Mechanism of hydrogen adsorption/absorption at thin Pd layers on Au(1 1 1)

Hydrogen adsorption and absorption at thin palladium deposits of 0.8-10 monolayers (ML) on Au(1 1 1) was studied in 0.1 M H₂SO₄ and HClO₄ using cyclic voltammetry, ac voltammetry, and impedance spectroscopy in the absence and in the presence of poison, crystal violet. Hydrogen adsorption on palladium is more reversible in sulfuric acid than in perchloric acid but it occurs at potentials 30 mV more positive in latter. The charge-transfer resistance exhibits a minimum at ∼0.27 V versus RHE and decreases with increasing in Pd deposit thickness in both acids. Adsorption capacitance at 0.8 ML Pd reaches maximum at the same potential. At other deposits the pseudo-capacitance starts to increase at lower overpotentials indicating the beginning of absorption, even at 2 ML Pd. The double layer capacitance is similar for all the deposits in sulfuric acid and it has a sharp maximum at 0.27 V versus RHE. In perchloric acid a broad maximum is observed. Crystal violet inhibits hydrogen adsorption but makes hydrogen absorption more reversible. The results suggest a fast direct hydrogen absorption mechanism that proceeds in parallel with slower hydrogen adsorption and indirect absorption.     

Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol

A clear ethanol based precursor sol obtained using diethanolamine has been utilized for the deposition of TiO₂ films annealed at different temperatures. The influence of annealing temperature on the structural, optical and electrochemical properties of TiO₂ thin films has been examined. Diethanolamine stabilizes the precursor sol due to its chelate forming ability with the alkoxides. It reacts as a tridentate ligand with the titanium isopropoxide. The threshold for the onset of crystallization in the films is identified at a temperature of 300 °C. The SEM study on the films elucidates segregation of irregularly shaped features into finer round clusters as a function of annealing temperature. As determined from the AFM study, the roughness parameter in the films has shown an increase with the annealing temperature. Photoluminescence measurements have given an indirect evidence for the presence of stoichiometric titanium oxide in the films. An optimum crystallite size and high ion storage capacity in the 300 °C annealed film has led to its superior electrochromic activity with the transmission modulation and coloration efficiency of the same film being 42% and 8.1 cm² C⁻¹, respectively at 550 nm. The highest degree of porosity in the 300 °C annealed film as established from the SEM study is also the reason behind its best electrochromic performance. In addition, the 300 °C annealed film also exhibits the fastest coloration switching kinetics.     

Confinement, composition, and spin-coating effects on the glass transition and stress relaxation of thin films of polystyrene and styrene-containing random copolymers: Sensing by intrinsic fluorescence

The glass transition temperatures (T_gs) of polystyrene (PS) and styrene/methyl methacrylate (S/MMA) random copolymer films are characterized by intrinsic fluorescence, i.e., monomer fluorescence from an excited-state phenyl ring and excimer fluorescence from an excited-state dimer of two phenyl rings. The T_g is determined from the intersection of the rubbery- and glassy-state temperature dependences of the integrated fluorescence intensity measured upon cooling from an equilibrated state. With PS, the effects of nanoconfinement on T_g and the transition strength agree with results from studies using probe fluorescence and ellipsometry. The T_g-nanoconfinement effect is “tuned” by copolymer composition. As S-content is reduced from 100 mol% to 22 mol%, the confinement effect changes from a reduction to an enhancement of T_g relative to bulk T_g. Intrinsic fluorescence is also a powerful tool for characterizing relaxation of residual stresses. Stresses induced by spin coating affect local conformations, which in turn affect excimer and monomer fluorescence and thereby integrated intensity. The heating protocol needed to achieve apparently equilibrated local conformations is determined by equivalence in the integrated intensities obtained upon heating and subsequent cooling. While partial stress relaxation occurs upon heating in the glassy state, full relaxation of local conformations requires that a film be heated above T_g for times that are long relative to the average cooperative segmental relaxation time. For example, in thin and ultrathin films, equilibration is achieved by heating slowly (∼1 K/min) to 15-20 K above T_g. Dilute solution fluorescence of PS and S/MMA copolymers is also characterized and compared to reports in the literature.     

奥氏体不锈钢细长轴的加工

针对奥氏体不锈钢细长轴难以加工的特点,提出了对其加工相应的工艺方法及注意事项。     

Nanocoating individual cohesive boron nitride particles in a fluidized bed by ALD

Experiments are conducted with alumina (Al₂O₃) deposition on a wide size range of hexagonal boron nitride (BN) platelet-like particles. Successful deposition of alumina films on these particles, with film thickness controllable at the Angstrom level, is observed based upon TEM imaging, ICP-AES, particle size distributions, and surface area analysis. While fluidizing, fine BN particles aggregate in the bed. The aggregates are the entities fluidizing, not the primary particles. However, individual particles are coated using Atomic Layer Deposition (ALD), not aggregates. Since ALD is a surface chemistry phenomenon, the films grow uniformly on every primary particle. BN particles are small platelets with different functional groups on the basal planes and edge planes. A small exposure to reagents [2.5×10⁶ Langmuir (L) per reagent per cycle], will only coat the edge planes of uncoated BN particles. A larger dose of 1×10⁸ L will coat the entire uncoated BN particle (edge and basal planes). After 10 ALD cycles of the 1×10⁸ L dose, the exposures can be reduced to 1×10⁶ L as the film is then growing on alumina and not BN. Peel strength data indicate that adhesion between the coated particles and a cured epoxy in a filled composite is ∼25% stronger than that of uncoated particles and the epoxy. The overall thermal conductivity drops ∼17% for an identical filler loading as expected due to the additional thermal resistance added by the film. However, the viscosity of an epoxy resin loaded with coated BN is as much as five times lower than that of the resin loaded with the same amount of uncoated BN. These results indicate that the loading of Al₂O₃ nanocoated BN particles in an epoxy matrix can be substantially increased relative to that of uncoated particles. The thermal conductivity of the more highly filled composite will be increased without adversely impacting filled resin viscosity or the peel strength of the cured material. This is the first reported study indicating that cohesive primary particles that fluidize as aggregates in a fluidized bed can be individually coated with a nano-thick ceramic film using ALD.     

Adhesion-Delamination Mechanics of a Prestressed Circular Film Adhered onto a Rigid Substrate

A thin circular film clamped at the periphery is adhered to the planar surface of a rigid cylindrical punch. An external tensile load is applied to the punch, causing the film to delaminate from the substrate and the circular contact edge to contract. The film spontaneously separates from the punch, or pulls off, when the contact radius reduces to a range between 0.1758 and 0.3651 of the film radius, depending on the magnitude of the residual membrane stress. The mechanical delamination process is derived by a thermodynamic energy balance based on a coupled interfacial adhesion and residual membrane stress. The theoretical model has significant implications in nanoforce measurement, microelectromechanical systems (MEMS) comprising active moveable films, and biological cell adhesion.     

Evaluation of the pseudocapacitance in RuO2 with a RuO2/GC thin film electrode

The pseudocapacitance of nanocrystalline RuO₂ with BET surface area of 42 m² g⁻¹ was evaluated using a RuO₂ modified Glassy Carbon (RuO₂/GC) thin film electrode. The charge storage behavior of the RuO₂/GC thin film electrode was studied from fast to slow scan cyclic voltammetry between various potential windows. The utilization of the thin film electrode method for nanocrystalline RuO₂ with known specific surface area allowed a semi-quantitative understanding of the electric double-layer capacitance (C_dl), adsorption related charge (C_ad), and the irreversible redox related charge (C_irr) per unit mass and surface area of RuO₂. Comparison of the cyclic voltammograms between different voltage windows revealed that the contribution from C_irr is especially dominant below 0.4 V (versus RHE) at slow scan rates.     

日照苏家村遗址出土钱山漾文化陶鬶的产地研究

日照苏家村遗址位于鲁东南沿海地区,是大汶口文化晚期至龙山文化早中期一处重要的环濠聚落。该遗址新出土的钱山漾文化细长颈袋足鬶(M45:5)作为目前已知南方系陶鬶布最北的一件,揭示出公元前2300年前后中国南北方的区域文化交流。本文通过对苏家村出土钱山漾文化红陶鬶、其他龙山文化红陶鬶及部分苏家村黑陶的主、微量元素分析,结合主成分分析揭示了苏家村本地生产钱山漾文化红陶鬶的可能性,表明龙山文化早中期的制陶业的发展可能伴随着南方系制陶工匠的迁徙。     

Mechanical properties of nano-structured Ti-Si-N films synthesized by cathodic arc evaporation

Ti_1−xSi_xN coatings were synthesized by cathodic arc evaporation with plasma-enhancing filter duct, using Ti₈₀Si₂₀ alloy target as cathodes. Optical emission study revealed that excitation, ionization and charge transfer reactions of the Ti-Si-N plasma occurred during the Ti_1−xSi_xN deposition process. The chemical content of Si varied from 3.3 to 6.0 at% in Ti_1−xSi_xN depending on the nitrogen partial pressure of the reaction chamber. All the Ti_1−xSi_xN coatings displayed a NaCl structure and a preferred (2 0 0) orientation parallel to the substrate surface. Among the studied Ti_1−xSi_xN coatings, the Ti_1−xSi_xN with 6 at.% Si possessed the highest hardness of 45 GPa and H³/E*² ratio of 0.527 GPa, indicating the best resistance to plastic deformation. We found that the structure and mechanical properties of the Ti_1−xSi_xN films were correlated with the nitrogen pressure and silicon content of the coatings.     

影响薄壁球墨铸铁白口倾向和球墨数量的因素分析

研究了不同的冷却速度、稀土加入量、碳量、硅量、Si／C、Mn／S及孕育处理等工艺时薄壁球墨铸铁球墨数量和白口深度的影响。结果表明，随着冷却速率增加，薄壁球墨铸铁石墨小球越多，但容易产生白口。冷速较大时，加入稀土元素进行孕育和控制碳当量，可以有效的消除薄壁球墨铸铁的白口现象，当Si／C大于0．80、Mn／S大于20时薄壁件白口倾向较小。