Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Heavy arsenic doping of silicon grown by atmospheric pressure selective epitaxial chemical vapor deposition

Selective epitaxial Si with a high arsenic concentration of 2.2×10¹⁹ atoms/cm³ was deposited at a high growth rate of 3.3 nm/min under atmospheric pressure. It was confirmed that this method had excellent selectivity and produced films having good crystalline quality, abrupt dopant profiles at the interfaces, and smooth surfaces. The growth mechanism is discussed in terms of the relationship between the effects of arsenic surface segregation and etching by hydrogen chloride.     

Streaming potential measurements on stainless steels surfaces: evidence of a gel-like layer at the steel/electrolyte interface

Electric charges at the surface of a passive stainless steel are generally considered as concentrated either in the passive film itself, or at the metal/passive film interface, or in the electrical double layer at the film solution interface. Rest potential time dependence after immersion of a passive surface in aqueous electrolytes suggests however that slow processes occur in the onset of the surface charge. Specific experiments, such as streaming potential measurements and electrochemical impedance spectroscopy in a thin electrolyte cell, were carried out for understanding better this phenomenon. An AISI 304 type austenitic stainless steel with polished or bright annealed surface finishes was immersed in NaCl aqueous solutions with various pH and chloride concentrations. The streaming potential time evolution shows two steps: a first rapid one (∼2 min) is attributed to the onset of the surface charge. The second step is much slower (approximately several hours) and possibly due to an interphase layer between the passive film and the solution. Following this idea, the whole kinetics is controlled by cation migration across the interphase when the pH is larger than the isoelectric pH (pH_iep), while chloride ions are incorporated in the interphase when pH < pH_iep. Impedance measurements allow determining both the kinetics of charge transport and the thin cell conductivity. When glass is used as reference material for the cell walls instead of stainless steel, the Nyquist plots show a high-frequency response. For stainless steel cell walls, a low-frequency response is observed, attributed to a slow charge reorganisation inside the interphase layer. The charge distribution at metal/electrolyte interface is discussed in terms of a gel-like layer which possibly takes place at the passive film/electrolyte interface.     

A disposable single-use electrochemical sensor for the detection of uric acid in human whole blood

We report here a non-enzymatic detecting electrode strip for fast monitoring of uric acid in human whole blood. A single-use amperometric uric acid sensor strip, incorporating a three-electrode configuration, has been fabricated on a polypropylene substrate using low cost screen-printing (thick-film) technology. Both the working and counter electrodes were prepared by screen-printing commercial carbon ink. The integration on the same support of pseudo-reference electrode was obtained by screen-printing a commercial silver ink and subsequent electrochemical pretreatment. Simply by placing a 20 μl human whole blood drop on the strip is enough for uric acid analysis by square-wave voltammetry. Real human whole blood samples were analyzed by this method and compared to the phosphotungstic acid clinical test procedure with satisfactory results.     

溶液温度对电化学沉积氧化亚铜薄膜相成分和显微结构的影响

用电化学方法在不锈钢基体上沉积多晶Ｃｕ２Ｏ薄膜并用Ｘ射线衍射和扫描电进行了分析研究了溶液温度对薄膜相组成、晶粒尺寸和择优取向的影响，当溶液的ＰＨ＝９，温度低于５０℃时得到的是Ｃｕ２Ｏ／Ｃｕ复相薄膜，纯Ｃｕ２Ｏ薄膜可在溶液温度高于５０℃时获得，纯Ｃｕ２Ｏ薄膜具有（１００）择优取向，实验发现薄膜的晶粒尺寸随溶液温度的增加从０．１２μｍ增加到０．６５μｍ。     

喷雾沉积快速凝固技术的发展与展望

喷雾沉积是制取大体积快凝材料的一种新工艺。本文综述了它的产生和发展，概述了其基本原理和过程控制。对该领域今后的发展动向，提出了一些新看法。     

Electrochemical noise analysis for estimation of corrosion rate of carbon steel in bicarbonate solution

We have investigated the electrochemical noise behavior of carbon steel in fully deaerated aqueous bicarbonate solutions, and discussed the optimum conditions of the noise analysis for estimating corrosion rate of the steel. Noise of the potential difference and of the short-circuit current between two identical steel coupons were successfully measured. The time-series noise patterns were transformed into frequency domain by fast Fourier transformation, and then their power spectrum densities (PSDs) at a frequency were determined to be compared with the corrosion rate. The PSDs of the potential and of the current varied with changing environmental factors of bicarbonate concentration, pH, and immersion time. The factors also controlled the corrosion rate of the steel. The PSDs were associated with the corrosion rate, and then it was found that the PSDs of the potential and of the current showed linear correlation with the corrosion rate in log-log scale. There was also linear relationship between the corrosion rate and a spectral noise resistance obtained from the PSDs of the potential and the current. The linearities of the three correlations were better at a lower analyzed frequency. Furthermore, the PSDs of the current and the noise resistance indicated more linear correlation with the corrosion rate than that of the potential. As the simplicity of the measurement system is additionally considered, it is concluded that the PSD of the current noise at an analyzed frequency of 3 mHz is the optimum conditions for estimating the corrosion rate from 10⁻² to 10⁰ A m⁻² in this study.     

Electrical and optical properties of oxygen doped GaN grown by MOCVD using N2O

Oxygen doped GaN has been grown by metalorganic chemical vapor deposition using N₂O as oxygen dopant source. The layers were deposited on 2″ sapphire substrates from trimethylgallium and especially dried ammonia using nitrogen (N₂) as carrier gas. Prior to the growth of the films, an AIN nucleation layer with a thickness of about 300? was grown using trimethylaluminum. The films were deposited at 1085°C at a growth rate of 1.0 μm/h and showed a specular, mirrorlike surface. Not intentionally doped layers have high resistivity (>20 kW/square). The gas phase concentration of the N₂O was varied between 25 and 400 ppm with respect to the total gas volume. The doped layers were n-type with carrier concentrations in the range of 4×10¹⁶ cm⁻³ to 4×10¹⁸ cm⁻³ as measured by Hall effect. The observed carrier concentration increased with increasing N₂O concentration. Low temperature photoluminescence experiments performed on the doped layers revealed besides free A and B exciton emission an exciton bound to a shallow donor. With increasing N₂O concentration in the gas phase, the intensity of the donor bound exciton increased relative to that of the free excitons. These observations indicate that oxygen behaves as a shallow donor in GaN. This interpretation is supported by covalent radius and electronegativity arguments.     

Effect of chloride ions on immersion plating of copper onto porous silicon from a methanol solution

The effect of chloride ions (Cl⁻) during the immersion plating of copper onto porous silicon (PS) from a methanol (MeOH) solution has been studied. The presence of Cl⁻ in the Cu²⁺ solution was found to slow down the rate of copper deposition, as confirmed by inductively coupled argon plasma emission spectroscopy and X-ray photoelectron spectroscopy measurements. The threshold concentration of Cl⁻ at which the deposition of copper is very severely diminished was found to be 0.1 M. The inhibition effect is discussed on the basis of the rest potential values of PS and polarization curve measurements. They revealed that the rest potential of PS upon dipping in these solutions appears to direct the metal deposition. Current density-potential curves show that at Cl⁻ concentrations higher than 0.1 M, the reduction of Cu ions proceeds in two steps; the reduction of Cu(II) to Cu(I) followed by the reduction of Cu(I) to Cu(0). This suggests that Cu(I) species in MeOH solution can be stable over a certain potential range and this stability of Cu(I) is responsible for the inhibition of metal deposition. Fourier transform infrared spectroscopy and scanning electron microscopy (SEM) were also performed to investigate the structural changes and characterizations of PS samples after the plating process.