Covalent modification of a glassy carbon surface by 4-aminobenzoic acid and its application in fabrication of a polyoxometalates-consisting monolayer and multilayer films

4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy measurement proves the presence of 4-carboxylphenylamine monolayer on the GCE. The redox responses of various electroactive probes were investigated on the 4-ABA-modified GCE. Electron transfer to Fe(CN)(6)(3-) in solutions of various pHs was studied by both cyclic voltammetry and electrochemical impedance analysis on the modified electrode. Changes in the solution pH value result in the variation of the terminal group charge state, based on which surface pK(a) values are estimated. The 4-ABA-modified GCE was used as a suitable charged substrate to fabricate polyoxometalates-consisting (POM-consisting) monolayer and multilayer films through layer-by-layer assembly based on electrostatic attraction. Cyclic voltammetry shows the uniform growth of these three-dimensional multilayer films. Taking K10H3[Pr-(SiMo7W4O39)(2)]. H2O (abbreviated as Pr(SiMo7W4)(2)), for example, the preparation and electrochemical behavior of its monolayer and multilayer film had been investigated in detail. This modification strategy is proven to be a general one suitable for anchoring many kinds of POMs on the 4-ABA-modified GCE.

Formation of a self-assembled monolayer of 2-mercapto-3-n-octylthiophene on gold

Monolayer assembly of 2-mercapto-3-n-octylthiophene (MOT) having a relatively large headgroup onto gold surface from its dilute ethanolic solutions has been investigated by electrochemistry. An electrochemical capacitance measurement on the permeability of the monolayer to aqueous ions, as compared with its alkanethiol counterpart [CH3(CH2)(9)SH (DT)] with a similar molecular length, shows that the self-assembled monolayers (SAMs) of MOT can be penetrated by aqueous ions to some extent. Furthermore, organic molecular probes, such as dopamine, can sufficiently diffuse into the monolayer because a diffusion-limited current peak is observed when the dopamine oxidation reaction takes place, showing that the monolayer is loosely packed or dominated by defects. But the results of electron transfer to aqueous redox probes (including voltammetry in Fe(CN)(6)(3-/4-) solutions and electrochemical ac impedance spectrum) confirm that the monolayer can passivate the gold electrode surface effectively for its very low ratio of pinhole defects. Moreover, a heterogeneous patching process involving addition of the surfactants into the SAMs provides a mixed or hybrid membrane that has superior passivating properties. These studies show that the MOT monolayer on the electrode can provide an excellent barrier for hydrated ionic probe penetration but cannot resist the organic species penetration effectively. The unusual properties of the SAMs are attributed to the entity of the relatively large thiophene moiety between the carbon chain and the thiol group.

He, Ne and Ar isotopic composition of Fe-Mn crusts from the western and central Pacific Ocean and implications for their genesis

The noble gas nuclide abundances and isotopic ratios of the upmost layer of Fe-Mn crusts from the western and central Pacific Ocean have been determined. The results indicate that the He and Ar nuclide abundances and isotopic ratios can be classified into two types: low He-3/He-4 type and high He-3/He-4 type. The low He-3/He-4 type is characterized by high He-4 abundances of 191x10(-9) cm(3.)STP(.)g(-1) on average, with variable He-4, Ne-20 and Ar-40 abundances in the range (42.8-421)x10(-9) cm(3.)STP(.)g(-1), (5.40-141)x10(-9)cm(3.)STP(.)g(-1), and (773-10976)x10(-9) cm(3.)STP(.)g(-1), respectively. The high He-3/He-4 samples are characterized by low He-4 abundances of 11.7x10(-9) cm(3.)STP(.)g(-1) on average, with He-4, Ne-20 and Ar-40 abundances in the range of (7.57-17.4)x10(-9) cm(3.)STP(.)g(-1), (110.4-25.5)x10(-9) cm(3.)STP(.)g(-1) and (5354-9050)x10(-9) cm(3.)STP(.)g(-1), respectively. The low He-3/He-4 samples have He-3/He-4 ratios (with RIRA ratios of 2.04-2.92) which are lower than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (447-543) which are higher than those of air (295.5). The high He-3/He-4 samples have He-3/He-4 ratios (with R/R-A ratios of 10.4-12.0) slightly higher than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (293-299) very similar to those of air (295.5). The Ne isotopic ratios (Ne-20/Ne-22 and Ne-21/Ne-22 ratios of 10.3-10.9 and 0.02774-0.03039, respectively) and the Ar-38/Ar-36 ratios (0.1886-0.1963) have narrow ranges which are very similar to those of air (the Ne-20/Ne-22, Ne-21/Ne-22, Ar-38/Ar-36 ratios of 9.80, 0.029 and 0.187, respectively), and cannot be differentiated into different groups. The noble gas nuclide abundances and isotopic ratios, together with their regional variability, suggest that the noble gases in the Fe-Mn crusts originate primarily from the lower mantle. The low He-3/He-4 type and high He-3/He-4 type samples have noble gas characteristics similar to those of HIMU (High U/Pb Mantle)- and EM (Enriched Mantle)-type mantle material, respectively. The low He-3/He-4 type samples with HIMU-type noble gas isotopic ratios occur in the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain and the Mid-Pacific Seamounts whereas the high He-3/He-4 type samples with EM-type noble gas isotopic ratios occur in the Line Island Chain. This difference in noble gas characteristics of these crust types implies that the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain, and the Mid-Pacific Seamounts originated from HIMU-type lower mantle material whereas the Line Island Chain originated from EM-type lower mantle material. This finding is consistent with variations in the Pb-isotope and trace element signatures in the seamount lavas. Differences in the mantle surce may therefore be responsible for variations in the noble gas abundances and isotopic ratios in the Fe-Mn crusts. Mantle degassing appears to be the principal factor controlling noble gas isotopic abundances in Fe-Mn crusts. Decay of radioactive isotopes has a negligible influence on the nuclide abundances and isotopic ratios of noble gases in these crusts on the timescale of their formation.

Net-like Ferromagnetic Mnsb Film Deposited on Porous Silicon Substrates

MnSb films were deposited on porous silicon substrates by physical vapor deposition (PVD) technique. Modulation effects due to the substrate on microstructure and magnetic properties of the MnSb film's were studied by scanning electron microscope (SEM), X-ray diffraction (XRD) and measurements of hysteresis loops. SEM images of the MnSb films indicate that net-like structures were obtained because of the special morphology of the substrates. The net-like MnSb films exhibit some novel magnetic properties different from the unpatterned referenced samples. For example, in the case of net-like morphology, the coercive field is as low as 60 Oe.

Anomalous Thermal Stability of Nd-Fe-Co-Al Bulk Metallic Glass

The thermal stability of Nd60Fe20Co10Al10 bulk metallic glass (BMG) has been studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), isochronal dilatation and compression tests. The results show that the glass transition of the BMG takes place quite gradually between about 460 and 650 K at a heating rate of 0.17 K/s. Several transformation processes are observed during continuous heating with the first crystallization process beginning at about 460 K, while massive crystallization takes place near the solidus temperature of the alloy. The positive heat of mixing between the two major constituents, Nd and Fe, and, consequently, a highly inhomogeneous composition of the attained amorphous phase are responsible for the anomalous thermal stability in this system. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Nonequilibrium microstructures and their evolution in a Fe-Cr-W-Ni-C laser clad coating

The laser-solidified microstructural and compositional characterization and phase evolution during tempering at 963 K were investigated using an analytical transmission electron microscope with energy dispersive X-ray analysis. The cladded alloy, a powder mixture of Fe, Cr, W, Ni, and C with a weight ratio of 10:5:1:1:1, was processed with a 3 kW continuous wave CO2 laser. The processing parameters were 16 mm/s beam scanning speed, 3 mm beam diameter. 2 kW laser power, and 0.3 g/s feed rate. The coating was metallurgically bonded to the substrate, with a maximum thickness of 730 mu m, a microhardness of about 860 Hv and a volumetric dilution ratio of about 6%. Microanalyses revealed that the cladded coating possessed the hypoeutectic microstructure comprising the primary dendritic gamma-austenite and interdendritic eutectic consisted of gamma-austenite and M7C3 carbide. The gamma-austenite was a non-equilibrium phase with extended solid solution of alloying elements and a great deal of defect structures, i.e. a high density of dislocations, twins, and stacking faults existed in gamma phase. During high temperature aging, in situ carbide transformation occurred of M7C3 to M23C6 and M6C. The precipitation of M23C6, MC and M2C carbides from austenite was also observed.

Preparation And Tribology Studies of Alkyl Carboxylic Acid Monolayer Films on Pei-Coated Glass Substrate

首次在涂敷PEI的玻璃表面上制备了癸酸及全氟癸酸的单分子层膜。研究了成膜机理及摩擦特性。结果表明。脱水剂DCCD促进了癸酸或全氟癸酸与PEI酞胺化的反应。导致两种羧酸在PEI表面产生了靠化学键（酞胺键）连接的稳定的单分子层膜,摩擦、磨损实验表明。单分子层有机膜的摩擦特性受膜的组成、表面能及有序性和堆积密度的重要影响。表面能越低,有序性和堆积密度越高。摩擦系数越低。与碳氢化合物相比。碳氟化合物形成的有序膜具有更高的强度和抗磨性能。

Room-temperature ferromagnetic semiconductor MnxGa1-xSb

Ferromagnetic semiconductor MnxGa1-xSb single crystals were fabricated by Mn-ions implantation, deposition, and the post annealing. Magnetic hysteresis-loops in the MnxGa1-xSb single crystals were obtained at room temperature (300 K). The structure of the ferromagnetic semiconductor MnxGa1-xSb single crystal was analyzed by Xray diffraction. The distribution of carrier concentrations in MnxGa1-xSb was investigated by electrochemical capacitance- voltage profiler. The content of Mn in MnxGa1-xSb varied gradually from x = 0.09 near the surface to x = 0 in the wafer inner analyzed by X-ray diffraction. Electrochemical capacitance-voltage profiler reveals that the concentration of p-type carriers in MnxGa1-xSb is as high as 1 1021 cm-3, indicating that most of the Mn atoms in MnxGa1-xSb take the site of Ga, and play a role of acceptors.

铁基抗高温磨损激光熔覆涂层强韧设计和研究II:Fe-Cr-C-W-Ni激光熔覆层的微观组织及性能

本文以对热工模具进行失效分析的基础上，利用激光熔覆技术，在５ＣｒＭｎＭｏ基础上设计并制备强韧兼备的抗高温磨损涂层。

Modeling Nonlinear Peeling of Ductile Thin Films-Critical Assessment of Analytical Bending Models Using FE Simulations

Three analytical double-parameter criteria based on a bending model and a two-dimensional finite element analysis model are presented for the modeling of ductile thin film undergoing a nonlinear peeling process. The bending model is based on different governing parameters: (1) the interfacial fracture toughness and the separation strength, (2) the interfacial fracture toughness and the crack tip slope angle, and (3) the interfacial fracture toughness and the critical Mises effective strain of the delaminated thin film at the crack tip. Thin film nonlinear peeling under steady-state condition is solved with the different governing parameters. In addition, the peeling test problem is simulated by using the elastic-plastic finite element analysis model. A critical assessment of the three analytical bending models is made by comparison of the bending model solutions with the finite element analysis model solutions. Furthermore, through analyses and comparisons for solutions based on both the bending model and the finite element analysis model, some connections between the bending model and the finite element analysis model are developed. Moreover, in the present research, the effect of different selections for cohesive zone shape on the ductile film peeling solutions is discussed.

Temperature Dependence of the Tribological Properties of Laser Re-Melted Al-Cu-Fe Quasicrystalline Plasma Sprayed Coatings

The aim of this study was to investigate the effect of temperature on tribological properties of plasma-sprayed Al-Cu-Fe quasicrystal (QC) coating after laser re-melting treatment. The laser treatment resulted in a more uniform, denser and harder microstructure than that of the as-sprayed coatings. Tribological experiments on the coatings were conducted under reciprocating motion at high frequency in the temperature range from 25 to 650 degreesC. Remarkable influence of temperature on the friction behavior of the coating was recorded and analyzed. Microstructural analysis indicated that the wear mechanisms of the re-melted QC coatings changed from abrasive wear at room temperature, to adhesive wear at 400 degreesC and severe adhesive wear at 650 degreesC owing to the material transfer of the counterpart ball. It was also observed that the ratio of the icosahedral (i)-phase to beta-Al-50(Fe,CU)(50) phase in the coating was higher after test at 400 'C than that at 650 'C. The variation of the ratio UP of coating and of the property of the counterpart ball and coating with the temperature are the two main factors influencing the wear mechanisms and value of the friction coefficient.

Deformation Behavior Of Fe-Based Bulk Metallic Glass During Nanoindentation

Fe-based bulk metallic glasses (BMGs) normally exhibit super high strength but significant brittleness at ambient temperature. Therefore, it is difficult to investigate the plastic deformation behavior and mechanism in these alloys through conventional tensile and compressive tests due to lack of distinct macroscopic plastic strain. In this work, the deformation behavior of Fe52Cr15Mo9Er3C15B6 BMG was investigated through instrumented nanoindentation and uniaxial compressive tests. The results show that serrated flow, the typical plastic deformation feature of BMGs, could not be found in as-cast and partially crystallized samples during nanoindentation. In addition, the deformation behavior and mechanical properties of the alloy are insensitive to the applied loading rate. The mechanism for the appearance of the peculiar deformation behavior in the Fe-based BMG is discussed in terms of the temporal and spatial characteristics of shear banding during nanoindentation.

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr( 110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr2CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/ near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.

Effect of Fe content on the thermal stability and dynamic mechanical behavior of NdAlNiCu bulk metallic glasses

The dependence of microstructure and thermal stability on Fe content of bulk Nd60Al10Ni10Cu20-xFex (0 less than or equal to x less than or equal to 20) metallic glasses is investigated by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and high-resolution transmission electron micrograph (HRTEM). All samples exhibit typical amorphous feature under the detect limit of XRD, however, HRTEM results show that the microstructure of Nd60Al10Ni10Cu20-xFex alloys changes from a homogeneous amorphous phase to a composite structure consisting of clusters dispersed in amorphous matrix by increasing Fe content. Dynamic mechanical properties of these alloys with controllable microstructure are studied, expressed via storage modulus, the loss modulus and the mechanical damping. The results reveal that the storage modulus of the alloy without Fe added shows a distinct decrease due to the main a relaxation. This decrease weakens and begins at a higher temperature with increasing Fe content. The mechanism of the effect of Fe addition on the microstructure and thermal stability in this system is discussed in terms of thermodynamics viewpoints. (C) 2004 Elsevier B.V. All rights reserved.