Oxidation of Ag–Sn–La Alloy Powders

The gas atomized Ag-9.26wt%Sn-0.44wt%La alloy powders were oxidized in air between 400 and 900 °C. The oxidation thermodynamics, kinetics and microstructure of the alloy were investigated. We suggested that the addition of La may accelerate oxidation of Sn and prevent the formation of the dense SnO₂ film. The suitable oxidation temperature of the alloy powders is 800 °C in air. After internal oxidation, many cracks were observed on the surface of the alloy powders. In addition, the whole oxidation process of the alloy powders is controlled by the oxygen diffusion. The diffusion coefficient of oxygen in the alloy powders at 800 °C is about 1.5 times larger than that at 700 °C on the initial stage of internal oxidation, while that is 4.5 times on the subsequent stage.     

Abnormal electric transport property and magnetoresistance stability of La–Sr–K–Mn–O system

The perovskite samples La1-x (Sr1-yKy )xMnO3 (y = 0.0, 0.2, 04, 0.6, 0.8) were prepared by the solid-state reaction method with comparatively low sintering temperature and with comparatively short sintering time, and the electric transport property and temperature stability of MR of this system were studied. The q-T curves show the abnormal phenomenon that with the increase of K doping amount, resistivity increases, and the insulator-metal transition temperature decreases, which is because the influence of the occupation disorder degree of A-site ions σ2 on the electric transport property of perovskite manganites is larger than that of the radius of A-site ions. In the temperature range below 225 K, MR increases continuously with the decrease of temperature, which is the characteristic of low-field magnetoresistance; in the comparatively wide temperature range near 250 K, the MR-T curves of all the samples are comparatively flat, and the value of MR almost does not change with temperature, which shows the temperature stability of magnetoresistance, and can be explained by the competition between the low-field magnetoresistance induced by spin-dependent tunneling of surface phase and the intrinsic magnetoresistance of grain phase. The magnetoresistance value of the sample with y = 0.8 keeps at (7.92 ± 0.36) % in the very wide temperature range of 225-275 K, and this is a good reference for the preparation of this kind of sample with practical application value in the future.     

Phase structure and electrochemical performances of Co-free La–Mg–Ni-based alloys with Nd/Sm partial substitution for La

In this paper, the Co-free hydrogen storage alloys with the nominal compositions of La0.75R0.05Mg0.20Ni3.40Al0.10(R = La, Nd and Sm) were prepared by induction melting, and then the phase structure and electrochemical properties of these alloys were comparatively investigated. It is found that the alloys mainly consist of(La, Mg)2Ni7phase, La Ni5 phase and(La, Mg)5Ni19phase.Refinement results further show that Nd substitution for La remarkably promotes the formation of La Ni5 phase, while Sm is beneficial for the formation of(La, Mg)5Ni19phase.At discharge current density of 1,875 m A g-1, the highrate dischargeability(HRD) of alloy electrodes increases by 13.9 % and 6.5 % with La substituted by Nd and Sm,respectively. The electrochemical kinetic measurements reveal that the exchange current density(I0), charge transfer resistance(R) and hydrogen diffusion coefficient(D) for the alloy electrode are all facilitated with Nd and Sm partial substitution for La. Subsequently, a linear correlation between the HRD1875 and the corresponding I0/D is found.     

Pressure effect on crystallization kinetics of an Al–La–Ni amorphous alloy

The pressure effect on the crystallization kinetics of an amorphous Al₈₉La₆Ni₅ alloy has been investigated by means of piston–cylinder measurements within a pressure range of 0–1.0 GPa. It was found that an applied pressure enhances the first primary crystallization, i.e. the precipitation of f.c.c.-Al from the amorphous phase. The crystallization temperature decreases from 495 to 440 K when the applied pressure increases from ambient to 0.9 GPa. Meanwhile, the thermal stability of the residual amorphous phase with the Al dispersion is elevated at higher pressures. The crystallization temperature of the residual amorphous phase increases by 35 K/GPa when the pressure increases. The observed pressure effect on the crystallization kinetics in the amorphous alloy, which cannot be interpreted by means of the pressure effect on atomic diffusion, may be well understood in terms of the volume change effect at the early stage of crystallization.     

Electrochemical formation of La–Al intermetallic compounds in fluoride melts

The electrochemical formation of La-Al alloys in LiF-CaF₂ molten salt on a molybdenum electrode at 1123 K was investigated by electrochemical techniques,such as cyclic voltammetry,square-wave voltammetry and open-circuit chronopotentiometry.The formation signals of four types of Al-La intermetallic compounds were observed.The Al-La alloy was obtained through galvanostatic electrolysis at 2.5 A·cm^-2 for 3 h.The phase composition and microstructure of the electrolytic product...     

Reaction mechanism of lanthanum nitrate-doped Mo–La material during solid–liquid spray doping processing

At three critical temperatures which were obtained by thermo-gravimetry-differential thermal analysis–differential scanning calorimetry(TG/DTG/DSC)curves of lanthanum nitrate crystal, the air thermal decomposition experiments and solid–liquid spray doping simulation procedures of lanthanum nitrate crystal were carried out, and their products were analyzed by X-ray diffraction(XRD). Meanwhile, the spray doping processing of Mo O_2–50 wt% La(NO_3)_3composite powder was undergone with lanthanum nitrate solution as the dopant,and doped Mo O_2 powder was analyzed by XRD. The results demonstrate that during the traditional solid–liquid spray doping processing, lanthanum nitrate, in the form of either crystal or aqueous solution, would be converted into La(NO_3)_3á_4H_2O by the dehydration reaction, rather than be decomposed to La_2O_3 and NO or NO_2. Therefore, it is inferred that the oxynitride gas produced from the process is attributed to the decomposition of residual HNO_3 in lanthanum nitrate crystal. The source of HNO_3 is supported by the chemical composition of lanthanum nitrate crystal.     

Glass formation in La-based La–Al–Ni–Cu–(Co) alloys by Bridgman solidification and their glass forming ability

Six La-based La–Al–Ni–Cu–(Co) alloys were subjected to a systematical study of glass formation by Bridgman unidirectional solidification at growth velocities between 0.1 and 4.82 mm/s at a temperature gradient of 15 K/mm. With increased Cu content the critical growth velocity for glass formation in La₅₅Al₂₅Cu_20−xNi_x (x=0–20) alloys shows a steep minimum at 10 at.% Cu, indicating the largest glass forming ability for the La₅₅Al₂₅Ni₁₀Cu₁₀ alloy. However, replacement of Ni by Co leads to a further decrease in the critical cooling rate for the La₅₅Al₂₅Ni₅Cu₁₀Co₅ alloy. Critical cooling rates for glass formation in the present alloys were also obtained through a study of their melting and solidification behaviours by thermal analytical measurement. The effect of alloying addition and the significance of reduced glass transition temperature for the glass forming ability of these alloys is discussed.     

The electrochemical hydrogen storage performances of Si-added La–Mg–Ni–Co-based A_2B_7-type electrode alloys

In order to improve the electrochemical cycle stability of the RE–Mg–Ni-based A2B7-type electrode alloys, a small amount of Si has been added into the alloys.The casting and annealing technologies were adopted to fabricate the La0.8Mg0.2Ni3.3Co0.2Six(x = 0–0.2) electrode alloys. The impacts of the addition of Si and annealing treatment on the structures and electrochemical performances of the alloys were investigated systematically. The results obtained by XRD and SEM show that all the as-cast and annealed alloys are of a multiphase structure, involving two main phases(La, Mg)2Ni7and La Ni5 as well as a residual phase La Ni3. Both adding Si and the annealing treatment lead to an evident change in the phase abundance and cell parameters of(La, Mg)2Ni7and La Ni5 major phases of the alloy without altering its main phase component. Moreover, the annealing treatment has the composition of the alloy distributed more homogeneously overall and simultaneously causes the grain of the alloy to be coarsened obviously. The electrochemical measurements indicate that adding Si and the annealing treatment give a significant rise to the influence on the electrochemical performances of the alloys. In brief, the cycle stability of the as-cast and annealed alloys evidently increases with the rising of Si content, while their discharge capacities obviously decrease under the same circumstances. Furthermore, the electrochemical kineticproperties of the electrode alloys, including the high rate discharge ability, the limiting current density(IL), hydrogen diffusion coefficient(D), and the charge-transfer resistance, first augment and then decline with the rising of Si content. Similarly, it is found that the above-mentioned electrochemical properties first mount up and then go down with the rising annealing temperature.     

Evolution of Microstructure,Residual Stress,and Tensile Properties of Mg–Zn–Y–La–Zr Magnesium Alloy Processed by Extrusion

The microstructure, texture, residual stress, and tensile properties of Mg–6 Zn–2 Y–1 La–0.5 Zr(wt%) magnesium alloy were investigated before and after extrusion process, which performed at 300 °C and 400 °C. The microstructural characterizations indicated that the as-cast alloy was comprised of α-Mg, Mg–Zn, Mg–Zn–La, and Mg–Zn–Y phases. During homogenization at 400 °C for 24 h, most of the secondary phases exhibited partial dissolution. Extrusion process led to a remarkable grain refi nement due to dynamic recrystallization(DRX). The degree of DRX and the DRXed grain size increased with increasing extrusion temperature. The homogenized alloy did not show a preferential crystallographic orientation, whereas the extruded alloys showed strong basal texture. The extrusion process led to a signifi cant improvement on the compressive residual stress and mechanical properties. The alloy extruded at 300 °C exhibited the highest basal texture intensity, the compressive residual stress and hardness, and yield and tensile strengths among the studied alloys.     

含La球化剂和含La孕育剂

由于混合稀土硅铁合金的价格远低于单一稀土,国内球铁生产迄今所用REMgSiFe球化剂都是采用混合稀土硅铁合金熔炼,然而研究发现,用单一稀土金属La代替混合稀上,可显著降低白口倾向,增加石墨球数,提高球化等级,消除铸件缩孔、缩松缺陷,获得质量优异的球铁铸件.因此,在铸造生产领域有针对性地开拓单一RE的应用,将是一件十分有意义的工作.     

Optimum glass formation at off-eutectic composition and its relation to skewed eutectic coupled zone in the La based La–Al–(Cu,Ni) pseudo ternary system

Glass formation and its relation to the dendritic and eutectic growth has been investigated for the La_100−x[Al_0.412(Cu,Ni)_0.588]_x (x=30–56.3) and La_86−yAl₁₄(Cu,Ni)_y (y=16–29) alloy systems. The experimental results show that in the La-rich pseudo ternary La–Al–(Cu,Ni) system, optimum glass formation actually occurs at an off-eutectic composition. A nearly fully amorphous rod with 12 mm in diameter can be obtained at an off-eutectic composition near La₆₂Al_15.7(Cu,Ni)_22.3, while only a 1.5 mm diameter rod can be obtained fully amorphous for the eutectic alloy La₆₆Al₁₄(Cu,Ni)₂₀. A strong dependence of GFA on the composition is observed for these alloys. In addition, formation of a composite (i.e. αLa dendrite reinforced glass matrix) in 12 mm diameter cast rods is observed over a wide range of composition, including the eutectic composition. It has been found that the GFA does not correlate well with the extent of the undercooled liquid region (ΔT_x) and is not even closely related to the reduced glass transition temperature (T_rg). These unusual observations in glass formation and its relation to the skewed eutectic coupled zone have been explained in terms of the competition between the growth of crystalline phases (i.e. eutectic and dendritic phases) and the formation of the amorphous phase.     

Degradation behaviors of La–Mg–Ni-based metal hydride alloys:structural stability and influence on hydrogen storage performances

The present work focuses on the structural stability upon hydrogenation of three typical La–Mg–Ni-based alloys:La_(2-)Mg Ni_9,La_3Mg Ni_(14)and La_4Mg Ni_(19).Structural changes during gaseous and electrochemical cycles were characterized,and the influence of the structure distortion on the hydrogen storage properties was concerned.Hydrogen-induced amorphization(HIA)and disproportionation of the three alloys have occurred during both the gaseous and electrochemical cycles.Structural stability of the phase structures in the La–Mg–Ni system is found to follow the order:La Ni_(5-)[(La,Mg)_5Ni_(19)[(La,Mg)_2Ni_7[(La,Mg)Ni_3[(La,Mg)Ni_2.HIA increases thermal stability of the metal hydrides and difficulty to dehydrogenation and leads to degradation of both the gaseous and electrochemical capacities.Interestingly,La_2Mg Ni_9with poor stability presents elevated discharge capability even at 60°C which can be attributed to increase in the hydrogen desorption capability and inhibition of the self-discharge induced by severe HIA at higher temperatures.In addition,HIA in the electrochemical reactions is obviously weaker than the extent during the gaseous cycles,which is mainly due to the slower hydrogenation speed.The development of HIA in the gaseous and electrochemical process is considered to follow the direct and gradual modes,respectively.     

Hydrogen storage behavior of nanocrystalline and amorphous La–Mg–Ni-based LaMg12-type alloys synthesized by mechanical milling

Nanocrystalline and amorphous LaMg₁₁Ni+x% Ni (x=100, 200, mass fraction) alloys were synthesized by mechanical milling. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. The gaseous hydrogen absorption and desorption properties were investigated by Sievert's apparatus and differential scanning calorimeter (DSC) connected with a H₂ detector. The results indicated that increasing Ni content significantly improves the gaseous and electrochemical hydrogen storage performances of the as-milled alloys. The gaseous hydrogen absorption capacities and absorption rates of the as-milled alloys have the maximum values with the variation of the milling time. But the hydrogen desorption kinetics of the alloys always increases with the extending of milling time. In addition, the electrochemical discharge capacity and high rate discharge (HRD) ability of the as-milled alloys both increase first and then decrease with milling time prolonging.     

Al−La

Tear-out PagesAlloy Phase Diagrams

Al−La     

Effects of La substitution on microstructure and hydrogen storage properties of Ti–Fe–Mn-based alloy prepared through melt spinning

The as-spun Ti_1–xLa_xFe_0.8Mn_0.2 (x=0, 0.01, 0.03, 0.06, 0.09, molar fraction) alloys were prepared by melt spinning. The effects of La substitution for Ti on the microstructure, hydrogen storage kinetics and thermodynamics of TiFe-type Ti–Fe–Mn-based alloy were investigated. The as-spun alloys hold the TiFe single phase, which transforms to TiFeH_0.06, TiFeH, and TiFeH₂ hydrides after hydrogenation. La substitution promotes the formation of micro-defects (such as dislocations and grain boundaries) in the alloys, thus facilitating hydrogen diffusion. In addition, the hydrogen storage kinetics properties are improved after introducing La element. With the rise of La content, the hydrogen storage capacity decreases firstly and then increases, but the absolute value of hydriding enthalpy change (|ΔH|) increases firstly and then reduces. When x=0.01, the maximum value of |ΔH| is obtained to be (25.23±0.50) kJ/mol for hydriding, and the alloy has the maximum hydrogen absorption capacity of (1.80±0.04) wt.% under the conditions of 323 K and 3 MPa.     

Oxidation of La–Sr–Mn-Coated Interconnector Alloys for Steam Electrolysis Under Pressure in Pure Oxygen and in Pure Steam

Pressurized steam electrolysis enables an efficient conversion of electric power from renewable energy sources into hydrogen for power-to-liquids processes. The interconnector material Crofer 22 APU, uncoated and coated by La_1?x Sr _x MnO₃ (LSM), deposited by thermal spray and by roll coating was studied in pure water vapor and pure oxygen at 850 °C and 30 bar. The uncoated Crofer 22 APU forms in both atmospheres a homogeneous oxide scale from an inner Cr₂O₃ and an outer MnCr₂O₄ layer. The chromia is locally undergrown by pits of MnCr₂O₄. With the LSM coating, the oxide scale is notably thinner in water vapor and the formation of pits is significantly reduced. In oxygen, this effect of the LSM coating is less pronounced. Chromium from volatile species was detected in the LSM coating, more in oxygen than in water vapor. After 3000 h in pure oxygen, Crofer 22 APU with thermally sprayed LSM shows breakaway oxidation.     

Preparation of Al–La master alloy by ultrasonic method and modification on Al alloy

In this study, two kinds of Al–La master alloys were prepared by ultrasonic method and ordinary mixmelting method, and both of the alloys were added into the Al alloy.Then, the microstructure of Al–La master alloy and the modification effect on the Al alloy were investigated using optical microscope(OM), X-ray diffraction(XRD), scanning electron microscope(SEM), and energy disperse spectroscopy(EDS).The results show that because of ultrasonic cavitation and streaming, the grain size of Al–La master alloy prepared by the ultrasonic method is refined, which distributes evenly.And, there is no gas hole,inclusion, or segregation in the Al–La master alloy with aAl, La, and La3Al11.Furthermore, Al–La master alloys show a nice modification for Al alloy, which is much better than that prepared by ordinary mix-melting method.     

Effect of La and Hf Additions on the High-Temperature Oxidation Resistance of High-Purity Fe–20Cr–5Al Alloy Foils

The oxidation behavior of 30- or 50-m thick high-purityFe–20 w/o-Cr–5 w/o Al alloy foil and similar alloy foilscontaining La and La–Hf was examined in cyclic-oxidation tests at1373 and 1473 K in air. The oxidation process proceeded in three stages. Inthe first stage, an Al₂O₃ scale grew until all the Alin the foil had been removed. In the second stage, a Cr₂O₃layer grew between the Al₂O₃ layer and the substrateon the alloys containing La or La–Hf, while a (Cr, Al)₂O₃layer formed on the alloy without La and La–Hf. In the third stage,breakaway oxidation occurred. The addition of La decreased the oxidationrate in both the first and the second stages. The addition of La–Hfdecreased the rate further. The growth rate of alloys containing La orLa–Hf in the second stage was found to be proportional to thediffusion rate of oxygen in the Al₂O₃ scale. Therefore,it is inferred that the inward oxygen diffusion rate in the Al₂O₃scale on the alloy containing La–Hf was reduced compared with that onthe alloy containing La, resulting in a decrease in the oxidation rate inthe first stage.     

化学计量比La/Mg对铸态及退火态La–Mg–Ni系A_2B_7型电极合金结构及电化学性能的影响（英文）

采用合金熔炼及退火处理的方法制备La-Mg-Ni系A2B7型La0.8+xMg0.2–xNi3.5(x=0-0.05)电极合金,并研究不同的化学计量比La/Mg对该合金的相结构和电化学性能的影响。通过X射线衍射(XRD)和扫描电子显微镜(SEM)对合金进行表征。结果表明:合金包含(La,Mg)2Ni7和La Ni5两个主相以及一些残余相La Ni3。随着La/Mg比率的增大,合金中的(La,Mg)2Ni7相含量降低,而La Ni5和La Ni3相的含量升高。La/Mg比的变化也使得合金电极的电化学性能发生显著变化。随着La/Mg比率的增加,铸态及退火态合金的放电容量降低,而循环稳定性明显改善。此外,合金电极的高倍率放电性能(HRD)、电化学阻抗谱(EIS)、Tafel极化曲线以及电势阶跃的测量均表明La/Mg比率的增加提高了合金的电化学动力学性能。