Influence of initial surface condition of lithium metal anodes on surface modification with HF

Surface modification of as-received lithium foils was carried out using acid-base reactions of the native surface films on lithium metal with HF. Two types of as-received lithium foils covered with different native films were used as samples for this surface modification. One was a lithium foil having a very thin native surface film and the other one had a thicker native surface film. The surface condition of the lithium metal was analysed by X-ray photoelectron spectroscopy before and after the surface modification using HF, and the coulombic efficiency was measured electrochemically. The thickness of the surface film on the modified lithium foils was related to the Li₂O layer thickness in the native film on the as-received lithium foils. The modified lithium foil which had the thinner native surface film provided more uniform deposition of lithium and a higher coulombic efficiency during charge and discharge cycles when propylene carbonate electrolyte with 1.0 m LiPF₆ was used as the electrolyte. These results show that the initial condition of the native surface film plays an important role in surface modification with HF.     

Synthesis of Nanowire TiO2 Thin Films by Hydrothermal Treatment and their Photoelectrochemical Properties

Nanowire TiO₂ thin films were successfully prepared on Ti metal substrates by hydrothermal treatment of calcined Ti foils in 10 M NaOH. The nanowire TiO₂ thin films exhibited much larger surface area and higher photoelectrochemical performance than the TiO₂ thin films prepared on Ti metal substrates by the calcination of Ti foil. These nanowire films were shown to act as an efficient photoanodes for the photoelectrochemical water splitting reaction.     

Joining of Al2O3 ceramic to Cu using refractory metal foil

Joining of Al₂O₃ ceramic to Cu has been conducted with Ag-26.7Cu-4.5Ti braze and refractory metal (W or Ta) foil. The interfacial microstructure in the joint with W foil is similar to that with Ta foil. The joining region in the joint consists of a reaction zone, braze zone I, refractory metal layer and braze zone II. The reaction zone of Cu₃Ti₃O with a thickness of about 5 μm develops close to Al₂O₃ side due to the reactions of Ti and Cu in the braze with Al₂O₃ substrate. The braze zones I and II are mainly composed of Ag- and Cu-based solid solutions. For the joint with W foil, the adsorption of Ti at the braze/W interfaces followed by the Ti diffusion into W foil occurs, whilst slight dissolution and diffusion of Ta into the brazes take place in the joint with Ta foil. The average shear strengths of joints with W and Ta foils are much higher than those without refractory metal foil, indicating the contribution of the refractory metal foil to the improvement of joint mechanical strength. Introduction of refractory metal foil in Al₂O₃/Cu joining is beneficial for the shift of joint residual stress distribution and the decrease of stress concentration in the joint since the coefficient of thermal expansion (CTE) of refractory metal layer approximately approaches that of Al₂O₃. Furthermore, a slight thickness increase of the Cu₃Ti₃O reaction zone in the joint with refractory metal foil may also give rise to the joint strength promotion.     

Effect of Ru and LaNiO3 barrier layers on lead zirconate titanate films grown on nickel-based metal foils by sol–gel process

Lead zirconate titanate [Pb(Zr_0.52, Ti_0.48)O₃ (PZT)] films were grown by sol–gel process on nickel and hastelloy foils. PZT perovskite phase was obtained at 650 °C annealing condition and surface topography showed uniform and dense microstructure. The characterization on dielectric properties indicates that diffusion of foil elements into the PZT and the formation of low capacitance interfacial layer occur during process. In order to reduce the diffusion effect of foil element and/or interfacial layer, barrier layers such as Ru(RuO₂) and LaNiO₃ layers were utilized on foil substrates. The increase of grain size was observed in PZT films grown on barrier layers. Dielectric properties are greatly improved without degrading ultimate dielectric breakdown strength.     

Formation of Al2O3–Nb2O5 composite oxide films on low-voltage etched aluminum foil by complexation–precipitation and anodizing

Niobium pentaoxide (Nb₂O₅) thin films were deposited on etched aluminum foils by complexation–precipitation followed by heat treatment. Then the Al₂O₃–Nb₂O₅ (Al–Nb) composite oxide films were formed by anodizing to increase the capacitance of anodized aluminum foils which are used in aluminum electrolytic capacitors. The composition and structure of niobium deposition layer were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), and the microstructures and dielectric properties of anodic oxide films were investigated by scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS) respectively. The results show that the niobium deposition layer after heat treatment existed in the form of crystalline Nb₂O₅. The aluminum foil with Nb₂O₅ coating can be anodized with higher efficiency and energy saving. Compared with that of normal anodized aluminum foils, the effective area of the anodized aluminum foils with Al–Nb composite oxide films had no apparent change. The specimens with Al–Nb composite oxide films anodized at 30 V exhibited about 20% higher specific capacitance than that of those with pure aluminum oxide films. It suggests that the method of complexation–precipitation is an effective way to increase the specific capacitance of anodized aluminum foils used in aluminum electrolytic capacitors.     

Effects of Cu interlayers on the microstructure and mechanical properties of Al2O3/AgCuTi/Kovar brazed joints

Al₂O₃ ceramic and Kovar alloy brazed joints were achieved using three types of Ag-based interlayers: a AgCuTi foil, a AgCuTi/Cu foil/AgCuTi multi-interlayer and a AgCuTi/Cu foam/AgCuTi multi-interlayer. The effects of the addition of Cu interlayers on the interfacial microstructure and mechanical properties of Al₂O₃/AgCuTi/Kovar brazed joints were investigated. When Kovar alloy and Al₂O₃ ceramic were brazed with 50 μm Cu foil at 900°C for 10 minutes, the Cu foil was completely dissolved in the liquid filler. A nearly continuous Cu layer remained in the joint when the thickness of the Cu foil reached 100 μm under the same brazing conditions. With the increase in Cu foil thickness, the thickness of Ti–O compounds + Ti₃Cu₃O reaction layer formed nearby the Al₂O₃ ceramic first increased and then remained the same. The Al₂O₃/Kovar joints brazed with 100 μm Cu foil at 900°C for 10 minutes showed a maximum shear strength of 138 MPa. A low brazing temperature was beneficial to maintain the original structure of the Cu foam. Furthermore, when the joints were brazed at 880°C for 10 minutes, the average shear strength of the Al₂O₃/AgCuTi/Cu foam/AgCuTi/Kovar joints was 140 MPa, which was 30 MPa higher than that of a single AgCuTi interlayer.     

Surface analysis of three aluminum foils and relation to hydrogen generation capability

We have successfully generated hydrogen using aluminum foil instead of aluminum powder from the perspective of improving safety. We analyzed the surface states of three aluminum foils and correlated their surface properties with hydrogen generation capability. The surfaces of the foils were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy, and atomic force microscopy. Hydrogen generation was performed by adding Ca(OH)₂ solution to the aluminum foil in water. The TOF-SIMS results showed that the Al foils have Al₂O ₃ ^- , AlO ₂ ^- , (OH)₂AlO^-, (Al₂O₃)OH^-, and (Al₂O₃)AlO ₂ ^- and related species on their surfaces. The amount of these species on the surface of an Al foil is linearly correlated with the hydrogen generation reaction rate.     

Preparation and Characterization of Copper Gallium Diselenide Thin Films from the Solgel‐Derived Precursors

A simple process for preparing CuGaSe₂ (CGS) absorber layers was developed in this study. The solgel‐derived Cu‐Ga‐O precursor paste with variable Ga³⁺/Cu²⁺ ratios was coated on glass substrates using a doctor‐blade technique. The precursor films were selenided with a selenium vapor at the temperature ranging from 250 to 550°C. The GIXRD patterns showed that single‐phase CuGaSe₂ through the whole films was obtained at a Ga³⁺/Cu²⁺ molar ratio of 1.5 on selenization at 450°C. The Raman measurements also indicated that the grown CuGaSe₂ thin films exhibited the chalcopyrite structure. The SEM images of the films reveal that with an increase in Ga/Cu ratio in the films, the amount of Cu₂Se particles on the surface of the film was reduced. The resistivity of the films was increased with the increase in Ga content in the films. The formation mechanism of CuGaSe₂ thin films was proposed based on the XRD and Raman measurements of the films. The binary copper selenides are formed first, and then these phases lead to the formation of CuGaSe₂.     

Fabrication of CuO nanoplatelets for highly sensitive enzyme-free determination of glucose

CuO nanoplatelets were grown on Cu foils by a one step, template free process. The structure and morphology of the CuO nanoplatelets were characterized by X-ray diffraction, scanning and transmission electron microscopy. The CuO nanoplatelets grown on Cu foil were integrated to be an electrode for glucose sensing. The electrocatalytic activity of the CuO nanoplatelets electrode for glucose in alkaline media was investigated by cyclic voltammetry and chronoamperometry. The electrode exhibits a sensitivity of 3490.7 μA mM⁻¹ cm⁻² to glucose which is much higher than that of most reported enzyme-free glucose sensors and the linear range was obtained over a concentration up to 0.80 mM with a detection limit of 0.50 μM (signal/noise = 3). Exhilaratingly, the electrode based on the CuO nanoplatelets is resistant against poisoning by chloride ion, and the interference from the oxidation of common interfering species, such as uric acid, ascorbic acid, dopamine and carbonhydrate compounds, can also be effectively avoided. Finally, the electrode was applied to analyze glucose concentration in human serum samples.     

CO Oxidation Behavior of Copper and Copper Oxides

Carbon monoxide oxidation activities over Cu, Cu₂O, and CuO were studied to seek insight into the role of the copper species in the oxidation reaction. The activity of copper oxide species can be elucidated in terms of species transformation and change in the number of surface lattice oxygen ions. The propensity of Cu₂O toward valence variations and thus its ability to seize or release surface lattice oxygen more readily enables Cu₂O to exhibit higher activities than the other two copper species. The non-stoichiometric metastable copper oxide species formed during reduction are very active in the course of CO oxidation because of its excellent ability to transport surface lattice oxygen. Consequently, the metastable cluster of CuO is more active than CuO, and the activity will be significantly enhanced when non-stoichiometric copper oxides are formed. In addition, the light-off behaviors were observed over both Cu and Cu₂O powders. CO oxidation over metallic Cu powders was lighted-off because of a synergistic effect of temperature rises due to heat generation from Cu oxidation as well as CO oxidation over the partially oxidized copper species.     

Novel synthesis of CuO nanofiber balls and films and their UV–visible light filteration property

Self-assembled cupric oxide (CuO) nanofiber balls and films were synthesized via a facile solvothermal route directly from cupric acetate monohydrate (Cu(CH₃COO)₂·H₂O) in water and ethanol without any chemical additions or high temperature treatment. The CuO balls with size of 150 nm–1.5 µm had rough surfaces which consisted of lots of about 10 nm nanofibers in diameter. The sizes of CuO balls were controllable by changing reaction time and volume ratio of water to ethanol. CuO nanofiber films were prepared with the aid of the in situ hydrolysis of Cu(CH₃COO)₂·H₂O coating layer on a substrate at 60 °C. CuO films showed excellent UV–visible light filteration property and could be used as a potential candidate of UV–visible light filter. Compared with traditional method to fabricate CuO films, neither precursor nor Cu substrate was needed in this study. This technique could be used to produce CuO films without being confined to our template and to produce CuO powders in large scale with low cost.     

The surface condition effect of Cu2O flower/grass-like nanoarchitectures grown on Cu foil and Cu film

Cu₂O flower/grass-like nanoarchitectures (FGLNAs) were fabricated directly on two category specimens of Cu foils and Cu film using thermal oxidation method. The FGLNAs are approximately 3.5 to 12 μm in size, and their petals are approximately 50 to 950 nm in width. The high compressive stress caused by a large oxide volume in the Cu₂O layer on the specimen surface played an important role in the growth of FGLNAs. The effects of surface conditions, such as the surface stresses, grain size, and surface roughness of Cu foil and Cu film specimens, on the FGLNA growth were discussed in detail.

PACS

81. Materials science; 81.07.-b Nanoscale materials and structures: fabrication and characterization; 81.16.Hc Catalytic methods     

Effect of Cu2O thin film on Cu–Sn alloy coated steel surface in promoting interfacial adhesion with rubber

In the present study, effect of Cu₂O film deposited via successive ionic layer adsorption and corresponding chemical reaction (SILAR method) on Cu–Sn coated steel substrate was explored for the purpose of improving the adhesion of steel with rubber. The effect of the relative alkali concentration in the oxide film deposition bath and the number of immersion cycles on the interfacial adhesion affecting the nature of oxide film deposited, its thickness and surface coverage were investigated. In the current study, Cu–Sn coated steel bead wire with coated surface roughness (R_a) around 2 μm showed an improvement of 33% in adhesion (in terms of pull out force) with an optimum alkali/Cu ion concentration of 25:1 with single dipping cycle attributed to an optimum oxide coating thickness of ~70 nm. Surface morphology study exhibited formation of thicker coating with increase in number of dipping cycles. Satisfactory thermal stability of the Cu₂O film was confirmed as no re-oxidation of the Cu₂O film to CuO was observed in the 200 °C heat treated samples.     

Preparation and characterization of cellulose-based nanocomposite hydrogel films containing CuO/Cu2O/Cu with antibacterial activity

In the present study, the influence of citric acid (CA) on hydrogel films composed of sodium carboxymethylcellulose (NaCMC), hydroxypropylmethylcellulose (HPMC), and CuO nanoflakes was investigated for their physicochemical, mechanical, thermal, and antibacterial properties. XRD patterns showed that the prepared hydrogel films revealed the crystalline phase for CuO/Cu₂O/Cu at 20% CA concentration. Laser micro-Raman spectroscopy confirmed the presence of CuO and Cu₂O in the films. Increase in CA concentration decreased the swelling degree and tensile strength and increased the decomposition temperature of NaCMC, HPMC, and CuO. According to FESEM and FETEM results, shape and size of CuO nanoflakes were completely changed into spherical nanoparticles with increase in CA concentration. HRTEM and inverse Fourier transform images showed that the d-spacing of CuO, Cu₂O, and Cu were correlated with XRD results. The prepared hydrogel films exhibited significant antibacterial activity and biocompatibility against HaCaT cells. All these data recommend that the prepared hydrogel films may be used for potential wound healing applications.     

Catalytic Fabrication of SiC/SiO2 coated graphite and its behaviour in Al2O3–C castable systems

SiC/SiO₂ coated graphite was prepared via a combined sol-gel coating and catalytic conversion route, using graphite flake and tetraethyl orthosilicate as the starting materials, and Fe(NO₃)₃·9H₂O as the catalyst precursor. X-ray diffraction analysis and microstructural examination revealed that a homogeneous coating comprising SiC and cristobalite (SiO₂) and covering the whole surface of graphite was formed. As prepared SiC/SiO₂ coated graphite exhibited better oxidation resistance and water wettability than its uncoated counterpart. Also, oxidation resistance and slag corrosion resistance of a model Al₂O₃–C castable using coated graphite as a carbon source were better than in the case of its counterpart using uncoated graphite.     

Tribological behavior of GNPs doped Al2O3 coating fabricated by SHVOF thermal spraying on cemented carbide

This paper aims to experimentally investigate the effect of graphene nanoplatelets (GNPs) doped Al₂O₃ coating deposited on the surface of cemented carbide substrate using suspension high velocity oxy fuel (SHVOF) thermal spraying technique. Scanning electron microscopy was applied to characterize GNPs doped Al₂O₃ feedstock, the surface morphologies of cemented carbide before and after spraying, and the wear track morphology of cemented carbide after wear tests. The phases of GNPs doped Al₂O₃ feedstock, uncoated and coated cemented carbide were analyzed by X-ray diffraction. The existence of GNPs was analyzed by Raman spectroscopy. A mixture of un-molten and molten splats formed on the surface of cemented carbide substrate after SHVOF thermal spray. The average coefficient of friction (CoF) of coated samples was slightly lower than that of uncoated samples, which might be due to the friction-reduction effect of GNPs. The wear rate of the samples was one order of magnitude higher than that of the alumina ball, showing that the wear of samples was the main wear between the friction couples. The wear mechanism of uncoated sample was mainly fatigue spalling, and that of cemented carbide substrate coated with GNPs doped Al₂O₃ coating was mainly plowing and abrasive wear.     

Ni Catalyst Coating on Fecralloy® Microchanneled Foils and Testing for Methane Steam Reforming

The procedure following the washcoating of three different Ni catalyst systems (MgO, Al₂O₃, and CeO₂/Al₂O₃ supported) on pretreated Fecralloy® microchanneled foils under controlled milling times and viscosities of the slurries is described. The activity of the prepared coatings is also presented. Four different series of coated foils were prepared: one per each catalyst system, keeping constant the average particle size on 5 μm, and one extra series to study the effect of reducing the average particle size of the MgO‐supported catalyst system to 3 μm. For each coating, scanning electron microscopy pictures were taken and specific surface areas and average densities of the catalyst layers were estimated. Finally, each series of coated foils was stacked and tested in a microreactor for the methane steam reforming (MSR) reaction under different conditions.     

Nanostructured CuO thin film electrodes prepared by spray pyrolysis: a simple method for enhancing the electrochemical performance of CuO in lithium cells

Nanostructured CuO thin films were prepared by using a spray pyrolysis method, copper acetate as precursor and stainless steel as substrate. The textural and structural properties of the films were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed thorough coating of the substrate and thickness of 450-1250 nm; the average particle size as determined from the AFM images ranged from 30 to 160 nm. The XRD patterns revealed the formation of CuO alone and the XPS spectra confirmed the presence of Cu²⁺ as the main oxidation state on the surface. The films were tested as electrodes in lithium cells and their electrochemical properties evaluated from galvanostatic and step potential electrochemical spectroscopy (SPES) measurements. The discharge STEP curves exhibited various peaks consistent with the processes CuO ⇔ Cu₂O ⇔ Cu and with decomposition of the electrolyte, a reversible process in the light of the AFM images. The best electrode exhibited capacity values of 625 Ah kg⁻¹ over more than 100 cycles. This value, which involves a CuO ⇔ Cu reversible global reaction, is ca. 50% higher than that reported for bulk CuO. The nanosize of the particles and the good adherence of the active material to the substrate are thought to be the key factors accounting for the enhanced electrochemical activity found.     

Methanol synthesis pathway over Cu/ZrO2 catalysts: a time‐resolved DRIFT 13C‐labelling experiment

X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been used to characterize a series of Cu/Ce/Al₂O₃ catalysts. Catalysts were prepared by incipient wetness impregnation using metal nitrate and alkoxide precursors. Catalyst loadings were held constant at 12 wt% CuO and 5.1 wt% CeO₂. Mixed oxide catalysts were prepared by impregnation of cerium first, followed by copper. The information obtained from surface and bulk characterization has been correlated with CO and CH₄ oxidation activity of the catalysts. Cu/Al₂O₃ catalysts prepared using Cu(II) nitrate (CuN) and Cu(II) ethoxide (CuA) precursors consist of a mixture of copper surface phase and crystalline CuO. The CuA catalyst shows higher dispersion, less crystalline CuO phase, and lower oxidation activity for CO and CH₄ than the CuN catalyst. For Cu/Ce/Al₂O₃ catalysts, Ce has little effect on the dispersion and crystallinity of the copper species. However, Cu impregnation decreases the Ce dispersion and increases the amount of crystalline CeO₂ present in the catalysts, particularly in Ce modified alumina prepared using cerium alkoxide precursor (CeA). Cerium addition dramatically increases the CO oxidation activity, however, it has little effect on CH₄ oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of surface modification on the dispersion of nanoscale α‐Al2O3 particles in a thermoplastic polyurethane matrix

In this study, two types of nanoscale α‐Al₂O₃ particles were used for preparation of α‐Al₂O₃/thermoplastic polyurethane (TPU) composites. These α‐Al₂O₃ particles were either coated or uncoated with stearic acid. For the uncoated α‐Al₂O₃/TPU composite, the results of field‐emission scanning electron microscopy (FE‐SEM) and energy dispersive X‐ray spectrometry indicate that uncoated α‐Al₂O₃ particles are significantly aggregated together. This aggregation is due to the poor compatibility between the inorganic filler (α‐Al₂O₃) and the organic matrix (TPU). The size of clusters is in the range from 5 to 20 μm. For the coated α‐Al₂O₃/TPU composite, FE‐SEM results indicate that most coated α‐Al₂O₃ particles are well dispersed in the TPU matrix. This phenomenon results from the effect of surface modifier (i.e., stearic acid) on α‐Al₂O₃ particles. Stearic acid can act as a compatibilizer to bridge the boundary between the TPU matrix and the α‐Al₂O₃ particle. Stearic acid is not only a suitable surface modifier for the nanoscale α‐Al₂O₃ particle, but also a good dispersant for the dispersion of nanoscale α‐Al₂O₃ particles in the TPU matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008