The Cu25 Nb75 and Ni45Nb55 amorphous films with about 500nm thickness were prepared by ion beam assisted deposition (IBAD). Potentiodynamic polarization measurement was adopted to investigate the corrosion resistance ...The Cu25 Nb75 and Ni45Nb55 amorphous films with about 500nm thickness were prepared by ion beam assisted deposition (IBAD). Potentiodynamic polarization measurement was adopted to investigate the corrosion resistance of samples and the tests were carried out respectively in 1mol/L H2SO4 and NaOH aquatic solution. The corrosion performance of the amorphous films was compared with that of multilayered and pure Nb films. Experimental results indicated that the corrosion resistance of amorphous films was better than that of the corresponding multilayers and pure Nb films for both Ni-Nb system with negative heat of formation and Cu-Nb system with positive heat of formation.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
[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
Amorphous metals are totally different from crystalline metals in regard to atom arrangement. Amorphous metals do not have grain boundaries and weak spots that crystalline materials contain, making them more resistant...Amorphous metals are totally different from crystalline metals in regard to atom arrangement. Amorphous metals do not have grain boundaries and weak spots that crystalline materials contain, making them more resistant to wear and corrosion. In this study, amorphous Fe-W alloy films were first prepared by an electroplating method and were then made hydrophobic by modification with a water repellent （heptadecafluoro-1,1,2,2-tetradecyl） trimethoxysilane. Hierarchical micro-nano structures can be obtained by slightly oxidizing the as-deposited alloy, accompanied by phase transformation from amorphous to crystalline during heat treatment. The mi-cro-nano structures can trap air to form an extremely thin cushion of air between the water and the film, which is critical to producing hydrophobicity in the film. Results show that the average values of capacitance, roughness factor, and impedance for specific surface areas of a 600°C heat-treated sample are greater than those of a sample treated at 500°C. Importantly, the coating can be fabricated on various metal substrates to act as a corrosion retardant.展开更多
The initial field electron emission degradation behaviour of original nano-structured sp^2-bonded amorphous carbon films has been observed, which can be attributed to the increase of the work function of the film in t...The initial field electron emission degradation behaviour of original nano-structured sp^2-bonded amorphous carbon films has been observed, which can be attributed to the increase of the work function of the film in the field emission process analysed using a Fowler-Nordheim plot. The possible reason for the change of work function is suggested to be the desorption of hydrogen from the original hydrogen termination film surface due to field emission current-induced local heating. For the explanation of the emission degradation behaviour of the nano-structured sp2-bonded amorphous carbon film, a cluster model with a series of graphite （0001） basal surfaces has been presented, and the theoretical calculations have been performed to investigate work functions of graphite （0001） surfaces with different hydrogen atom and ion chemisorption sites by using first principles method based on density functional theory-local density approximation.展开更多
Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour d...Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour deposition system under the different deposition conditions. It was proposed that there was no direct correlation between the photosensitivity and the hydrogen content （CH） as well as H-Si bonding configurations, but for the stability, they were the critical factors. The experimental results indicated that higher substrate temperature, hydrogen dilution ratio and lower deposition rate played an important role in improving the microstructure of a-Si：H films. We used hydrogen elimination model to explain our experimental results.展开更多
The room temperature stability and crystallization of amorphous Nd_xFe_(1-x)thin films with x=0.06—0.90,prepared by flash evaporation at 77 K,were investigated by X-ray diffraction and TEM observation.The amorphous N...The room temperature stability and crystallization of amorphous Nd_xFe_(1-x)thin films with x=0.06—0.90,prepared by flash evaporation at 77 K,were investigated by X-ray diffraction and TEM observation.The amorphous Nd_xFe_(1-x)films are stable at room temperature when 0.19<x<0.50.Crystallized phases grow along the surface of film as very thin flakes and become thick only at relatively high temperatures.After complete crystallization,the Nd_xFe_(1-x)films with x<0.50 are composed of Nd_2Fe-(17)and metal Nd,but no NdFe2,a phase expected to occur by phase diagram.展开更多
In order to study the influence of nitrogen incorporated into amorphous carbon films, nitrogenated amorphous carbon films have been deposited by using surface wave plasma chemical vapor deposition under various ratios...In order to study the influence of nitrogen incorporated into amorphous carbon films, nitrogenated amorphous carbon films have been deposited by using surface wave plasma chemical vapor deposition under various ratios of N2/CH4 gas flow. Optical emission spectroscopy has been used to monitor plasma features near the deposition zone. After deposition, the samples are checked by Raman spectroscopy and x-ray photo spectroscopy (XPS). Optical emission intensities of CH and N atom in the plasma are found to be enhanced with the increase in the N2/CH4 gas flow ratio, and then reach their maximums when the N2/CH4 gas flow ratio is 5%. A contrary variation is found in Raman spectra of deposited films. The intensity ratio of the D band to the G band (Id/Ig) and the peak positions of the G and D bands all reach their minimums when the N2/CH4 gas flow ratio is 5%. These show that the structure of amorphous carbon films has been significantly modified by introduction of nitrogen.展开更多
Direct current metal filtered cathodic vacuum arc （FCVA） and acetylene gas （C2H2） were wielded to synthesize Ti-containing amorphous carbon films on Si （100）. The influence of substrate bias voltage and acetylen...Direct current metal filtered cathodic vacuum arc （FCVA） and acetylene gas （C2H2） were wielded to synthesize Ti-containing amorphous carbon films on Si （100）. The influence of substrate bias voltage and acetylene gas on the microstructure and mechanical properties of the films were investigated. The results show that the phase of TiC in the （111） preferential crystallographic orientation exists in the film,and the main existing pattern of carbon is sp2. With increasing the acetylene flow rate,the contents of Ti and TiC phase of the film gradually reduce; however,the thickness of the film increases. When the substrate bias voltage reaches -600 V,the internal stress of the film reaches 1.6 GPa. The micro-hardness and elastic modulus of the film can reach 33.9 and 237.6 GPa,respectively,and the friction coefficient of the film is 0.25.展开更多
Hydrogenated amorphous silicon （a-Si： H） films were deposited on Si （100） and glass substrates by dielectric barrier discharge enhanced chemical vapour deposition （DBD-CVD） in （SiH4＋H2） atmosphere at room te...Hydrogenated amorphous silicon （a-Si： H） films were deposited on Si （100） and glass substrates by dielectric barrier discharge enhanced chemical vapour deposition （DBD-CVD） in （SiH4＋H2） atmosphere at room temperature. Results of the thickness measurement, SEM （scanning electron microscope）, Raman, and FTIR （Fourier transform infrared spectroscopy） show that with the increase in the applied peak voltage, the deposition rate and network order of the films increase, and the hydrogen bonding configurations mainly in di-hydrogen （Si-H2） and poly hydrogen （SiH2）n are introduced into the films. The UV-visible transmission spectra show that with the decrease in SiH4/ （SiHn＋H2） the thin films＇ band gap shifts from 1.92 eV to 2.17 eV. These experimental results are in agreement with the theoretic analysis of the DBD discharge. The deposition of a-Si： H films by the DBD-CVD method as reported here for the first time is attractive because it allows fast deposition of a-Si： H films on large-area low-melting-point substrates and requires only a low cost of production without additional heating or pumping equipment.展开更多
The short-range order structures of Fe_xGe_(1-x) amorphous thin films,(x=8.7,19.1 and 28.5%)have been studied by means of X-ray absorption spectrum.The nearest neighbors around a Ge or an Fe atom are constituted by tw...The short-range order structures of Fe_xGe_(1-x) amorphous thin films,(x=8.7,19.1 and 28.5%)have been studied by means of X-ray absorption spectrum.The nearest neighbors around a Ge or an Fe atom are constituted by two coordinate sub-shells with a very short dis- tance,In two films with lower Fe content,structural parameters of the nearest neighbors around a Ge atom are very near to that in amorphous germanium,and the positions of Fe at- oms are randomly substitutional.But when x=28.5%,some great changes occur on the short-range order structure of a-Fe_xGe_(1-x) film:its structure deviates from continuous ran- dora network and tends toward dense random packing of atoms.Meanwhile,there is a strong- er interaction between near neighboring Fe-Ge atoms in a-Fe_xGe_(1-x) films.展开更多
The perpendicular anisotopy,coercivity and Kerr rotation angle of the amorphous Tb_(32)Fe_(54)Co_(14) films were studied.The X-ray,electron diffraction,XPS and AES profile con- firmed that no obvious change in their a...The perpendicular anisotopy,coercivity and Kerr rotation angle of the amorphous Tb_(32)Fe_(54)Co_(14) films were studied.The X-ray,electron diffraction,XPS and AES profile con- firmed that no obvious change in their amorphous structure and oxygen concentration is ob- served after annealing at 100℃,while their properties alter evidently under bending stress.It seems to be believed that the perpendicular anisotropy in the Tb_(32)Fe_(54)Co_(14) films mainly arises from the induced stress during preparation and the magnetostriction coupling stress,as well as,the thermal instability of the film relates closely to the stress relaxation during annealing.展开更多
The amorphous Ml-Ni films were prepared by means of ion beam sputtering the electrochemical hydrogen storage,discharge ability and durability of amorphous film electrodes are investigated,The results show that the max...The amorphous Ml-Ni films were prepared by means of ion beam sputtering the electrochemical hydrogen storage,discharge ability and durability of amorphous film electrodes are investigated,The results show that the maximum capacities of the amorphous MlNi_(1.79),MlNi_(2.52),and MlNi_(3.44) samples are 90,100 and 142 mAh/g,respectively,and the MlNi_(3.44) amorphous film does not off and disintegrate into fine particles a fier more than 580 cycles.展开更多
Amorphous hydrogenated carbon thin films have been deposited with benzene plasma in an electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition system. The characteristic of Benzene discharge plas...Amorphous hydrogenated carbon thin films have been deposited with benzene plasma in an electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition system. The characteristic of Benzene discharge plasma has been monitored by Mast spectrometry. It shows that the majority of the plasma species in the downstream ECR Plasma with benzene as gas source are acetylene, ethylene and higher mass species. In the experiments, the effects of the substrate temperature on the deposition rates have been emphatically studied. The structures of the films were analyzed by FTIR and Ramam spectrum.The results show that when the substrate temperature rises, the deposition rate drops down, the hydrogen Foment decreases, with the higher SP3 content being presented in the film.展开更多
Electrical properties of C/Ni films are studied using four mosaic targets made of pure graphite and stripes of nickel with the surface areas of 1.78,3.21,3.92 and 4.64%.The conductivity data in the temperature range o...Electrical properties of C/Ni films are studied using four mosaic targets made of pure graphite and stripes of nickel with the surface areas of 1.78,3.21,3.92 and 4.64%.The conductivity data in the temperature range of400-500 K shows the extended state conduction.The conductivity data in the temperature range of 150-300 K shows the multi-phonon hopping conduction.The Berthelot-type conduction dominates in the temperature range of 50-150 K.The conductivity of the films in the temperature range about 〈 50 K is described in terms of variable-range hopping conduction.In low temperatures,the localized density of state around Fermi level（F）for the film deposition with 3.92% nickel has a maximum value of about 56.2×10^（17）cm^（-3）eV^（-1） with the minimum average hopping distance of about 3.43 × 10^（-6） cm.展开更多
Amorphous silicon films are prepared at lower temperature of 350 ℃ by new catalytic chemical vapor deposition method.In the method,material gases (SiH 4 and H 2) are decomposed by catalytic reaction at given temper...Amorphous silicon films are prepared at lower temperature of 350 ℃ by new catalytic chemical vapor deposition method.In the method,material gases (SiH 4 and H 2) are decomposed by catalytic reaction at given temperature,so a-Si films are deposited on substrates.It is found that a-Si films with high quality can be obtain,such as high photosensitivity of 10 6,low spin density of 2.5×10 16 cm -3 .展开更多
a-C:F films are deposited by microwave electron cyclotron resonance (ECR)plasma chemical vapor deposition (CVD) using trifluoromethane (CHF3) and benzene (C6H6) as source gases at different microwave powers. The radic...a-C:F films are deposited by microwave electron cyclotron resonance (ECR)plasma chemical vapor deposition (CVD) using trifluoromethane (CHF3) and benzene (C6H6) as source gases at different microwave powers. The radicals in plasma originating from source gases dissociation are analyzed by relative irradiance measurement. The bonding configurations and binding state of a-C:F films are measured with Fourier-transformed infrared spectrometer (FTIR) and x-ray photoelectron spectroscopy (XPS). The results show that a-C:F films are mainly composed of CF radical at lower powers but of CF2 radical at higher powers. The deposition of films is related to the radicals generated in plasma and the main bonding configurations are dependent on the ratio of CF to CF2 radicals in films.展开更多
Fluorinated amorphous carbon films were deposited using microwave electron cyclotron resonance chemical vapor deposition (ECR-CVD) reactor with CF4 and C8H6 as source gas and were annealed in nitrogen ambience for the...Fluorinated amorphous carbon films were deposited using microwave electron cyclotron resonance chemical vapor deposition (ECR-CVD) reactor with CF4 and C8H6 as source gas and were annealed in nitrogen ambience for the investigating of their thermal stability .The relative concentration of C=C bond and optical bandgap were obtained by Fourier Transform Infrared (FTIR) spectroscopy and Ultraviolet-Visible (UV-VIS ) spectrum, respectively. It has been demonstrated that there is a close relationship between relative concentration of C=C bond and optical bandgap, and the films deposited at a higher microwave power have a lower optical bandgap and a better thermal stability.展开更多
Theamorphous magnetoelastic Fe66Co17Si1B6 thin films have been deposited by dc magnetron sputtering. A lot of ＂nano-trenches＂ have been observed on the fdm surfaces by AFM. The permeability of amorphous Fe66COlTSilB...Theamorphous magnetoelastic Fe66Co17Si1B6 thin films have been deposited by dc magnetron sputtering. A lot of ＂nano-trenches＂ have been observed on the fdm surfaces by AFM. The permeability of amorphous Fe66COlTSilB6 thin films was measured within the frequency range of 0.6GHz-10.2 GHz. The ferromagnetic resonance frequency was found to be 1.2 GHz. MFM shows that the domain of thin film is a maze-type pattern, which indicates that an out-of-plane magnetic anisotropy exists. The out-of-plane anisotropy is believed due to the stress-induced magnetic anisotropy. It can be inferred that the internal stress is tensile stress and normal to the film plane. Index Terms展开更多
CN x films were made by a facing targets sputtering ( FTS) systemon the Si(100) substrate under different N 2 partial pressure. XRD, XPS, FTIR and Raman Spectroscopy( RS) were measured to investigate the str...CN x films were made by a facing targets sputtering ( FTS) systemon the Si(100) substrate under different N 2 partial pressure. XRD, XPS, FTIR and Raman Spectroscopy( RS) were measured to investigate the structure and the binding state of the film. The films are amorphous and the N/C increases with the N 2 partial pressure increasing and reaches 0 46 when the N 2 pressure is 100%. The N incorporated C forms N sp 2C and N sp 3C mainly and there is a small amount of C≡N.展开更多
基金This work was supported in part by National Naturul Science Foundation of China(No.19875027)the Ministry of Science and Technology of China(No.G20000672071)by the Administration of Tsinghua University.
文摘The Cu25 Nb75 and Ni45Nb55 amorphous films with about 500nm thickness were prepared by ion beam assisted deposition (IBAD). Potentiodynamic polarization measurement was adopted to investigate the corrosion resistance of samples and the tests were carried out respectively in 1mol/L H2SO4 and NaOH aquatic solution. The corrosion performance of the amorphous films was compared with that of multilayered and pure Nb films. Experimental results indicated that the corrosion resistance of amorphous films was better than that of the corresponding multilayers and pure Nb films for both Ni-Nb system with negative heat of formation and Cu-Nb system with positive heat of formation.
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.
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financially supported by the National Magnetic Confinement Fusion Science Program(No.2010GB106003)the National Natural Science Founda-tion of China(No.91023037)
文摘Amorphous metals are totally different from crystalline metals in regard to atom arrangement. Amorphous metals do not have grain boundaries and weak spots that crystalline materials contain, making them more resistant to wear and corrosion. In this study, amorphous Fe-W alloy films were first prepared by an electroplating method and were then made hydrophobic by modification with a water repellent （heptadecafluoro-1,1,2,2-tetradecyl） trimethoxysilane. Hierarchical micro-nano structures can be obtained by slightly oxidizing the as-deposited alloy, accompanied by phase transformation from amorphous to crystalline during heat treatment. The mi-cro-nano structures can trap air to form an extremely thin cushion of air between the water and the film, which is critical to producing hydrophobicity in the film. Results show that the average values of capacitance, roughness factor, and impedance for specific surface areas of a 600°C heat-treated sample are greater than those of a sample treated at 500°C. Importantly, the coating can be fabricated on various metal substrates to act as a corrosion retardant.
文摘The initial field electron emission degradation behaviour of original nano-structured sp^2-bonded amorphous carbon films has been observed, which can be attributed to the increase of the work function of the film in the field emission process analysed using a Fowler-Nordheim plot. The possible reason for the change of work function is suggested to be the desorption of hydrogen from the original hydrogen termination film surface due to field emission current-induced local heating. For the explanation of the emission degradation behaviour of the nano-structured sp2-bonded amorphous carbon film, a cluster model with a series of graphite （0001） basal surfaces has been presented, and the theoretical calculations have been performed to investigate work functions of graphite （0001） surfaces with different hydrogen atom and ion chemisorption sites by using first principles method based on density functional theory-local density approximation.
文摘Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour deposition system under the different deposition conditions. It was proposed that there was no direct correlation between the photosensitivity and the hydrogen content （CH） as well as H-Si bonding configurations, but for the stability, they were the critical factors. The experimental results indicated that higher substrate temperature, hydrogen dilution ratio and lower deposition rate played an important role in improving the microstructure of a-Si：H films. We used hydrogen elimination model to explain our experimental results.
文摘The room temperature stability and crystallization of amorphous Nd_xFe_(1-x)thin films with x=0.06—0.90,prepared by flash evaporation at 77 K,were investigated by X-ray diffraction and TEM observation.The amorphous Nd_xFe_(1-x)films are stable at room temperature when 0.19<x<0.50.Crystallized phases grow along the surface of film as very thin flakes and become thick only at relatively high temperatures.After complete crystallization,the Nd_xFe_(1-x)films with x<0.50 are composed of Nd_2Fe-(17)and metal Nd,but no NdFe2,a phase expected to occur by phase diagram.
基金Natural Science Foundation of Anhui Province(No.03044702)National Natural Science Foundation of China(No.19835030)
文摘In order to study the influence of nitrogen incorporated into amorphous carbon films, nitrogenated amorphous carbon films have been deposited by using surface wave plasma chemical vapor deposition under various ratios of N2/CH4 gas flow. Optical emission spectroscopy has been used to monitor plasma features near the deposition zone. After deposition, the samples are checked by Raman spectroscopy and x-ray photo spectroscopy (XPS). Optical emission intensities of CH and N atom in the plasma are found to be enhanced with the increase in the N2/CH4 gas flow ratio, and then reach their maximums when the N2/CH4 gas flow ratio is 5%. A contrary variation is found in Raman spectra of deposited films. The intensity ratio of the D band to the G band (Id/Ig) and the peak positions of the G and D bands all reach their minimums when the N2/CH4 gas flow ratio is 5%. These show that the structure of amorphous carbon films has been significantly modified by introduction of nitrogen.
文摘Direct current metal filtered cathodic vacuum arc （FCVA） and acetylene gas （C2H2） were wielded to synthesize Ti-containing amorphous carbon films on Si （100）. The influence of substrate bias voltage and acetylene gas on the microstructure and mechanical properties of the films were investigated. The results show that the phase of TiC in the （111） preferential crystallographic orientation exists in the film,and the main existing pattern of carbon is sp2. With increasing the acetylene flow rate,the contents of Ti and TiC phase of the film gradually reduce; however,the thickness of the film increases. When the substrate bias voltage reaches -600 V,the internal stress of the film reaches 1.6 GPa. The micro-hardness and elastic modulus of the film can reach 33.9 and 237.6 GPa,respectively,and the friction coefficient of the film is 0.25.
基金the National Natural Science Foundation of china(No.50372060)
文摘Hydrogenated amorphous silicon （a-Si： H） films were deposited on Si （100） and glass substrates by dielectric barrier discharge enhanced chemical vapour deposition （DBD-CVD） in （SiH4＋H2） atmosphere at room temperature. Results of the thickness measurement, SEM （scanning electron microscope）, Raman, and FTIR （Fourier transform infrared spectroscopy） show that with the increase in the applied peak voltage, the deposition rate and network order of the films increase, and the hydrogen bonding configurations mainly in di-hydrogen （Si-H2） and poly hydrogen （SiH2）n are introduced into the films. The UV-visible transmission spectra show that with the decrease in SiH4/ （SiHn＋H2） the thin films＇ band gap shifts from 1.92 eV to 2.17 eV. These experimental results are in agreement with the theoretic analysis of the DBD discharge. The deposition of a-Si： H films by the DBD-CVD method as reported here for the first time is attractive because it allows fast deposition of a-Si： H films on large-area low-melting-point substrates and requires only a low cost of production without additional heating or pumping equipment.
文摘The short-range order structures of Fe_xGe_(1-x) amorphous thin films,(x=8.7,19.1 and 28.5%)have been studied by means of X-ray absorption spectrum.The nearest neighbors around a Ge or an Fe atom are constituted by two coordinate sub-shells with a very short dis- tance,In two films with lower Fe content,structural parameters of the nearest neighbors around a Ge atom are very near to that in amorphous germanium,and the positions of Fe at- oms are randomly substitutional.But when x=28.5%,some great changes occur on the short-range order structure of a-Fe_xGe_(1-x) film:its structure deviates from continuous ran- dora network and tends toward dense random packing of atoms.Meanwhile,there is a strong- er interaction between near neighboring Fe-Ge atoms in a-Fe_xGe_(1-x) films.
文摘The perpendicular anisotopy,coercivity and Kerr rotation angle of the amorphous Tb_(32)Fe_(54)Co_(14) films were studied.The X-ray,electron diffraction,XPS and AES profile con- firmed that no obvious change in their amorphous structure and oxygen concentration is ob- served after annealing at 100℃,while their properties alter evidently under bending stress.It seems to be believed that the perpendicular anisotropy in the Tb_(32)Fe_(54)Co_(14) films mainly arises from the induced stress during preparation and the magnetostriction coupling stress,as well as,the thermal instability of the film relates closely to the stress relaxation during annealing.
文摘The amorphous Ml-Ni films were prepared by means of ion beam sputtering the electrochemical hydrogen storage,discharge ability and durability of amorphous film electrodes are investigated,The results show that the maximum capacities of the amorphous MlNi_(1.79),MlNi_(2.52),and MlNi_(3.44) samples are 90,100 and 142 mAh/g,respectively,and the MlNi_(3.44) amorphous film does not off and disintegrate into fine particles a fier more than 580 cycles.
基金Nature Science Foundation of Jiangsu Province, P.R.China
文摘Amorphous hydrogenated carbon thin films have been deposited with benzene plasma in an electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition system. The characteristic of Benzene discharge plasma has been monitored by Mast spectrometry. It shows that the majority of the plasma species in the downstream ECR Plasma with benzene as gas source are acetylene, ethylene and higher mass species. In the experiments, the effects of the substrate temperature on the deposition rates have been emphatically studied. The structures of the films were analyzed by FTIR and Ramam spectrum.The results show that when the substrate temperature rises, the deposition rate drops down, the hydrogen Foment decreases, with the higher SP3 content being presented in the film.
文摘Electrical properties of C/Ni films are studied using four mosaic targets made of pure graphite and stripes of nickel with the surface areas of 1.78,3.21,3.92 and 4.64%.The conductivity data in the temperature range of400-500 K shows the extended state conduction.The conductivity data in the temperature range of 150-300 K shows the multi-phonon hopping conduction.The Berthelot-type conduction dominates in the temperature range of 50-150 K.The conductivity of the films in the temperature range about 〈 50 K is described in terms of variable-range hopping conduction.In low temperatures,the localized density of state around Fermi level（F）for the film deposition with 3.92% nickel has a maximum value of about 56.2×10^（17）cm^（-3）eV^（-1） with the minimum average hopping distance of about 3.43 × 10^（-6） cm.
文摘Amorphous silicon films are prepared at lower temperature of 350 ℃ by new catalytic chemical vapor deposition method.In the method,material gases (SiH 4 and H 2) are decomposed by catalytic reaction at given temperature,so a-Si films are deposited on substrates.It is found that a-Si films with high quality can be obtain,such as high photosensitivity of 10 6,low spin density of 2.5×10 16 cm -3 .
文摘a-C:F films are deposited by microwave electron cyclotron resonance (ECR)plasma chemical vapor deposition (CVD) using trifluoromethane (CHF3) and benzene (C6H6) as source gases at different microwave powers. The radicals in plasma originating from source gases dissociation are analyzed by relative irradiance measurement. The bonding configurations and binding state of a-C:F films are measured with Fourier-transformed infrared spectrometer (FTIR) and x-ray photoelectron spectroscopy (XPS). The results show that a-C:F films are mainly composed of CF radical at lower powers but of CF2 radical at higher powers. The deposition of films is related to the radicals generated in plasma and the main bonding configurations are dependent on the ratio of CF to CF2 radicals in films.
文摘Fluorinated amorphous carbon films were deposited using microwave electron cyclotron resonance chemical vapor deposition (ECR-CVD) reactor with CF4 and C8H6 as source gas and were annealed in nitrogen ambience for the investigating of their thermal stability .The relative concentration of C=C bond and optical bandgap were obtained by Fourier Transform Infrared (FTIR) spectroscopy and Ultraviolet-Visible (UV-VIS ) spectrum, respectively. It has been demonstrated that there is a close relationship between relative concentration of C=C bond and optical bandgap, and the films deposited at a higher microwave power have a lower optical bandgap and a better thermal stability.
文摘Theamorphous magnetoelastic Fe66Co17Si1B6 thin films have been deposited by dc magnetron sputtering. A lot of ＂nano-trenches＂ have been observed on the fdm surfaces by AFM. The permeability of amorphous Fe66COlTSilB6 thin films was measured within the frequency range of 0.6GHz-10.2 GHz. The ferromagnetic resonance frequency was found to be 1.2 GHz. MFM shows that the domain of thin film is a maze-type pattern, which indicates that an out-of-plane magnetic anisotropy exists. The out-of-plane anisotropy is believed due to the stress-induced magnetic anisotropy. It can be inferred that the internal stress is tensile stress and normal to the film plane. Index Terms
文摘CN x films were made by a facing targets sputtering ( FTS) systemon the Si(100) substrate under different N 2 partial pressure. XRD, XPS, FTIR and Raman Spectroscopy( RS) were measured to investigate the structure and the binding state of the film. The films are amorphous and the N/C increases with the N 2 partial pressure increasing and reaches 0 46 when the N 2 pressure is 100%. The N incorporated C forms N sp 2C and N sp 3C mainly and there is a small amount of C≡N.
