含钪、铒的Al-0.8%Mg-0.6%Si合金的低周疲劳行为

对固溶+人工时效(T6)处理的挤压变形Al-0.8%Mg-0.6%Si,Al-0.8%Mg-0.6%Si-0.2%Sc和Al-0.8%Mg-0.6%Si-0.3%Er合金进行了低周疲劳试验,探讨了合金的低周疲劳变形和断裂行为.结果表明,低周疲劳变形期间,含Sc,Er合金可以呈现循环应变硬化、循环应变软化和循环稳定;添加稀土元素Sc可提高合金的循环变形抗力,且含0.2%Sc的合金在疲劳变形期间发生双系滑移;含Sc,Er合金的弹性应变幅和塑性应变幅与断裂时的载荷反向周次的关系可分别用Basquin和Coffin-Manson公式来描述,其中Al-0.8%Mg-0.6%Si-0.2%Sc合金的塑性应变幅与断裂时的载荷反向周次之间呈双线性关系;含Sc,Er合金的疲劳裂纹均是以穿晶方式萌生于试样表面,并以穿晶方式扩展.     

LiCl-KCl熔盐体系中镨(Ⅲ)在镍电极上的电化学行为

采用循环伏安、 方波伏安、 计时电位和开路计时电位等电化学方法研究了Pr(Ⅲ)离子在共晶LiCl-KCl熔盐中Ni电极上的电化学行为及Pr-Ni合金化机理. 结果表明, Pr(Ⅲ)离子的电化学还原过程为三电子转移的一步反应. 与惰性Mo电极上的循环伏安曲线相比, Pr(Ⅲ) 离子在活性Ni电极的循环伏安曲线上还出现了4对氧化还原峰, 表明Pr(Ⅲ)离子在Ni电极上发生欠电位沉积, 是由于生成不同的Pr-Ni金属间化合物. 采用X射线衍射仪和扫描电子显微镜-能谱仪等对恒电位电解的产物进行了表征. 结果表明, 在不同电位下进行恒电位电解时, 每个电位上只得到一种Pr-Ni金属间化合物, 分别为PrNi₂, PrNi₃, Pr₂Ni₇和PrNi₅.     

Co-diffusion with a slow species in zeolites: cyclic experimentation and advanced modeling

In this study, a new experimental method based on cyclic breakthrough curves is presented, in order to estimate the co-diffusion coefficients for mixtures at high adsorption loadings. For this purpose, cyclic liquid phase breakthrough curves of mixtures of 2-methylpentane 3-methylpentane (fast-diffusing species) and 2,2-dimethylbutane (slow-diffusing species) have been measured experimentally for different feed compositions at 185°C. Estimation of Langmuir coefficients and self-diffusivities was attempted from simple binary breakthrough curves with the above components using a modified Maxwell-Stefan-type model. However, for the slow-diffusing species, the parameters cannot be estimated accurately from such experiments, because the quantity of 22DMB entering the zeolite network in the experiment duration is not sufficient. On the other hand, a clear influence of the slow diffusing species (22DMB) on the fast diffusing species (3MP) breakthrough curves during cycles has been demonstrated. This phenomenon confirms that 22DMB slowly accumulates in the adsorbent during the cycles, and that is becomes therefore possible to estimate the 22DMB parameters from the cyclic data.     

Dy(Ⅲ)离子在LiCl-KCl熔盐中的电化学行为及Dy-Ni金属间化合物的选择性制备

采用循环伏安、方波伏安和开路计时电位等电化学方法研究了Dy(Ⅲ)离子在LiCl-KCl 共晶盐中的电化学行为及Dy-Ni 合金形成的电化学机理. 循环伏安和方波伏安法研究表明, Dy(Ⅲ)离子的电化学还原过程为三个电子转移的一步反应. 与惰性W电极相比, Dy(Ⅲ) 离子在Ni 电极上的循环伏安曲线多出了三对氧化还原峰,是由于Dy与Ni 形成了合金化合物, 导致Dy(Ⅲ)离子在活性Ni 电极发生了欠电位沉积. 采用X射线衍射(XRD)和扫描电子显微镜(SEM)附带能量散射谱(EDS)对恒电位(-1.6, -1.8 和-2.0 V)电解制备的Dy-Ni 合金进行分析, 分别获得了DyNi₅, Dy₂Ni₇和DyNi₂金属间化合物. 实验结果表明, 通过控制电位进行恒电位电解可以有选择性地制备不同的金属间化合物.     

Electrosorption of hydrogen into palladium-gold alloys

Hydrogen electrosorption into Pd-Au alloys has been studied in acidic solutions (1 M H₂SO₄) using cyclic voltammetry. Pd-Au electrodes with limited volume were prepared by electrochemical co-deposition. It was found that the maximum H/(Pd+Au) ratios decrease monotonically with increasing gold content and reach zero at ca. 70 at% Au. Similarly to the case of Pd limited volume electrodes, two peaks in the hydrogen region, corresponding to two types of sorbed hydrogen, are observed on voltammograms for Pd-rich alloys. The hydrogen capacity, H/(Pd+Au), measured electrochemically, depends on the sweep rate in the cyclic voltammetry experiments, which suggests that two different mechanisms for hydrogen desorption from the Pd-Au alloy are possible. After a strong decrease of Pd concentration at the electrode surface, caused by long cyclic polarization to sufficiently anodic potentials, the amount of absorbed hydrogen is still significant for alloys initially rich in Pd. The results obtained from CO adsorption experiments suggest that only Pd atoms are active in the hydrogen absorption/desorption process. Electronic Publication     

表面修饰纳米TiO2的贮氢合金电极的光充电行为

Nanocrystalline anatase-type TiO2 was prepared by the hydrolysis-precipitaiton method, the rare earth hydrogen storage alloys were modified with the as-prepared TiO2 and the photocharging behavior, and cyclic voltammetry curves and EIS spectra were measured. The experimental results show that the potential has little shift under the light irradiation for the unmodified electrode. However, for the TiO2 modified electrode, a remarkable shift of the potential to negative direction (up to -0.835 V) takes place under the light irradiation, which means the generation of H atom on the electrode surface under the light irradiation. The EIS results also indicate that there exists the absorption of H atom and the following diffusion of H atom into the hydrogen storage alloys under the light irradiation. The FEM observations on the electrode surface show that a large amount of microcracks appear on the electrode surface. These microcracks may be induced by the bulk expansion when the generated hydrogen atoms were absorbed by the hydrogen storage alloys.     

Pr(Ⅲ)离子在LiCl-KCl熔体中Bi膜W电极上的电化学行为

采用循环伏安、方波伏安、计时电位和开路计时电位等电化学方法研究了Pr（Ⅲ）离子在LiCl-KCl-BiCl₃熔体中W电极上的电化学行为。循环伏安和方波伏安的研究表明,Pr在预先沉积的Bi膜电极上发生欠电位沉积是由于生成了Pr-Bi金属间化合物,导致Pr（Ⅲ）在Bi膜电极上的还原电位比在W电极上还原电位更正。从开路计时电位曲线可以观察到两相共存的Pr-Bi金属间化合物的两个平台。利用开路计时电位计算了723-873 K温度范围内Pr在Pr-Bi合金中的活度和偏摩尔Gibbs自由能以及Pr-Bi金属间化合物的生成Gibbs自由能。通过恒电位电解,在液态Bi电极上得到了Pr-Bi合金,并采用X射线衍射（XRD）和扫描电子显微镜（SEM）附带能量散射谱（EDS）对样品进行了表征,结果表明所得到的Pr-Bi金属间化合物为PrBi₂和PrBi。     

Shrinking-core modeling of binary chromatographic breakthrough

Most chromatographic processes involve separation of two or more species, so development of a simple, accurate multicomponent chromatographic model can be valuable for improving process efficiency and yield. We consider the case of breakthrough chromatography, which has been considered in great depth for single-component modeling but to a much more limited degree for multicomponent breakthrough. We use the shrinking core model, which provides a reasonable approximation of particle uptake for proteins under strong binding conditions. Analytical column solutions for single-component systems are extended here to predict binary breakthrough chromatographic behavior for conditions under which the external transport resistance is negligible. Analytical results for the location and profile of displacement effects and expected breakthrough curves are derived for limiting cases. More generally, straightforward numerical results have also been obtained through simultaneous solution of a set of simple ordinary differential equations. Exploration of the model parameter space yields results consistent with theoretical expectations. Additionally, both analytical and numerical predictions compare favorably with experimental column breakthrough data for lysozyme-cytochrome c mixtures on the strong cation exchanger SP Sepharose FF. Especially significant is the ability of the model to predict experimentally observed displacement profiles of the more weakly adsorbed species (in this case cytochrome c). The ability to model displacement behavior using simple analytical and numerical techniques is a significant improvement over current methods.     

Salient features of the electrical double layer structure on mechanically renewed gold-silver electrodes in aqueous solutions of a surface-inactive electrolyte

The behavior of electrodes, which are made of binary Au-Ag alloys (Ag content 1–15 at %) and renewed by mechanical cutting in aqueous solutions of sodium fluoride, is studied with the aid of cyclic voltammetry and impedance methods. It is established that, in the region of potentials corresponding to ideal polarizability, the differential capacitance of the electrical double layer rapidly changes with time elapsed after the renewal of the surface of the electrodes. The change in the capacitance is brought about by the exit of silver atoms into a surface layer. The implication is that silver is the surface-active component in these alloys. The rate of the surface segregation of silver atoms depends on the electrode potential. The segregation rate substantially increases upon going into the region that corresponds to positive charges of the silver electrode surface and to the beginning of adsorption of atomic oxygen on the electrode. Based on phenomenological models, a method for processing capacitance curves is realized, which links experimentally observed time effects to variations that occur in the surface composition, and assumptions concerning the mechanism of relaxation processes that are responsible for the observed time effects are put forth. Explicit data on the effect, which is exerted by mechanical renewal on the composition of the surface layer of Au-Ag alloys at different distances from the interface with a vacuum, are obtained with the aid of an x-ray photoelectron spectroscopy method. It is established that the surface layer (～0.5 nm) is enriched by silver atoms as compared with the alloy’s bulk.     

热处理对La4MgNi19储氢电极合金结构和性能的影响

以感应熔炼和不同的热处理工艺制备了La₄MgNi₁₉合金, 用X射线衍射(XRD)和电化学测试系统研究了该合金的相结构和电化学性能. 结构分析表明: 当热处理工艺为900 °C+水淬时, 合金主要由CaCu₅结构的LaNi₅相和少量未知相组成; 当热处理工艺为900 °C退火时, 合金主要由Pr₅Co₁₉、Ce₅Co₉结构的(La, Mg)₅Ni₁₉相及少量CaCu₅结构的LaNi₅相组成. 淬火和退火后合金的电化学循环稳定性(S₁₀₀)分别为49.7%及76.0%, 合金电极的电化学性能和相结构密切相关. 退火热处理有利于生成Pr₅Co₁₉、Ce₅Co₉型相. 在La-Mg-Ni 系储氢合金中, La₄MgNi₁₉合金电化学循环稳定性不及La₃MgNi₁₄合金.     

铝电极在LiNO3-KNO3熔盐中的电化学行为

采用循环伏安和恒电位电解法考察了铝电极在LiNO3-KNO3熔盐中的电化学行为. 实验结果表明, 在该熔盐中, 锂离子在铝电极上的电还原过程伴随着新生态的锂原子向电极内部的随后扩散步骤; 锂原子进入铝电极后与铝发生合金化, 形成β-LiAl合金和γ-LiAl合金; 锂离子在铝电极上的还原过程受还原态锂在铝基体内的扩散步骤控制. 循环伏安实验发现, 铝电极在该熔盐中的氧化和还原峰电流都先随循环次数增加而增大, 最后基本上趋于稳定. 这表明铝电极在该熔盐体系中具有较好的电化学稳定性.     

体外电化学测试对镁合金体内降解行为的预测

可生物降解镁合金因同时具有优良的生物相容性和力学性能,在生物医学界显示出其作为新型骨科内植入物的巨大潜在优势和市场前景。目前,作为制约镁合金医用产业化的关键因素,即过快的降解速率已经成为研究重点。本文回顾了体外电化学测试技术对镁合金抗腐蚀性能的研究,并分析了模拟腐蚀体系对镁合金腐蚀行为的影响;同时评估了电化学测试方法作为快速有效预测镁合金体内降解性能前期分析手段的可行性与局限性。最后,对如何发展更合理的体外电化学测试技术来预测镁合金体内降解提出了可能的解决方法及构思。     

Cyclic voltammetric behavior of Pd–Pt–Rh ternary alloys

The electrochemical behavior of Pd–Pt–Rh alloys has been investigated using cyclic voltammetry (CV). The alloys were prepared by electrochemical codeposition as limited volume electrodes (less than 1 m in thickness). The morphology of the alloy surface and bulk compositions were examined by the SEM/EDAX method. Surface oxides generation (oxygen adsorption) and oxides reduction (oxygen desorption) currents together with hydrogen adsorption and hydrogen absorption signals can be distinguished on CV curves. During potential cycling through the full hydrogen–oxygen potential range Rh and Pd are preferentially dissolved, which is reflected in a dramatic transformation in the voltammogram shape. The composition changes involve not only the surface but also some atomic layers beneath the surface.     

缺陷对混合稀土贮氢合金性能的影响

贮氢合金是一种重要的功能材料。在多种贮氢合金中,AB~5型稀土系贮氢合金的应用最为广泛。本文用正电子湮没技术(PAT)对AB~5型混合稀土贮氢合金的缺陷进行了研究,并结合X射线衍射(XRD)测试、循环伏安(CV)测试以及合金容量的测定,对合金的结构及性能进行了研究。结果表明,合金微观缺陷的存在能大幅度提高金的性能。     

Protein adsorption and transport in dextran-modified ion-exchange media. II. Intraparticle uptake and column breakthrough

Protein transport behavior was compared for the traditional SP Sepharose Fast Flow and the dextran-modified SP Sepharose XL and Capto S resins. Examination of the dynamic binding capacities (DBCs) revealed a fundamental difference in the balance between transport and equilibrium capacity limitations when comparing the two resin classes, as reflected by differences in the locations of the maximum DBCs as a function of salt. In order to quantitatively compare transport behavior, confocal microscopy and batch uptake experiments were used to obtain estimates of intraparticle protein diffusivities. For the traditional particle, such diffusivity estimates could be used to predict column breakthrough behavior accurately. However, for the dextran-modified media, neither the pore- nor the homogeneous-diffusion model was adequate, as experimental dynamic binding capacities were consistently lower than predicted. In examining the shapes of breakthrough curves, it was apparent that the model predictions failed to capture two features observed for the dextran-modified media, but never seen for the traditional resin. Comparison of estimated effective pore diffusivities from confocal microscopy and batch uptake experiments revealed a discrepancy that led to the hypothesis that protein uptake in the dextran-modified resins could occur with a shrinking-core-like sharp uptake front, but with incomplete saturation. The reason for the incomplete saturation is speculated to be that protein initially fills the dextran layer with inefficient packing, but can rearrange over time to accommodate more protein. A conceptual model was developed to account for the partial shrinking-core uptake to test whether the physical intuition led to predictions consistent with experimental behavior. The model could correctly reproduce the two unique features of the breakthrough curves and, in sample applications, parameters found from the fit of one breakthrough curve could be used to adequately match breakthrough at a different flow rate or batch uptake behavior.     

Electrochemical characterisation of dental alloys: its possibilities and limitations

Dental alloys are metallic biomaterials which have a broad variation of composition compared to technical alloys. It is therefore in the interest of patients and technicians to conduct a good assessment of the electrochemical behaviour of dental alloys in order to collect information about their corrosion resistance. The purpose of this work was to demonstrate possibilities and limitations of two electrochemical techniques: the voltammetry of immobilised microparticles (ViMP) onto lead, and cyclic voltammetry measurements with the help of the mini-cell system (MCS). Based on fingerprints obtained from ViMP it was possible to analyse and differentiate the dental alloys. The results obtained by MCS were comparable with ViMP, but give a better understanding of the corrosion behaviour of the materials.     

Ligand Conformation Dictates Membrane and Endosomal Trafficking of Arginine‐Glycine‐Aspartate (RGD)‐Functionalized Mesoporous Silica Nanoparticles

Recent breakthrough research on mesoporous silica nanoparticle (MSN) materials has illustrated their significant potential in biological applications due to their excellent drug delivery and endocytotic behavior. We set out to determine if MSN, covalently functionalized with conformation specific bioactive molecules (either linear or cyclic RGD ligands), behave towards mammalian cells in a similar manner as the free ligands. We discovered that RGD immobilized on the MSN surface did not influence the integrity of the porous matrix and improved the endocytosis efficiency of the MSN materials. Through competition experiments with free RGD ligands, we also discovered a conformation specific receptor–integrin association. The interaction between RGD immobilized on the MSN surface and integrins plays an important role in endosome trafficking, specifically dictating the kinetics of endosomal escape. Thus, covalent functionalization of biomolecules on MSN assists in the design of a system for controlling the interface with cancer cells.     

Ligand conformation dictates membrane and endosomal trafficking of arginine-glycine-aspartate (RGD)-functionalized mesoporous silica nanoparticles

Recent breakthrough research on mesoporous silica nanoparticle (MSN) materials has illustrated their significant potential in biological applications due to their excellent drug delivery and endocytotic behavior. We set out to determine if MSN, covalently functionalized with conformation specific bioactive molecules (either linear or cyclic RGD ligands), behave towards mammalian cells in a similar manner as the free ligands. We discovered that RGD immobilized on the MSN surface did not influence the integrity of the porous matrix and improved the endocytosis efficiency of the MSN materials. Through competition experiments with free RGD ligands, we also discovered a conformation specific receptor-integrin association. The interaction between RGD immobilized on the MSN surface and integrins plays an important role in endosome trafficking, specifically dictating the kinetics of endosomal escape. Thus, covalent functionalization of biomolecules on MSN assists in the design of a system for controlling the interface with cancer cells.     

Selected electrochemical properties of Pd–Au alloys: hydrogen absorption and surface oxidation

Hydrogen absorption into and surface oxidation of Pd–Au alloys in acidic solutions were studied by cyclic voltammetry (CV) and chronoamperometry (CA) coupled with the electrochemical quartz crystal microbalance (EQCM). The influence of alloy bulk and surface composition on the process of oxidation of absorbed hydrogen was examined. The stresses induced by hydrogen insertion in Pd–Au alloys were compared with the case of pure Pd. The potential corresponding to the formation of a monolayer of surface oxide was determined for Pd–Au alloys of different surface states. Electrochemical dissolution of Pd–Au alloys was investigated.     

Electrocatalytic Oxidation of Perfluoroalkylvinyl Ethers in Fluorosulfonic Acid

Direct anodic oxidation of perfluoroalkylvinyl ethers R_FOCF=CF₂ (PVE) and terminal fluoroolefins R_FCF=CF₂ (TFO) in fluorosulfonic acid is studied using cyclic voltammetry; electrolysis at a monitored potential; and analyses of synthesized products by ¹⁹F NMR, gas-liquid chromatography, and chromato-mass spectrometry, with simultaneous preparative isolation of the products. Proposals on some regularities of the direct oxidation of PVE and TFO are made. The corrosion behavior of platinum, iridium, and their alloys is studied. The formation of oxide films on various electrode materials and a fluorosulfate film on glassy carbon is found to correlate with catalytic activity in reactions of direct oxidation of perfluoroolefins.