恒电位阳极极化,Potentiostatically anodic polarization,音标,读音,翻译,英文例句,英语词典
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-> 恒电位阳极极化
1)&&Potentiostatically anodic polarization
恒电位阳极极化
2)&&galvanostatic anodic polarization
恒电流阳极极化
Effectiveness of a new corrosion inhibitor in simulated pore solutions and mortar specimens was investigated through potentiodynamic scan,galvanostatic anodic polarization,and weight loss.
通过动电位扫描、恒电流阳极极化和失重法评价了自制的LN有机复合型钢筋阻锈剂在模拟孔溶液和砂浆中的阻锈效果,并探讨了阻锈机理。
3)&&potentiostatic polarization
恒电位极化
The process of electroless Ni-P plating on W-Cu alloy in NiSO_4-H_2PO~-_2system induced by potentiostatic polarization was studied.
试验通过恒电位极化诱发法在N iSO4-H2PO2-体系中实现了钨铜合金表面的化学镀镍磷。
4)&&amperometric i-t curves
恒电位阳极极化时间-电流曲线
The properties of micro-arc anodized films were evaluated by electrochemical impedance spectroscopy (EIS), amperometric i-t curves and potentiodynamic polarization curve method.
利用电化学方法(电化学阻抗谱、恒电位阳极极化时间-电流曲线和极化曲线)对制备得的微弧氧化膜的耐蚀性进行检测,同时研究了氧化时间、电解液温度等参数对镁合金微弧氧化所成膜性能的影响。
5)&&Potentiodynamic anodic polarization
动电位阳极极化
The electrochemical corrosion characteristics were investigated by measuring the potentiodynamic anodic polarization curves in the electrolyte of picric acid in China.
国内首次使用苦味酸电解液测定动电位阳极极化曲线研究电化学腐蚀特征,找到临界钝化电流密度和二次活化电流密度作为特征参数分析材料的电化学极化性能,多元线性回归得到测算FATT的模型,它可以评估转子钢老化程度,测算FATT精度在±20℃之内。
6)&&polarization potential
(阳极的)极化电位
补充资料：环状阳极极化曲线
分子式：CAS号：性质：钝性金属在含有氯离子的溶液中，用稳态慢速电位扫描方法，先向正电位方向，然后再向负电位方向扫描所测得的呈环状的阳极极化曲线。如图示(图暂缺)。Eb为孔蚀击穿电位，此时钝化膜开始破坏产生孔蚀；Ep为孔蚀保护电位，此时钝化膜重新愈合修补好，金属恢复钝态。这是表征金属对孔蚀敏感性的两个基本电化学参数，可评价金属的孔蚀倾向。
说明：补充资料仅用于学习参考，请勿用于其它任何用途。Corrosion Science 52 (–1624Contents lists available at ScienceDirectCorrosion Sciencejournal homepage: www.elsevier.com/locate/corsciCurrent oscillations during the anodic dissolution of copper in tri?uoroacetic acid? ? ? Neboj?a I. Potkonjak a,*, Tanja.N. Potkonjak b, Stevan.N. Blagojevic a, Boris Dudic c, Danijela V. Randjelovic daDepartmant of Electrochemistry, Institute of General and Physical Chemistry, P.O. Box 551, 11000 Belgrade, Serbia Town Planning Institute of Belgrade, Palmoticeva 30, 11000 Belgrade, Serbia c Faculty of Biology, University of Belgrade, Studenstki trg 3, 11000 Belgrade, Serbia d IChTM - Institute of Microelectronic Technologies and Single Crystals, P.O. Box 147, 11000 Belgrade, Serbiaba r t i c l ei n f oa b s t r a c tA phenomenon of current oscillators was characterized crosswise active–passive potential region during the electrodissolution of copper electrode in tri?uoroacetic acid (TFA). The current density-potential curves show two transition points. A potential region of current oscillations was found as a part of limiting current region. The Cu|TFA electrochemical oscillator was found to displaying rich dynamical response on varying the temperature and the applied potential. The Cu|TFA system display current oscillation behaviour from the mono-periodic to the mixed-mode (relaxation type). Changes of the electrode surface structure and morphology were investigated by X-ray diffraction spectroscopy, atomic forced microscopy and optical microscopy. ? 2010 Elsevier Ltd. All rights reserved.Article history: Received 21 July 2009 Accepted 11 February 2010 Available online 16 February 2010 Keywords: A. Copper B. Polarization B. Potentiostatic C. Acid corrosion C. Passivity1. Introduction Numerous electrochemical (metal|electrolyte) systems seem to exhibit non-linear dynamical behaviour in the form of current or potential oscillations during the electrodissolution-passivation of various metals in corrosive electrolyte solutions [1,2]. Ever since middle of nineteen century when unstable steady behaviour of electrochemical system has been observed for the ?rst time, spontaneous oscillations of electric current or potential, continuously seem to amaze electrochemists and theorists of non-linear dynamics. Particularly, current oscillations and features that issue this phenomenon are still extensively investigated [3–10]. Copper is known for plenty of favourable physical, chemical and mechanical properties which resulting in widely exploitation of copper in different types of industry (computer, microelectronic, automobile, energetic, etc.). Due to its broad application, corrosion of copper is considered as a signi?cant issue. Therefore, investigation of corrosion and corrosion inhibition of copper are widely studied. [11–15]. Inhibition of corrosion can be effectively applied only if mechanism that leads to corrosion is thoroughly understood. Electrochemical nature of corrosion–passivation phenomenon can consequently lead to appearance of current or potential oscillations. Such oscillations contain information on corrosion/ passivation processes at the surface of electrode. Current oscillatory phenomenon, during electrodissolution of metal in corrosive media, can be used in distinction between general and pitting cor* Corresponding author. Tel.: +381 11 ; fax: +381 11 . E-mail address:
(N.I. Potkonjak). X/$ - see front matter ? 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.rosion. Namely, Pagitsas et al. correlate the type of current oscillation periodicity with the type of corrosion [3,4]. It appears that, mono-periodic oscillation can be associated with general corrosion and complex oscillations with pitting corrosion. Although current oscillations are mostly observed and studied as a phenomenon and a tool for developing of non-linear dynamic theory, its applicability in corrosion science can be of a great interest. Current oscillations during the copper electrodissolution have been widely investigated in inorganic acidic aqueous electrolytes [16–23]. On contrary, only a few experimental achievements have been reported on the sustained current oscillations during the copper electrodissolution in organic acidic aqueous [24,25] or nonaqueous [7] electrolytes. Namely, Kiss et al. [24], quantitatively characterized the bifurcations leading to current oscillations during anodic electrodissolution of a copper in sodium acetate-glacial acetic acid electrolyte. Li et al. [25], reported rich dynamical behaviour of copper|trichloroacetic acid electrochemical oscillator. In this study, some new experimental details concerning current oscillatory behaviour during anodic electrodissolution of copper in 0.5 M tri?uoroacetic acid (TFA) are presented, as well as changes of the electrode structure and morphology that can lead to the understanding of the origin of this phenomenon. Since it was discovered in 1922, TFA has proved to be a signi?cant chemical in pharmaceutical and agricultural, as well as in many other specialized applications [26]. Conway and Novak [27] used TFA as chosen anhydrous solvent for investigation of oscillatory kinetics in electrochemical oxidation of hydrogen at platinum electrode. Although corrosion ability of TFA toward copper is well known, some ?rst observations on the current oscillatory phenomena ofN.I. Potkonjak et al. / Corrosion Science 52 (–16241619the Cu|TFA electrochemical system was reported in 2006 by Potkonjak et al. [10]. 2. Experimental The electrochemical measurements were performed in a threeelectrode electrolytical cell. The stationary working electrode was a copper rod (Goodefellows, 99.99% purity). The working electrode was embedded in plastic capillary, and sealed with resin leaving only the disk-end surface of the rod (0.5 mm in diameter) exposed to the electrolyte solution. Prior to each experiment the working electrode was abraded by a series of wet sandings at different grit size (320, 600, 800,
and 2000). After the mechanical polishing, the electrode was rinsed with alcohol and deionized water (18 MX cm) in an ultrasonic bath for 2 min in order to remove polishing residues. The reference electrode was the saturated calomel electrode (SCE). A Luggin capillary was used between the reference electrode and the working electrode in order to minimize the IR potential drop, the tip of capillary was set 2 mm away from the working electrode surface. Large-area cylindrical platinum net served as the counter electrode. Potential values were measured and are reported with respect to the SCE electrode. Electrolyte solutions were prepared from spectroscopic grade TFA (Sigma, T-6340) and deionized water. A volume of 100 ml of 0.5 M TFA electrolyte solution was used. Before each electrochemical measurement the electrolyte solution in the cell was deoxygenated with puri?ed nitrogen by continuous bubbling for 10 min. In order to avoid dissolution of oxygen into the electrolyte, puri?ed nitrogen was continuously passed above electrolyte surface during measurements. Electrochemical experiments were performed using Solartron SI 1286 electrochemical interface, supported with corrosion measurement software (CorrWare?). Linear sweep voltammetry was performed by applying positive scan from 0 to 1050 mV. The scan rates chosen were 2 and 10 mV s?1. Cyclic voltammteric (CV) measurements were carried out in the following manner: potential was scanned in positively (forward) direction from 0 to 750 mV (SCE), subsequently scanned negatively (backward) to 0 mV (SCE). The scan rate in CV measurements was 10 mV s?1. The potentiostatic measurements were performed on four different potentials: 510, 520, 545, 555 and 575 mV (SCE). The XRD characterization of the copper electrode was carried out by using an X-ray diffractometer (Philips APD PW-1710). Morphology of copper electrode was investigated by the atomic force microscopy (AFM), AutoProbe CP-Research SPM (TM Microscopes – Veeco) in the contact AFM mode and Stereomicroscope Stermi 2000 (Carl Zeiss) equipped with Canon Powershot A80. 3. Results and discussion Fig. 1 shows the current density–potential (j-E) anodic polarization curve for the Cu electrode in 0.5 M TFA, taken under a quasi-potentiostatic conditions (dE/dt = 2 mV s?1). Linear sweep voltammetry was carried out in order locate the potential region of current oscillations DEOSC. The j-E polarization curve provides very useful information about electrochemical and mass-transport processes occurring in the Cu|TFA interface. Namely, as shown in Fig. 1, three main potential regions can be distinguished in the polarization curve. In the region I active electrodissolution of copper takes place, this region is often named the active region. The active region could be further divided in to two sub-regions: the Tafel region, located at lower potentials, were j exponential increases with E, according the Tafel behaviour (log j – E); a sub-region that follows the Tafel region, located at higher potentials, were the j increases linearly with E. In the region II, the formation of broad anodic peak isFig. 1. j-E polarization curve of the dissolution of copper electrode in 0.5 M tri?uoroacetic acid during forward potential sweep at 298 K. Scan rate 2 mV s?1. Insert shows Tafel polarization curve for electrodissolution of copper in low-potential active region.observed. The appearance of this anodic peak suggests to the formation of the ?lm on the surface of copper electrode. This can be looked as consequence of following processes. During the electrodissolution of the electrode a large quantity of copper ions are present in the electrode/electrolyte interface, in order to preserve the electroneutrality, TFA? anions migrated towards the electrode surface and H+ ions migrate towards bulk solution. As a result, the formation of the ?lm on the surface of the copper electrode was encouraged by the precipitation of the saturated concentration of copper and TFA? anions in the electrode/electrolyte interface. The mass-transfer limited current plateau or the limiting current region, region-III, is established when the formation and the dissolution of a ?lm on the surface of the electrode proceeds at equal rates. As observed, the region DEOSC is a part of the limiting current region. In order to evaluate the number of electrons involved in the initial dissolution step, the Tafel analysis was applied. From the slope of the plot g vs. log j, presented in the insert of Fig. 1, were g / V represents the applied overpotential and j/A cm?2 the resulting (measured) current, the valence of the discharge ion, n, can be evaluated according following equation, known as Tafel slope [28]:ba ?glog j?2:3RT  Tafel slope ?1 ? b?nF?1?were T is absolute temperature, F(= 96,485 C mol?1) the Faraday constant, b (= 0.5) the charge transfer symmetry factor and R(= 8.314 J mol?1 K?1) the gas constant. Tafel analysis revealed that the Tafel slope is 120 mV dec?1. The value of n, derived from Eq. (1), for electrodissolution of Cu in TFA is calculated to be nominally 1, suggesting that one electron is involved in the initial dissolution of corroding copper electrode (Cu ? Cu+ + e?) in TFA. X-ray diffraction (XRD) patterns of the copper electrode, before electrochemical measurements and after it was previously electrochemically treated with 0.5 M TFA at 550 mV (SCE) for 100 s is presented in Fig. 2. Comparative analysis of XRD patterns have shown that practically all peaks could be indexed, belonging to metallic copper. The existence of a re?ection at 2h % 8° on XRD pattern of an electrochemically treated copper electrode could not be indexed. We believe that the origin of this peak is related to the existence of thick salt ?lm, formed on the electrode surface. This assumption is based on the fact on the re?ections belonging to the Cu2O were not observed on the XRD pattern, therefore the origin of ?lm should be a salt formed between Cu+ and TFA? ions. Additionally, formation of a white ?lm on the surface of copper1620N.I. Potkonjak et al. / Corrosion Science 52 (–1624Fig. 2. XRD patterns of the copper electrode: (a) after electrochemical treatment with 0.5 M tri?uoroacetic acid at 550 mV (SCE) for 100 s and (b) before electrochemical treatment.electrode, during current oscillations, was con?rmed by stereomicroscopy picture, Fig. 3. Similar observations were reported by Cooper et al. [16], Lee et al. [17] and by Basset and Hudson [19,20]. In these articles current oscillations were obtained during copper electrode electrodissolution in the presence of electrolyte containing Cl? ions, the observed porous white ?lm, in these experiments was assigned to the CuCl salt. In order to study this quantitative description of the origin of current oscillatory phenomena we applied atomic forced microscopy (AFM). Copper electrode was exposed to four different potentials inside and outside region DEosc. First ?nal potential was chosen to be in the active region, 420 mV (SCE). Second and third ?nal potential were deliberately chosen to be in the region DEosc, 520 and 620 mV (SCE) and fourth potential was selected to be more positively then DEosc, 800 mV (SCE). The electrode was potentiodynamically scanned up to the desirable potential with the scan rate of 10 mV s?1. Thereupon, experiment was stopped and the tip of electrode, exposed to the electrolyte, was sliced and transfer to the glassy vessel previously deoxygenated with nitrogen gas. AFM images of the copper electrode are presentedFig. 3. Photograph of the copper electrode polarized at 550 mV (SCE) for 100 s in 0.5 M tri?uoroacetic acid.in the Fig. 4. Obtained results have shown that investigated electrode have non-porous surface if the ?nal potentials were chosen to be outside region DEosc (Fig. 4, image A and D). In contrast, the porous surface of copper electrode was observed when ?nal potentials were inside region DEosc (Fig. 4, image B and C). Based on these observations it may be conclude that the porosity of electrode surface is in close relation with appearance of current oscillation of copper electrode in TFA solution. This stand point con?rms following observation, when the electrode was driven potentiodynamically from active region through region DEosc all the way to the limiting current region were current oscillations were not observed (more positively than DEosc) the lack of surface porosity is observed (Fig. 4, image D). The in?uence of surface porosity on the appearance of current oscillations was mathematically analyzed by Russel and Newman [29] and by Koper and Sluyters [30]. In order to investigate the temperature effect on the region DEOSC, temperature of the electrochemical cell was varied in a range from 25 to 45 °C. The j-E curves were obtained by linear polarization voltammetry applied from 0.0 V vs. SCE toward more positive, with the scan rate of 10 mV s?1. The domains of j-E polarization curves showing the region DEOSC at various temperatures are presented in Fig. 5. The region DEOSC was found to exist in the temperature range from 25 to 40 °C. The given system achieved maximal oscillatory response at 30 °C. That is, the largest DEOSC region and the height of amplitude and frequency of current oscillations were found on this temperature. The overall current oscillatory behaviour of the electrochemical system is inhibited by temperatures which are either lower or higher than 30 °C. Comparative analysis of DEOSC regions at 25 and 30 °C suggest that increase of temperature promote dynamical oscillatory response of the system. The region DEOSC at 30 °C is wider, i.e. the increasing temperature moves the bifurcation point at higher anodic potential toward more positive one, widening of DEOSC. This means that at 30 °C current oscillatory behaviour has been activated in the limiting current region where the electrode shows stable steady-state at 25 °C. On the other hand increasing of temperature above 30 °C results in decrease of overall current oscillatory behaviour of the system. The increase of temperature, higher than 30 °C, inhibits current oscillations. Furthermore, current oscillation were not observed at 45 °C, instead of that the electrode have overturned from limiting current to active dissolution. It appear that increase of temperature, above some critical value, calm down oscillatory behaviour of current, eventually promoting dissolution process of copper electrode at higher temperatures (&45 °C) if compared with precipitation process at the electrode surface. The above result imply to complex in?uence of the temperature on a processes which are responsible for current oscillatory behaviour. In order to investigate the effect of the applied potential on the current oscillations, the copper electrode was polarized at several potentials ranging from 510 to 570 mV (SCE) at 25 °C in 0.5 M TFA. As can been seen from the Fig. 6, in the potential region of current oscillations closer to the low potential stable steady-state, SS1, the typical mono-periodic current oscillation are observed at 510 V (SCE). The mono-periodic oscillations are not of the relaxation type but almost sinusoidal. As applied potential was increased at 520 mV (SCE), a small-amplitude oscillation was observed on the left shoulder of large amplitude one, Fig. 7. Still, oscillatory behaviour can be described more as sinusoidal. The number of small-amplitude oscillations increases with further increasing of the applied potential, Fig. 8. The electrochemical Cu/TFA system entered a complex temporal oscillatory behaviour known as mixed-mode oscillations (MMOs). Mixed-mode oscillations consist of a mixture of two distinctly kinds of oscillation: small-amplitude (harmonic) oscillations and large-amplitude (relaxation) oscillations [24]. Furthermore, as applied potentialN.I. Potkonjak et al. / Corrosion Science 52 (–16241621Fig. 4. AFM images of the copper surface electrode after it was polarized potentiodynamically with scan rate 10 mV s?1 up to ?nal potential: (A) 420, (B) 520, (C) 620 and (D) 800 mV (SCE).Fig. 5. Oscillatory domain (DEOSC) in the anodic j-E polarization curves of the dissolution copper electrode in 0.5 M tri?uoroacetic acid at various temperatures. Scan rate 10 mV s?1.was increased, immediately after the large-amplitude oscillation, current oscillation behaviour vanished for a period of time. It is no doubt that system changes it dynamical behaviour from unstable steady-state to stable steady-state. Since this steady-state is unstable, system re-enters non steady-state indicated by the birth of harmonic oscillations. MMOs of the Cu|TFA oscillator manifest itself in a complicated bifurcation sequences known as periodic– chaotic sequences [31]. These oscillations can be considered as a kind of bursting oscillations. Bursting oscillations, de?ned by van Venrooij and Koper, are complex waveform in which relatively si-lent steady-state-like phases are interrupted with highly active phases of strong oscillations [32]. In our case, large-amplitude oscillations appear in periodic sequences and small-amplitude oscillation in chaotic. Number of small-amplitude oscillations differs from sequence to sequence chaotically, but no matter to that, it was noticed a linear relationship between number of smallamplitude oscillations and the lifetime-period of oscillatory sequence (ss), Fig. 9. The transient from mono-periodic to MMOs oscillations could be explained in light of changes of the electrode surface porosity.1622N.I. Potkonjak et al. / Corrosion Science 52 (–1624Fig. 6. The sequence of current oscillations for the Cu|0.5 M TFA system at 510 mV (SCE) on 25 °C.Fig. 9. Linear relationship between number of small-amplitude oscillations and its length-period taken the sequence of current oscillations for the Cu|0.5 M TFA system at 570 mV (SCE) on 25 °C.Fig. 7. The sequence of current oscillations for the Cu|0.5 M TFA system at 520 mV (SCE) on 25 °C.Fig. 8. The sequence of current oscillations for the Cu|0.5 M TFA system at 570 mV (SCE) on 25 °C.current oscillations with small amplitude and high frequency. With increase of ?nal potential in region DEosc, porosity of surface seams to decrease and pores size increased (about 5 lm). This change of surface morphology is manifested through the increase of current oscillations amplitude and the decrease of it frequency. Obtained results of the potentiostatic experiments enable bifurcation analysis of the electrochemical Cu/TFA system. The amplitude of current oscillations was found to be proportional to |E ? Ebif1|0.5, were E is the applied potential and Ebif1 is the bifurcation potential on the pathway from low potential stable steady states (SS1) to oscillatory state (OSC), Fig. 10 A. This behaviour suggest to the existence of Hopf-type bifurcation when the system is moved throughout SS1 ? OSC. On the other hand, as can be seen from Fig. 10B, the period of oscillations (s) increases as potential is closer to the second bifurcation point, transition from OSC to high potential stable steady-state SS2. The existence of period lengthening by varying of applied potential as controllable parameter suggested on saddle-type bifurcation point on pathway OSC ? SS2. Furthermore, the existence of the hysteresis loop of the potential region of current oscillations was proved trough cyclic voltammetry, like proposed by Koper [33]. The hysteresis loop was observed between the forward and the following backward potential scan, Fig. 9. The existence of hysteresis, indicates the existence of generalized Hopf bifurcation for transition SS1 ? OSC and saddle-loop bifurcation for transition OSC ? SS2 [33–35]. Bifurcation analysis of the electrochemical Cu|TFA system have show that the investigated system can be used as a model in understanding of the origin of current oscillatory behaviour observed during metal electrodissolution in organic acids. The increase of the amplitude of current density oscillations with increase of the scan rate from 2 mV s?1 (Fig. 1) to 10 mV s?1 (Fig. 11) can also be observed. The increase of amplitude of current density oscillations is due to the increased scan rate. This may suggest that dynamic of potential sweep could interfere in ?lm formation/dissolution, since anodic processes taking place on these potentials are time-depending. However, no reliable power law can be extracted from these observations. The similar results were obtained by Koper and Aguda [36]. 4. Conclusions The existence of the potential region of current oscillations was observed during electrodissolution of copper electrode in 0.5 MNamely, the surface porosity seams to decrease with increasing ?nal potential in region DEosc, (Fig. 4, image B and C). High surface porosity of the electrode with small pore size (less than 1 lm in diameter), Fig. 4 image B, results in appearance of mono-periodicN.I. Potkonjak et al. / Corrosion Science 52 (–16241623ical oscillator is a capable to generate various types of current oscillations (mono-periodic and mixed-mode oscillations). Monoperiodic oscillations were found to be more sinusoidal than relaxation type. Mixed-mode oscillations were found to consist of small-amplitude (harmonic) oscillations followed by one large (relaxation) one. Number of small-amplitude oscillation increases with increasing applied potential. Obtained mixed-mode oscillations could be considered as bursting oscillations, with the periodic–chaotic sequences interrupted by silent steady-state-like phases. A generalized Hopf bifurcation and a saddle-type bifurcation were noticed at transition points. The current oscillatory behaviour is assigned to periodically formation and dissolution of porous white ?lm on the surface of the copper electrode. The existence of the porous ?lm on the surface of the electrode was observed with optical microscopy and its porosity was analyzed by atomic force microscopy.Acknowledgement Grateful acknowledgment is made to the Ministry of Science and Technological Development of Republic Serbia for support of this research under Project No. 142025.References[1] J.L. Hudson, T.T. Tsotsis, Electrochemical reaction dynamics: a review, Chem. Eng. Sci. 49 (–1572. [2] K. Krischer, Spontaneous formation of spatiotemporal pattern at the electrode electrolyte|interface, J. Electroanal. Chem. 501 (. [3] M. 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