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31.
Our 1D + 1D model of DMFC reveals a new effect. At infinitely small total current in the cell, near the channel inlet forms a “bridge”, a narrow region with finite local current density. The bridge short-circuits the electrodes, thus reducing cell open-circuit voltage. In our previous work the effect is described for the case of equal methanol λa and oxygen λc stoichiometries. In this Letter, we analyze the general case of arbitrary λa and λc. In the case of λa > λc current may occupy finite domain of the cell surface. Asymptotic solution for the case of λa λc shows, that the size of this domain is proportional to oxygen stoichiometry. In the opposite limit of λa λc local current exponentially decreases with the distance along the channel. Asymptotic solutions suggest that the bridge forms regardless of the relationship between λa and λc. In all cases local current density in the bridge increases with the rate of methanol crossover and decreases with the growth of the “rate-determining” stoichiometry. The expression for voltage loss at open-circuit is derived. 相似文献
32.
Mathematical apparatus, which makes it possible to perform calculations of the current-voltage characteristics of cathodes of fuel cells with a solid polymer electrolyte in conditions where there are present extraneous diffusion restrictions is proposed. In so doing, the partial pressure of oxygen and the absolute pressure of gas in the gas chamber may assume any values. First of all presented are the results of calculations of the current-voltage characteristics intrinsic to active layers of the air and oxygen cathodes, which are performed under the assumption that the extraneous diffusion restrictions are absent altogether. Thereafter, in the same conditions (at the same parameters that characterize the active layer of a cathode), obtained are results of a calculation of the current-voltage characteristics inherent in the air and oxygen cathodes in the presence of extraneous diffusion restrictions. Afterward there is performed an analysis of the way a gas-diffusion layer restricts the process of generation of current in a cathode and of what measures should be taken in order for the extraneous diffusion restrictions to become less significant. 相似文献
33.
L. M. Korotaeva T. Ya. Rubinskaya V. P. Gul'tyai 《Russian Journal of Electrochemistry》2003,39(11):1203-1210
It is shown that the electrocatalytic hydrogenation (ECH) of trans-2-allyl-6-R-1,2,3,6-tetrahydropyridines (R = Me, All, Ph) on a nickel cathode (Nidisp/Ni) in 40-% aqueous DMF in the presence of excess AcOH yields products of total hydrogenation of all double bonds—relevant trans-2-propyl-6-R1-piperidines (R1 = Me, Pr, Ph). Selective hydrogenation of terminal double bonds of allyl substituents in piperideines under study with the retention of the intracycle double bond may be realized on a copper cathode (Cuann), provided the stoichiometric ratio between AcOH and the initial substance is observed exactly. In either case, at points of maximum selectivity of ECH processes, the ratio c
AcOH/c
ini = n+ 1, where nis the number of hydrogenated bonds. The difference in the ECH mechanisms on the Cuann and Nidisp/Ni cathodes is discussed. The results of hydrogenation of the trans-2-allyl-6-R-1,2,3,6-tetrahydropyridines at the Cuann and Nidisp/Ni cathodes confirm the general character of regularities discovered earlier during ECH of citral. 相似文献
34.
Methane, mixed with argon, has been polymerized by means of a hollow-cathode discharge system. Two types of cathodes were studied; one was made of a solid solution of 81% tungsten and 19% platinum, while the other was of pure tungsten. Under identical operating conditions, a higher polymer yield was found in the case of the platinum cathode (90% against 70% for tungsten). The work function of the solid solution was estimated to be 6.3 eV, compared with 4.4 eV for tungsten. In terms of the data available, the thermionic current, which is the main source of energetic electrons, is about one order of magnitude lower for the solid solution cathode when compared with the tungsten cathode thermionic current. However, the polymer yield observed is higher in the former case. The concentration of the CH species in the hollow cathode was found to differ greatly for the cathodes tested and was about 5 times higher in the case of tungsten-platinum cathodes. Since no excited platinum vapor could be detected in the gas phase, the increase in CH concentration was attributed to a catalytic effect of the cathode inside surface. An evaluation of the plasma polymer deposition rate yields 70 nm·s–1 for the platinum-tungsten type hollow cathode and 42 nm·s–1 for the tungsten one. In both cases, the deposition rate is much higher than those obtained from the most widely used methods for plasma polymer deposition (0.10–1.0 nm·s–1) implying methane-argon mixtures, and is comparable to the results obtained with a new type of plasma polymer deposition reactor described in the literature. 相似文献
35.
Guadalupe Fortuño 《Plasma Chemistry and Plasma Processing》1988,8(1):19-34
A parametric study of the etching of Si and SiO2 by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF4, CF3Cl, CF2Cl2, and CFCl3 (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO2 as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF2. The activation energy for the etching reaction of Si during CF4 RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO2 depended more strongly on the sheath voltage than on the F-to-Cl ratio. 相似文献
36.
37.
《Surface and interface analysis : SIA》2003,35(5):445-449
Surface states of polydimethylsiloxane (PDMS) treated by plasma were investigated by x‐ray photoelectron spectroscopy and surface voltage decay. X‐ray photoelectron spectroscopy confirmed the formation of a silica‐like (SiOx, x = 3–4) oxidative surface layer. This layer increased in thickness with increasing exposure duration of plasma. Plasma exposure lowers the surface resistivity from 1.78 × 1014 to 1.09 × 1013 Ω □?1 with increasing plasma treatment time. By measuring the decay time constant of surface voltage, the calculated surface resistivity was compared with the value measured directly by a voltage–current method; good agreement between the two methods was obtained. It was observed that plasma treatment led to a decrease in the thermal activation energy of the surface conduction from 31.0 kJ mol?1 for an untreated specimen to 21.8 kJ mol?1 for a plasma‐treated specimen for 1 h. Our results allow the examination of effects of plasma on the electrical properties of PDMS. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
38.
《Arabian Journal of Chemistry》2022,15(7):103933
In this study, a fingerprint-activity relationship modeling between chemical fingerprints and antirheumatic activity was established, and multivariate statistical analysis was used to evaluate the quality of Taxilli Herba (TH) from different hosts. Characteristic fingerprints of 20 batches of TH samples were generated by high-performance liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry (HPLC-Triple TOF-MS/MS), and the similarity analysis was calculated based on thirteen common characteristic peaks by hierarchical clustering analysis (HCA). Subsequently, nine efficacy markers were discovered by combining fingerprints and antirheumatic activity through grey correlation analysis (GCA) and bivariate correlation analysis (BCA). Meanwhile, the content of 5 constituents in 9 markers was determined by high-performance liquid chromatography coupled with triple quadrupole-linear ion trap tandem mass spectrometry (HPLC-QTRAP-MS/MS). The comprehensive quality of TH was assessed using multivariate statistical analysis, including principal components analysis (PCA) and technique for order preference by similarity to ideal solution (TOPSIS). The results showed that a high dose of TH extract could markedly ameliorate arthritis damage compared to other doses, with flavonoids playing an important role in the antirheumatic activity. The comprehensive quality of samples from Morus alba L. (SS) was superior to those from Liquidambar formosana Hance (FXS). The present study will demonstrate the markers associated with efficacy, and provide an applicable strategy for more comprehensive quality control and evaluation of TH. 相似文献
39.
N. M. Bogdanovich V. P. Gorelov V. B. Balakireva T. A. Demyanenko 《Russian Journal of Electrochemistry》2005,41(5):576-581
The phase composition and electroconduction in air of solid electrolytes (Ce0.8Sm0.2)1 − x
CuxO2 − δ (CSCu), where x = 0, 2, 5, 10, and 20 mol % and which are synthesized using the ceramic technology, are studied. Adding an additive of CuO lowers the CSCu sintering temperature by 100– 200°C and leads to the formation of single-phase solid solutions of a fluorite type up to x = 10 mol %. The electroconductivity of the CSCu electrolytes remains practically invariant upon adding up to 5 mol % Cu and equals 0.089–0.095 and 0.017–0.021 S cm−1 at 800 and 600°C. The sintering, adhesion, and electroconductance of composite cathodes based on La0.8Sr0.2MnO3 with 40% CSCu and their electrochemical behavior in air in the temperature interval 900–1000°C on carrying electrolyte Zr0.9Y0.1O1.95 with a CSCu sublayer containing 2 mol % Cu are studied.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 656–661.Original Russian Text Copyright © 2005 by Bogdanovich, Gorelov, Balakireva, Dem’yanenko. 相似文献
40.
Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that
- Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
- Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
- Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
- Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.