Diffusion of Hydrogen in Amorphous NiCrFeSiB Alloy

The diffusion of hydrogen in amorphous NiCrFeSiB alloy has been studied by electrochemicalmethod. In the temperature range of 20~50℃, diffusion coefficient of hydrogen in the alloy fol-lows the equation' D(cm2/s)= 9.27x10-8exp(-53.4 kJ/RT). At room temperature the diffusion.coefficient D and the solubility Co are 6.125x 10-12 cm2/s and 0.007 mol/cm3, respectively.When As2O3 is added into the cathodic solution or the charging current density is increased, thediffusion coefficient and solubility increase, and the difFusion activation energy decreases. Theinfluence of amorphous structure on diffusion and solution of hydrogen is discussed.     

Thermal Stability of Amorphous Hydride Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45)

The thermal stability of amorphous ternary hydrides Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45) and their corre-sponding amorphous binary alloys Mg_(50)Ni_(50) and Mg_(30)Ni_(70) were studied with X-ray diffraction(XRD) and differential scanning calorimetry(DSC). Samples of the amorphous alloys were preparedby mechanical alloying and the amorphous hydrides were obtained by charging the alloys with gas-eous hydrogen at 3.0 MPa and 423 K. It was found that the amorphous hydrides released most oftheir hydrogen before the crystallization of the essentially hydrogen depleted amorphous alloy. Thecrystallization temperature of amorphous Mg_(50)Ni_(50)H_(54) elevated and that of amorphousMg_(30)Ni_(70)H_(45) did not change in relation to the original binary amorphous alloy. This is very excep-tional for amorphous hydrides. The reason for the effects of hydrogen absorption/desorption on thecrystallization of amorphous alloys was discussed.     

Application of the Hydrogen Diffusion Model to the Hydrogen Permeation

The model of hydrogen diffusion formerly de-veloped [1] has been applied successfully to thehydrogen permeation experiment results of threekinds of materials,α—Fe,Fe—Ti alloy and Fe—Ti—Calloy by the mathematical fitting method.From thefitting results it was shown that the model can re-fiect well the diffusion of hydrogen in the materialswith trapping.The obtained trapping parameters(αand β)can be used to explain well the diffusion ofhydrogen in the samples with trapping.     

Electrical conductivity of Pd47Ni47Si6 amorphous membrane while hydrogen permeation

Hydrogen diffusion through an amorphous membrane causes local disorders in the structure which can be detected through the measurement of changes of the electrical conductivity. Detecting these changes and comparing them directly with the amount of the permeated hydrogen provides information on the efficiency of separation, which can be used in hydrogen sensor and analyzer technology. This paper presents the results of electrical resistivity measurement of Pd₄₇Ni₄₇Si₆ alloy amorphous membrane while hydrogen permeation flux was being changed along with the temperature. It was found that hydrogen changes the nature of the resistivity and the temperature coefficient of resistivity is negative, however, starting from the temperature of 365 K, its value becomes smaller. In order to explain this phenomenon thorough and detailed measurements of phase transitions were made with the use of differential scanning calorimetry and X-ray diffractometry. On the basis of the research an attempt was made to explain the recorded changes of electrical conductivity.     

Microstructure of Differently Annealed NanocrystallineFe_(72.7)Cu_1Nb_(1.8)Mo_2Si_(13)B_(9.5) Alloy

The microstructure of differently annealed nanocrystalline Fe72.7Cu1Nb1.8Mo2Si13B9.5 alloy was investigated by using Mssbauer spectroscopy and transmission electron microscope. The specimens were isochronally annealed at temperatures between 480℃ and 600℃ for 0.5 h. The experimental results show that the microstructure mainly consists of the nanoscale bcc α-Fe(Si) grains and the residual amorphous matrix phase. A trace paramagnetic phase was found for annealing about above 500℃. The volume fraction of cr-Fe(Si) grain increases with increasing annealing temperature, whereas the average size of grain is almost unchanged above 480℃ up to 580℃. The calculated thickness of the intergranular layer of the residual amorphous matrix clearly decreases with increasing annealing temperature.     

TEM Investigations of Thermal Stability of Nanocrystamne Co_(81)Cr_(19)

In situ transrnission electron microscopic observations were carried out to study the thermal stability of nanocrystalline Co81 Cr19 (n-Co81 Cr19) alloy prepared by d.c. sputtering, The TEM results show that the originally existed nanocrystalline phase hcp-CoCr is thermally stable, no apparent grain growth was observed until annealing to the final stage at.800℃. But the evolution of .microstructure of amorphous oxide Co2Cro4. which is formed duting in situ annealing. is drastically affected by the electron irradiation. In the electron irradiated area. the newly formed amorphous oxide Co2CrO4crystallizes at about 550℃. and grows into fine crystals finally. However, in the electron nonirradiated area, the amorphous oxide Co2CrO4 crystallizes at about 630℃. and grows into large strip shaped crystals during afterward annealing. the space between strip shaped crystals are also fine grained hcp-CoCr alloy. XRD analysis result of the thick film Co81 Cr19 is in good agreement with that of in situ TEM for the excellent stability of hcp-CoCr     

一种氢渗透模型的构建及其在Nb基渗氢合金中的应用

基于Fick第二定律,推导出了一种新的氢渗透数学模型,并成功编制了相应的Matlab计算程序。根据该模型,建立了一种计算Nb基渗氢合金氢扩散系数和溶解系数的新方法;通过对Nb基合金在不同温度下的实例计算,并与实验和文献结果相比较,证实了本模型的可行性和有效性。     

Ordering of the α-Fe(Si) Crystallization Phase in Annealed Fe_(73.5)Cu_1Mo_3Si_(13.5)B_9 Alloy

The ordering of the α-Fe(Si) crystallization phase in annealed Fe73.5Cu1Mo3Si13.5B9 alloy has been studied using XRD method. The α-Fe(Si) phase in Fe73.5Cu1Mo3Si13.5B9 alloy annealed at 460℃ for 1 h consists of the DO3-type ordered region with spherical shape and disordered region. The size of DO3 ordered region increases with the annealing temperature. When the annealing temperature is 560℃, the size of the ordered region in the α-Fe(Si) grain is 14.0nm,which is nearly as large as that of the α-Fe(Si) grain (14.2 nm) and the degree of order of the α-Fe(Si) phase is about 0.78. When Fe73.5Cu1 Mo3Si13.5B9 amorphous alloy is annealed at 520℃, with the increment of the annealing time, the shape of the DO3 ordered region in the α-Fe(Si) phase is spheroidal at the beginning of the annealing and becomes spherical and has asize of 12.8 nm when the annealing time is 60 min. In addition, the DO3 superlattice lines of the α-Fe(Si) phase will vanish if Fe73.5Cu1Mo3Si13.5 B9 amorphous alloy is annealed for 1 h at 750℃.     

316L不锈钢基体氧化铝涂层的氢渗透性能

在316L不锈钢上采用金属有机化学气相沉积(MOCVD)法沉积了氧化铝涂层。使用XRD、SEM分析氧化铝涂层的物相和微观形貌, 采用气相氢渗透装置对涂层氢渗透行为进行表征。结果表明, 973 K退火处理后涂层为非晶氧化铝, 涂层均匀、完整, 厚度为190 nm。氧化铝涂层的氢渗透压力指数为0.56~0.78, 说明氢渗透过程机制为表面过程和体扩散过程共同控制。氧化铝涂层的表观氢渗透率为P = 1.99×10^-6 exp(-117×10³/RT) mol/(m·s·Pa^1/2)。氧化铝涂层的氢渗透激活能为117 kJ/mol, 远高于316L不锈钢的66.6 kJ/mol, 涂层对氢的渗透具有明显的阻挡作用。此外, 在873~973 K氧化铝涂层对316L不锈钢的氢渗透阻挡因子(PRF)为59~119, 涂层氢渗透阻挡性能优异。     

Effect of ordering on the rate of diffusion and permeation of hydrogen in a Ni3Fe alloy

The effect of ordering on the diffusion, permeability, and solubility of hydrogen in an Ni₃Fe alloy was studied. It was established that changes in these properties were associated with changes in preexponential factors in the expressions for their temperature dependence. The activation energies for diffusion and permeation and the heat of solution of hydrogen are the same for alloy specimens in the ordered and disordered state.Translated from Fiziko-Khimicheskaya Mekhanika Materialov, Vol. 5, No. 5, pp. 597–601, September–October, 1969.     

Hydrogen Permeation and Diffusion in Low-carbon Steels and 16Mn Steel

In the present work. the hydrogen permeation and diffusion in two low-carbon steels. # 10 and #20. and 16Mn stee1 over the temperature range of 80 to 330℃ were investigated using gaseous permeation technique. The temperature dependence of hydrogen permeability. diffusivity and solubility for the three steels was obtained in the form of the Arrhenius equations. It was shown that the hydrogen permeability of the 16Mn steel is somewhat lower than that of the two low-carbon steels.whereas the hydrogen diffusivity is lowered in the order of #10, #20 and 16Mn but the activation energy of diffusion is much the same for the three steels. The difference in the diffusivity was attributed to the increase of ferrite-cementite interface areas with the refinement of pearlitic structure in the steels     

用表面偏析法研究磷原子在Ni_(84)P_(16)非晶合金中的扩散

用 AES 原位加热的方法研究了 Ni_(84)P_(16)非晶合金中磷原子的表面偏析现象。在实验温度范围内,磷向自由表面的偏析是由体扩散控制的,表面浓度 C_S 随退火时间 t 的变化符合 Hoffmann—Erlewein关系(H—E关系)。在250—350℃温区内,磷原子单独向表面偏析,扩散系数 D 位于1.1×10~(-24)—9.0×10~(-22)m~2s~(-1)之间,D 与 T 符合 Arrhenius 关系,其中指数前因子 D_0=2.81×10~(-6)m~2s~_(-1),扩散激活能E_0=1.70eV。在380℃退火时,晶化产生的晶界加速 P 偏析,同时促进 Ni 向自由表面扩散。     

熔体快淬对纳米晶和非晶Mg20Ni10-xCox(x≈0～4)合金电化学贮氢性能的影响

为了改善Mg2Ni型合金的电化学贮氢性能,用Co部分替代合金中的Ni.用快淬工艺制备了纳米晶和非晶Mg20Ni10-xCox(x=0、1、2、3、4)贮氢合金,分析了铸态及快淬态合金的微观结构,测试了合金的电化学贮氢性能.研究了Co替代Ni及快淬工艺对合金电化学贮氢性能的影响.结果表明,Co替代Ni不改变合金的Mg2Ni主相,但形成了第二相MgCo2.在快淬(x=0)合金中没有发现非晶相,但快淬(x=4)合金显示了纳米晶、非晶结构,表明Co替代Ni提高了Mg2Ni型舍金的非晶形成能力.熔体快淬显著的改善了合金的电化学贮氢性能,合金放电容量和电化学循环稳定性均随淬速的增加而增加.     

氢在不同成分和显微组织的Mg-Ni合金电极中的扩散能力研究

采用机械球磨的方法,制备了不同成分和显微组织的MgxNi(x=1%、1.5%、2%(原子分数))合金粉,并采用X射线衍射(XRD)和扫描电子显微镜的方法研究了Mg/Ni比对机械球磨过程中Mg-Ni合金粉末组织结构演变的影响。在不同的电位扫描速度下,对具有不同Mg/Ni比和显微组织结构的Mg-Ni合金电极循环伏安曲线进行了测量,并由此计算出了氢在这些电极中的扩散系数,分析了合金成分和显微组织对Mg-Ni合金电极中氢扩散能力的影响。其结果表明,降低Mg/Ni比,能提高Mg-Ni合金在球磨过程中非晶相的形成能力,Mg-Ni和Mg1.5Ni合金获得完全非晶相的球磨时间分别是120和160h。在由细小、分散并且完全非晶态的Mg-Ni合金颗粒制备的电极中,氢表现出较强的扩散能力,其扩散系数为1.98×10-8cm2/s。     

Crystallization Study of Cu_(56)Zr_7Ti_(37) Metallic Glass by Electrical Resistivity Measurement

In this paper,the crystallization behaviour of amorphous Cu56Zr7Ti37 alloy using thermal electrical resistivity(TER) and differential scanning calorimetry(DSC) studies has been described.Isochronal TER and DSC measurements indicate that crystallization occurs in two stages.Isothermal crystallization studies of the alloy by TER show that the kinetics conforms to Johnson-Mehl-Avrami model.Avrami exponents derived from kinetics,between 1.1 and 1.2,imply that the crystallization processes are diffusion controlled with near zero nucleation.Activation energy has been found to increase with the transformed volume fraction.A plausible explanation has been presented by separating the contributions due to nucleation and crystal growth towards total activation energy.     

Surface modification of AB(2) and AB(5) hydrogen storage alloy electrodes by the hot-charging treatment

The effect of the hot-charging treatment on the performance ofAB2 and AB5 hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (VPR), the high rate discharge ability (HRDA), the diffusion coefficient of hydrogen DH and the discharge capacity of the AB2 hydrogen storage alloy electrode. The SEM analysis showed that the hot-charging treatment brings about a Ni-rich surface due to the dissolution of Zr oxides. It is also very helpful for the improvement of the kinetic properties of AB2 hydrogen storage alloy electrode because the microcracking o.f the surface results in fresh surface. This can be the basic modification treatment for NiMH battery used in electric vehicles (EVs) in the future. But for AB5 type alloys, the treatment has the disadvantage of impairing the comprehensive electrochemical properties, because the surface of the alloy may be corroded during the treatment. The mechanism of the surface modification of the electrode is also proposed.     

非晶软磁合金Co_(65)Fe_4Ni_2Si_(15)B_(14)的纳米晶化动力学研究

采用差示扫描量热分析(DSC)和X射线衍射技术(XRD)研究了非晶态合金Co_(65)Fe_4Ni_2Si_(15)B_(14)的非等温晶化动力学.结果表明,初始晶化的晶化峰值温度T_p与升温速率β呈线性关系:T_p=11.49lnβ+795.43.采用Kissinger和Doyle-Ozawa方法计算了表观晶化激活能E_a,分别为471.68kJ/mol和461.50kJ/mol.进一步研究发现,该非晶合金的晶化为多阶段的连续形核直至饱和的过程;当进入稳定晶化阶段时,剩余非晶的局域晶化激活能逐渐下降,非晶基体的热稳定性降低,这是由B原子的高温扩散导致的.同时,局域Avrami指数n(α)也反映了不同晶化阶段的形核长大机制.     

Stoichiometric NbTiAl_3 (γ1 Phase) Alloy in Ti-Al-Nb Ternary System

The microstructure and phase constitution in stoichiometric NbTiAl3 (γ1 phase) alloy treated at 1000℃ were examined by metallography and X-ray diffraction. The alloy microstructure is mainly γ1 phase containing η second phase [(Ti,Nb)Al3] less than 1%. DTA analysis shows no phase transformation from room temperature to 1200℃. In the diffusion couple of NbTiAl3 with 7-TiAl compound, clear phase boundary and composition jump exist between γ1 and γ phase.These results further confirm the existence of γ1 single phase at 1000℃ in Ti-Al-Nb ternary system.     

Hydrogen transport in metals: Integration of permeation,thermal desorption and degassing

A modelling suite for hydrogen transport during electrochemical permeation, degassing and thermal desorption spectroscopy is presented. The approach is based on Fick's diffusion laws, where the initial concentration and diffusion coefficients depend on microstructure and charging conditions. The evolution equations are shown to reduce to classical models for hydrogen diffusion and thermal desorption spectroscopy. The number density of trapping sites is found to be proportional to the mean spacing of each microstructural feature, including dislocations, grain boundaries and various precipitates. The model is validated with several steel grades and polycrystalline nickel for a wide range of processing conditions and microstructures. A systematic study of the factors affecting hydrogen mobility in martensitic steels showed that dislocations control the effective diffusion coefficient of hydrogen. However,they also release hydrogen into the lattice more rapidly than other kind of traps. It is suggested that these effects contribute to the increased susceptibility to hydrogen embrittlement in martensitic and other high-strength steels. These results show that the methodology can be employed as a tool for alloy and process design, and that dislocation kinematics play a crucial role in such design.     

Diffusion bonding of TiAl based alloy to Ti–6Al–4V alloy using amorphous interlayer

Powder metallurgical TiAl based alloy and Ti–6Al–4V (TC4) alloy were diffusion bonded at 915 °C for 1 h under a pressure of 80 MPa. Single Ti‐based amorphous or Ni‐based amorphous foil was utilized as an interlayer during diffusion bonding process. The tensile mechanical properties of the diffusion bonded joints between TiAl based alloy and TC4 alloy were tested. The fracture surface and microstructure characteristic of these joints were also observed carefully by scanning electron microscope. The TiAl based alloy with a fully lamellar microstructure is more suitable for diffusion bonding to TC4 alloy. Adding a Ti‐based amorphous interlayer is more conducive to the element diffusion, giving rise to the improvement in the mechanical properties of the diffusion bonded joints. Results also show that the diffusion bonded joints form a metallurgical bond and fracture in a brittle manner.