
Co87Nb10Zr3,Co76Nb19Zr5,Co64Nb26Zr10 and Co64Nb16Zr20 amorphous films were deposited on noncrystalline glass substrates by DC unbalanced magnetron sputtering. The compositions of amorphous films were tailored in the l...Co87Nb10Zr3,Co76Nb19Zr5,Co64Nb26Zr10 and Co64Nb16Zr20 amorphous films were deposited on noncrystalline glass substrates by DC unbalanced magnetron sputtering. The compositions of amorphous films were tailored in the light of the individual deposition rate of Co,Nb and Zr. The amorphous films with the anticipated composition were prepared by means of co-sputtering Co,Nb and Zr targets simultaneously. It is indicated that there is interaction among three targets during co-sputtering. The morphology and composition of the films were observed by SEM,AFM and EDS. The structure and magnetic property were measured by XRD and physical property measurement system(PPMS) . The coercivity changes with the composition,varying from 240 to 1 600 A/m. After vacuum isothermal annealing at temperatures of 475,500,525 and 550 ℃ for 15 and 30 min,respectively,it is found that high Nb content is beneficial to improving thermal stability of amorphous films. The crystallized films have the mean grain size of 2-19 nm.展开更多
The crystallization kinetics of amorphous (Nd3.6Pr5.4Fe83Co3B5) and the preparation of α-Fe/Nd2Fe14B nanocomposite magnets by controlled melt-solidification of (Nd3.6Pr5.4Fe83Co3B5) was investigated by employing DTA,...The crystallization kinetics of amorphous (Nd3.6Pr5.4Fe83Co3B5) and the preparation of α-Fe/Nd2Fe14B nanocomposite magnets by controlled melt-solidification of (Nd3.6Pr5.4Fe83Co3B5) was investigated by employing DTA, XRD, and TEM. The results show that a metastable intermediate phase (Nd8Fe27B24) prior to α-Fe and Nd2Fe14B phases is crystallized as the amorphous Nd3.6Pr5.4Fe83Co3B5 is heated to 1 223 K. The crystallization activation energy of α-Fe and Nd8Fe27B24 phases is larger at the beginning stage of crystallization, and then it decreases with crystallized fraction x for the former and has little change when x is below 70% for the latter, which essentially results in an α-Fe/Nd2Fe14B microstructure with a relatively coarse grain size about 20-60 nm and a non-uniform distribution of grain size in the annealed alloy. The α-Fe/Nd2Fe14B nanocomposite magnets with a small average grain size about 14 nm and a quite uniform grain size distribution were prepared by controlled melt-solidification of (Nd3.6Pr5.4Fe83Co3B5) at a wheel speed of 20 m·s-1 during melt-spinning. The magnets show a high maximum energy product of （BH）max = 194 kJ·m-3, which is nearly twice of that of the nanocomposite magnets made by annealing the amorphous Nd3.6Pr5.4Fe83Co3B5 precursor alloy.展开更多
In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4...In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).展开更多
ZrO2-mullite nano-ceramics were fabricated by in-situ controlled crystallizing from SiO2-Al2O3-ZrO2 amorphous bulk. The thermal transformation sequences of the SiO2-Al2O3-ZrO2 amorphous bulk were investigated by X-ray...ZrO2-mullite nano-ceramics were fabricated by in-situ controlled crystallizing from SiO2-Al2O3-ZrO2 amorphous bulk. The thermal transformation sequences of the SiO2-Al2O3-ZrO2 amorphous bulk were investigated by X-ray diffraction, infrared spectrum, scanning electron microscope and differential scanning calorimetric. And the mechanical properties of the nano-ceramics were studied. The results show that the bulks are still in amorphous state at 900 ℃ and the t-ZrO2 forms at about 950 ℃ with a faint spinel-like phase which changes into mullite on further heating. ZrO2 and mullite become major phases at 1 100 ℃ and an amount of m-ZrO2 occur at the same time. The sample heated at 950 ℃ for 2 h and then at 1 100 ℃ for 1 h shows very dense and homogenous microstructure with ball-like grains in size of 20-50 nm. With the increase of crystallization temperature up to 1 350 ℃, the grains grow quickly and some grow into lath-shaped grains with major diameter of 5 μm. After two-step treatment the highest micro-hardness, flexural strength and fracture toughness of the samples are 13.72 GPa, 520 MPa and 5.13 MPa·m1/2, respectively.展开更多
Impact wear behaviors of Hadfield manganese steel at different impact angles were investigated. The results of impact wear tests show that there exists a critical impact load for Hadfield steel. The wear rate suddenly...Impact wear behaviors of Hadfield manganese steel at different impact angles were investigated. The results of impact wear tests show that there exists a critical impact load for Hadfield steel. The wear rate suddenly turns down after some impact cycles when the impact load is greater than the critical load. The critical impact load is smaller than 8.2 J in this research because the nano-sized austenitic grains embedded in amorphous delay the crack propagation in subsurface. From high resolution transmission electron microscope (HRTEM) examination of subsurface microstructure, it is found that a large amount of nano-sized grains embedded in bulk amorphous matrix are fully developed and no martensitic transformation occurs during the impact wear process. The analytical results of worn surface morphology and debris indicate that the initiation of crack, propagation and spalling are restricted in the amorphous phase, resulting in the size distribution of debris in nano-sizes, which is the reason why the wear rate of Hadfield steel is greatly decreased at high impact load.展开更多
The Al-Ni-Y alloy powder was prepared by rapid solidification technology of inert gas atomization. The diameter of amorphous powder is less than 12 μm. The effects of atomization gas on cooling velocity, morphology,...The Al-Ni-Y alloy powder was prepared by rapid solidification technology of inert gas atomization. The diameter of amorphous powder is less than 12 μm. The effects of atomization gas on cooling velocity, morphology, microstructure and microhardness of powder and fine powder ratio were investigated.The results show that the morphology, microstructure and microhardness of powder and fine powder ratio are affected by cooling velocity changed through atomization gas. The cooling velocity of inert gas atomization is more than 1×10~4 K/s. The larger the cooling velocity, the finer the powder, and the smoother the surface of powder; the smaller the diameter of powder, the larger the microhardness of powder.展开更多
基金Major Science and technology projects of Anhui Province (202103a05020003)。
文摘[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.
基金supported by the National Key R&D Program of China(2018YFA0702001)National Natural Science Foundation of China(22371268,22301287)+3 种基金Fundamental Research Funds for the Central Universities(WK2060000016)Anhui Provincial Natural Science Foundation(2208085J09,2208085QB33)Collaborative Innovation Program of Hefei Science Center,CAS(2022HSC-CIP020)Youth Innovation Promotion Association of the Chinese Academy of Science(2018494)and USTC Tang Scholar.
文摘The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.
基金support on this research from the Talent Training Program of Yunnan of China(Grant Nos.202005AC160041 and KKXY202252002)the"Xingdian Talent"Industry Innovation Talent Program in Yunnan Province(Grant No.XDYC-CYCX-2022-0042)。
文摘At present,the most common preparation method of amorphous boron powder is magnesium thermal reduction method,but the amorphous boron powder obtained by this method mostly contains impurities such as magnesium and oxygen which are difficult to remove,and these impurities will seriously affect the application of amorphous boron powder and need to be strictly removed.In this research,the acid-insoluble impurities were modified through sintering and quenching,while the magnesium impurities were optimized via ultrasonic acid leaching.We observed that the quenching temperature played a crucial role in determining the efficiency of magnesium impurity removal.The results show that the magnesium content in amorphous boron powder can be reduced from 5.67%to 2.40%by quenching the amorphous boron powder at 800°C and using ultrasonic assisted acid leaching.Furthermore,the oxidation reaction of boron is influenced by the powder's particle size and specific surface area,with the effective activation energy being intimately tied to both these factors.Post-quenching and acid leaching,we observed an increase in the specific surface area of the boron powder samples,leading to enhanced activity.In conclusion,our study presents an effective strategy to mitigate magnesium impurities and elevate the performance of amorphous boron powder,offering promising avenues for advancing its utilization across diverse industries.
文摘Interfacial adhesion between carbon fibers(CF)and polyetherketoneketone(PEKK)is a key factor that affects the mechanical performances of their composites.It is therefore of great importance to impregnate the CF bundles with PEKK as effi-ciently as possible.We report that PEKK with a good dispersion in a mixed solution of 4-chlorophenol and 1,2-dichloroethane can be introduced onto CF surfaces by solution impregnation and curing at 280,320,340 and 360℃.The excellent wettability or infiltra-tion of the PEKK solution guarantees a full covering and its tight binding to CFs,making it possible to evaluate the interfacial shear strength(IFSS)with the microdroplet method.The interior of the CF bundles is completely and uniformly filled with PEKK by solu-tion impregnation,leading to a high interlaminar shear strength(ILSS).The maximum IFSS and ILSS reached 107.8 and 99.3 MPa,respectively.Such superior shear properties are ascribed to the formation of amorphous PEKK in the small spaces between CFs.
文摘Flow based Erosion e corrosion problems are very common in fluid handling equipments such as propellers, impellers, pumps in warships, submarine. Though there are many coating materials available to combat erosionecorrosion damage in the above components, iron based amorphous coatings are considered to be more effective to combat erosionecorrosion problems. High velocity oxy-fuel(HVOF)spray process is considered to be a better process to coat the iron based amorphous powders. In this investigation, iron based amorphous metallic coating was developed on 316 stainless steel substrate using HVOF spray technique. Empirical relationships were developed to predict the porosity and micro hardness of iron based amorphous coating incorporating HVOF spray parameters such as oxygen flow rate, fuel flow rate, powder feed rate, carrier gas flow rate, and spray distance. Response surface methodology(RSM) was used to identify the optimal HVOF spray parameters to attain coating with minimum porosity and maximum hardness.
基金Project(51002025) supported by the National Natural Science Foundation of China
文摘The preparation process of amorphous nanometer boron powders through combustion synthesis was investigated, and the effects of the reactant ratio, the heating agent and the milling rate on the activity and particle size of amorphous boron powders were studied. The results show that the boron powders exist in the form of an amorphous phase which has the crystallinity lower than 30.4%, and the panicle size of boron powder decreases with an increase of the high-energy ball milling rate. The purity of amorphous boron powder is 94.8% and panicle sizes are much smaller than 100 nm when the mass ratio of B2O3/Mg/KClO3 is 100：105：17 and the ball milling time is 20 min with the milling rate of 300 r/min. At the same time, the amorphous boron nano-fibers appear in the boron powders.
基金Project(2005-5) supported by the Postdoctoral Foundation of Central South University, ChinaProject(2005038560) supported by the Postdoctoral Science Foundation of China
文摘Rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy was prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter in a continuous or isothermal heating mode. phase transformation was investigated, with a special interest in primary crystallization, by using an in-situ examination of X-ray diffractometry （XRD） and high resolution transmission electron microscopy （HRTEM）. The results show that, the whole devitrification of rapidly solidified Al87NiyCu3Nd3 amorphous alloy involves two main processes of primary crystallization and secondary crystallization that consist mainly of two reactions. For primary crystallization, the apparent activation energies, EIso and EKis and growth activation energies Eg are about 153, 166 and 288 kJ/mol, respectively. The interdiffusion of Al atoms is a rate-controlled step of formation of the a（Al） particles, but slow diffusion of Ni and Nd atoms plays a significant role in retarding growth of the α （Al） particles. For secondary crystallization, EIso, EKis and Eg of the first reaction are about 291,208 and 290 kJ/mol, and those of the second reaction are about 367, 269 and 372 kJ/mol. The two reactions of secondary crystallization are controlled mainly in an interface-controlled three-dimensional mode, depending mainly on slow diffusion of Ni and Nd atoms.
基金supported by the Special Funds for Major States Basic Research Project (No. TG20000264-06) of MOST, China
文摘Ti/Cr (atomic ratio 3:4) amorphous alloy was prepared by ball milling the rapidly quenched Ti/Cr ribbons for 30h, and then milled with MgH_2 for 50 h under Ar atmosphere to obtain MgH_2-30wt. % Ti/Cr composite. The XRD results indicate that MgH_2 decomposed partly during ball milling process. The brittle MgH_2 and the mechanical driving force resulted in a highly dispersive distribution of the Ti/Cr amorphous phase in the Mg matrix. The favorable hydrogenation performance is mainly attributed to the com...
基金Projects(51161015,51371094)supported by the National Natural Science Foundation of China
文摘Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous hydrogen storage characteristics were investigated. The XRD, TEM and SEM linked with EDS detections reveal that the as-spun Nd-free alloy holds an entire nanocrystalline structure but a nanocrystalline and amorphous structure for the as-spun Nd-added alloy, implying that the addition of Nd facilitates the glass forming in the Mg_2Ni-type alloy. Furthermore, the degree of amorphization of the as-spun Nd-added alloy and thermal stability of the amorphous structure clearly increase with the spinning rate rising. The melt spinning ameliorates the hydriding and dehydriding kinetics of the alloys dramatically. Specially, the rising of the spinning rate from 0(the as-cast was defined as the spinning rate of 0 m/s) to 40 m/s brings on the hydrogen absorption saturation ratio(R_5~a)(a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increasing from 36.9% to 91.5% and the hydrogen desorption ratio(R_(1 0)~d)(a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) rising from 16.4% to 47.7% for the(x=10) alloy, respectively.
基金Project(2007CB607602) supported by the National Basic Research Program of China
文摘Co87Nb10Zr3,Co76Nb19Zr5,Co64Nb26Zr10 and Co64Nb16Zr20 amorphous films were deposited on noncrystalline glass substrates by DC unbalanced magnetron sputtering. The compositions of amorphous films were tailored in the light of the individual deposition rate of Co,Nb and Zr. The amorphous films with the anticipated composition were prepared by means of co-sputtering Co,Nb and Zr targets simultaneously. It is indicated that there is interaction among three targets during co-sputtering. The morphology and composition of the films were observed by SEM,AFM and EDS. The structure and magnetic property were measured by XRD and physical property measurement system(PPMS) . The coercivity changes with the composition,varying from 240 to 1 600 A/m. After vacuum isothermal annealing at temperatures of 475,500,525 and 550 ℃ for 15 and 30 min,respectively,it is found that high Nb content is beneficial to improving thermal stability of amorphous films. The crystallized films have the mean grain size of 2-19 nm.
文摘The crystallization kinetics of amorphous (Nd3.6Pr5.4Fe83Co3B5) and the preparation of α-Fe/Nd2Fe14B nanocomposite magnets by controlled melt-solidification of (Nd3.6Pr5.4Fe83Co3B5) was investigated by employing DTA, XRD, and TEM. The results show that a metastable intermediate phase (Nd8Fe27B24) prior to α-Fe and Nd2Fe14B phases is crystallized as the amorphous Nd3.6Pr5.4Fe83Co3B5 is heated to 1 223 K. The crystallization activation energy of α-Fe and Nd8Fe27B24 phases is larger at the beginning stage of crystallization, and then it decreases with crystallized fraction x for the former and has little change when x is below 70% for the latter, which essentially results in an α-Fe/Nd2Fe14B microstructure with a relatively coarse grain size about 20-60 nm and a non-uniform distribution of grain size in the annealed alloy. The α-Fe/Nd2Fe14B nanocomposite magnets with a small average grain size about 14 nm and a quite uniform grain size distribution were prepared by controlled melt-solidification of (Nd3.6Pr5.4Fe83Co3B5) at a wheel speed of 20 m·s-1 during melt-spinning. The magnets show a high maximum energy product of （BH）max = 194 kJ·m-3, which is nearly twice of that of the nanocomposite magnets made by annealing the amorphous Nd3.6Pr5.4Fe83Co3B5 precursor alloy.
基金Projects(51161015,51371094)supported by National Natural Science Foundations of ChinaProject(2011ZD10)supported by Natural Science Foundation of Inner Mongolia,China
文摘In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).
基金Project(2003AA332040) supported by the National High Technology Research and Development Program of China
文摘ZrO2-mullite nano-ceramics were fabricated by in-situ controlled crystallizing from SiO2-Al2O3-ZrO2 amorphous bulk. The thermal transformation sequences of the SiO2-Al2O3-ZrO2 amorphous bulk were investigated by X-ray diffraction, infrared spectrum, scanning electron microscope and differential scanning calorimetric. And the mechanical properties of the nano-ceramics were studied. The results show that the bulks are still in amorphous state at 900 ℃ and the t-ZrO2 forms at about 950 ℃ with a faint spinel-like phase which changes into mullite on further heating. ZrO2 and mullite become major phases at 1 100 ℃ and an amount of m-ZrO2 occur at the same time. The sample heated at 950 ℃ for 2 h and then at 1 100 ℃ for 1 h shows very dense and homogenous microstructure with ball-like grains in size of 20-50 nm. With the increase of crystallization temperature up to 1 350 ℃, the grains grow quickly and some grow into lath-shaped grains with major diameter of 5 μm. After two-step treatment the highest micro-hardness, flexural strength and fracture toughness of the samples are 13.72 GPa, 520 MPa and 5.13 MPa·m1/2, respectively.
基金Project(59771048) supported by the National Natural Science Foundation of China project(2002AA302509) supportedby the High Technology Research and Development Program of China
文摘Impact wear behaviors of Hadfield manganese steel at different impact angles were investigated. The results of impact wear tests show that there exists a critical impact load for Hadfield steel. The wear rate suddenly turns down after some impact cycles when the impact load is greater than the critical load. The critical impact load is smaller than 8.2 J in this research because the nano-sized austenitic grains embedded in amorphous delay the crack propagation in subsurface. From high resolution transmission electron microscope (HRTEM) examination of subsurface microstructure, it is found that a large amount of nano-sized grains embedded in bulk amorphous matrix are fully developed and no martensitic transformation occurs during the impact wear process. The analytical results of worn surface morphology and debris indicate that the initiation of crack, propagation and spalling are restricted in the amorphous phase, resulting in the size distribution of debris in nano-sizes, which is the reason why the wear rate of Hadfield steel is greatly decreased at high impact load.
文摘The Al-Ni-Y alloy powder was prepared by rapid solidification technology of inert gas atomization. The diameter of amorphous powder is less than 12 μm. The effects of atomization gas on cooling velocity, morphology, microstructure and microhardness of powder and fine powder ratio were investigated.The results show that the morphology, microstructure and microhardness of powder and fine powder ratio are affected by cooling velocity changed through atomization gas. The cooling velocity of inert gas atomization is more than 1×10~4 K/s. The larger the cooling velocity, the finer the powder, and the smoother the surface of powder; the smaller the diameter of powder, the larger the microhardness of powder.
