Microstructure and plasma corrosion behavior of yttria coatings prepared by the aerosol deposition method

Particle contamination arising from inner ceramic components of the plasma etching equipment has become a serious issue. Yttria (Y₂O₃) coatings prepared via aerosol deposition (AD) have demonstrated superior plasma resistance in the reduction of particle contamination. The superior particle contamination performance of Y₂O₃ coatings prepared by AD has been speculatively attributed to its unique microstructure; however, the relationship between the coatings’ microstructure and plasma corrosion behavior has been insufficiently clarified. Herein, we investigated the relationship between the microstructure and plasma corrosion behavior of Y₂O₃ coatings prepared by the AD method and compared the results with those for coatings prepared by other coating methods. When internal pores are present, these internal pores were selectively plasma corroded; plasma corrosion marks reflecting their pore shape were formed, and the surface roughness increased with increasing plasma exposure time. However, when no internal pores were present, as in the case of the AD coating, the surfaces were homogeneously corroded and maintained their initial surface. As the risk of particle contamination caused by the corrosion of the plasma-resistant coatings is greatly increased with surface roughness, we concluded that the Y₂O₃ coating prepared via AD will contribute greatly to reducing particle contamination.     

The corrosion behavior of sputter-deposited aluminum-tungsten alloys

Thin films on aluminum-tungsten alloys were prepared by co-deposition of pure aluminum and pure tungsten, each sputtered by an independently controlled magnetron source, on glass and sapphire substrates. Completely amorphous films were obtained in the Al₈₀W₂₀-Al₆₇W₃₃ composition range. Passivity and corrosion behavior of amorphous Al-W alloys were investigated in 1 M deaerated hydrochloric acid solution using polarization and impedance spectroscopy measurements and have been correlated with the properties of pure alloy components. Tungsten and sputter-deposited Al-W thin films are inherently passive materials while aluminum undergoes pitting corrosion in hydrochloric acid solution. The passive film formed at the OCP on each alloy possesses excellent electric and dielectric properties comparable to those of the isolating film on tungsten. The absolute impedance increases with increasing tungsten content in the alloy. According to electrochemical polarization measurements, alloying Al with W in solid solution significantly enhances the material's resistance to pitting corrosion by shifting the breakdown potential above 2000 mV (Al₆₇W₃₃) and lowering the corrosion rate at the OCP by more than two orders of magnitude. The most likely mechanism explaining the passivity of amorphous Al-W alloys, the Solute Vacancy Interaction Model (SVIM), involves the formation of complexes between highly oxidized solute atoms (W⁺⁶) and mobile cation vacancies, which restrict the transport of Cl⁻ through the oxide film and inhibit its breakdown in hydrochloric acid solution. The role that film stress relaxation effects and microscopic defects in amorphous Al-W films, of the some composition, and deposited on various substrates play in their corrosion resistance is discussed.     

Electronic structure and pitting behavior of 3003 aluminum alloy passivated under various conditions

Passivity of aluminum (Al) alloy 3003 in air and in aqueous solutions without and with chloride ions was characterized by electrochemical measurements, including cyclic polarization, electrochemical impedance spectroscopy (EIS), localized EIS and potential of zero charge, Mott-Schottky analysis and secondary ion mass spectroscopy (SIMS) technique. Stability, pitting susceptibility and repassivation ability of Al alloy 3003 under various film-forming conditions were determined. Results demonstrated that passive films formed on 3003 Al alloy in air and in Na₂SO₄ solution without and with NaCl addition show an n-type semiconductor in nature. The passive film formed in chloride-free solution is most stable, and that formed in chloride-containing solution is most unstable, with the film formed in air in between. Pitting of Al alloy 3003 passivated both in air and in aqueous solutions is inevitable in the presence of chloride ions. There is the strongest capability for the air-passivated Al alloy 3003 to repassivate, and the weakest repassivating capability for Al alloy 3003 passivated in chloride-containing solution. The resistance of the passivated Al alloy 3003 to pitting corrosion is dependent on the competitive effects of pitting (breakdown of passive film) and repassivation (repair of passive film). According to the differences between corrosion potential and potential of zero charge, passive film formed in air has the strongest capability to adsorb chloride ions, while the film formed in chloride-containing solution the least. Chloride ions causing pitting of passivated Al alloy 3003 in air and in chloride-free solution come from the test solution, while those resulting in pitting of passivated Al alloy 3003 in chloride-containing solution mainly exist in the film during film-forming stage.     

机械合金化Ni-20Cr合金电化学腐蚀行为研究

利用电化学方法以及化学浸泡法,结合XRD、TEM等表面分析技术,研究了机械合金化Ni-20Cr及粗晶Ni-20Cr合金在质量分数为3.5%NaCl溶液中的电化学腐蚀性能。结果表明机械合金化方法制备的Ni-20Cr合金的电化学腐蚀性能要低于粗晶Ni-20Cr合金。相对于粗晶合金,晶粒细化是合金机械合金化后耐蚀性能降低的主要原因。     

Localized corrosion of ultrafine-grained Al-Mg model alloys

The present study investigates passivity and localized corrosion of ultrafine-grained (UFG) binary Al-alloys with 0.5, 1 and 2 wt.% of magnesium subjected to three different equal-channel angular pressing (ECAP) pass numbers. The alloys were investigated by electrochemical techniques and surface analyses in different NaCl solutions and compared with their conventionally grained (CG) counterparts. The results of potentiodynamic polarization experiments indicated that the breakdown potential slightly decreased with increasing the ECAP pass number for all alloying series. Major differences are present in the pit transition potential (E_ptp), in that the potential shifts to more negative values with increasing number of passes in all series. EIS measurements showed no differences in corrosion resistance with increasing the number of ECAP passes at the open circuit state compared to their CG counterparts, indicating that passive layer properties are not affected by volume fraction of grain boundaries and dislocation density. Furthermore, serious pitting occurred for the coarse grained alloys in a kind of laterally spreading crystallographic filiform corrosion. In contrast, the UFG material exhibits solely local crystallographic pitting corrosion propagating in depth. The results indicate that UFG Al-Mg alloys tend with increasing pass number to deep localized pitting corrosion which leads to a hindered repassivation behavior compared to its CG counterpart, reflected in the negative shift in E_ptp.     

A characterization of the inhibiting effect of Cu on metastable pitting in dilute Al-Cu solid solution alloys

Copper additions to aluminum decrease susceptibility to pit initiation provided that Cu is retained in solid solution. This can be observed as an increase in pitting potential with increasing Cu content in an alloy. To further understand this effect, metastable pitting of high purity Al, Al-0.2Cu and Al-2.0Cu exposed to 0.1 M NaCl solutions has been examined in detail. Results show that 0.2 wt.% Cu additions decrease the metastable pit initiation rate by more than an order of magnitude and slow the pit growth rate mainly by decreasing the peak pit current attained. In an Al-2.0 wt.% alloy, metastable pitting events were too rare for rigorous study. Repassivation of metastable pits occurs by a two-stage process in Al-0.2 wt.% Cu alloy. The repassivation rate during the first stage is identical to that of high purity Al and appears to be completely unaffected by Cu in the alloy or in the pit solution. In the second stage, repassivation is slow, but is not believed to affect ultimate pit stability. Overall, Cu additions decrease the probability of stable pit formation by decreasing metastable pit initiation and growth rates.     

Effect of Al content on the corrosion behavior of Mg-Al alloys in aqueous solutions of different pH

The effect of systematic increase of Al content on the electrochemical behavior of the Mg-Al alloys in aqueous solutions of different pH was investigated. Different electrochemical methods such as open-circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy, EIS, were used to investigate the electrochemical behavior of the alloys in aqueous solutions. The results have shown that Mg-5Al is easily corroded due to the microgalvanic effect between α-phase and β-phase, its corrosion rate is even higher than that of Mg itself. The increase of Al content increases the corrosion resistance of the alloy due to the formation of the β-phase (Mg₁₇Al₁₂) together with the Mg α-phase. The ranking of the corrosion rate of these alloys was Mg-5Al > Mg > Mg-10Al ≅ Mg-15Al. The corrosion rates of the alloys in acidic solutions are pronouncedly high compared to those measured in neutral or basic solutions. The impedance measurements are in consistence with the polarization techniques and the impedance data were fitted to theoretical data obtained according to an equivalent circuit model describing the electrode/electrolyte interface.     

Electrochemical properties and corrosion protection of stainless steel for hot water tank

The state in which a stainless steel (STS) exhibits a very low corrosion rate is known as passivity, which is self-healing in a wide variety of environments. However, for those STS the corrosion includes pitting, crevice corrosion, galvanic corrosion, hydrogen embrittlement and stress corrosion cracking etc. And the corrosion resistance of STS is affected by area ratio, solution temperature and solution condition etc. Corrosion characteristics of STS 304, welding parts STS 316, STS 329 and STS 444 were investigated with parameters such as corrosion potential, galvanic current measurements, cathodic and anodic polarization behaviors as a function of area ratio and solution temperature in solution for hot water tank. It was found that galvanic current is affected by the area ratio, temperature and a kind of STS for hot water tank. Corrosion potential of welding part STS 316 was lower than that of STS 304, STS 329, STS 444 in solution for #1, #2 hot water tank. Therefore, it is suggested that the welding part STS 316 acts as anode for the other STSs. The amplitude of galvanic current between welding parts STS 316 and STS 304, STS 329, STS 444 in #1 solution is smaller than that in #2 solution. This is the reason that chloride ion quantity in #2 solution is more than that for #1 solution. And then welding part STS 316 corrodes easily by acting as anode compared to the other STS.     

Localized corrosion of Al90Fe5Gd5 and Al87Ni8.7Y4.3 alloys in the amorphous, nanocrystalline and crystalline states: resistance to micrometer-scale pit formation

The role of isothermal aging on the localized corrosion behavior of Al₉₀Fe₅Gd₅ and Al₈₇Ni_8.7Y_4.3 alloys was characterized in 0.6 M NaCl solution. The pitting (E_pit) and repassivation (E_rp) potentials were both increased ∼400 mV by the presence of transition and rare earth metal additions in supersaturated solid solution and amorphous structure. A statistical distribution in E_pit observed on small electrodes was due, in part, to the sensitivity of this critical potential to the presence of a population of critical surface flaws that serve as pit initiation sites. Mechanistic insight on the spacing of critical flaws was enabled by varying the tested electrode surface area. E_rp was not dependent on electrode surface area due to the similarity of pit depths in all electrode sizes. The critical potentials were also characterized after heat treating the amorphous ribbons isothermally at 150 °C for 25 h and 550 °C for 1 h. The former produced Al-rich nanocrystals embedded in the remaining amorphous matrix while the latter produced a fully crystalline condition containing intermetallic phases. Notably, the improved resistance to the formation of micrometer-scale pits was not lost compared with the fully amorphous condition when small Al-rich nanocrystals were present in an amorphous matrix. However, improvement in pitting corrosion resistance was completely lost in the fully crystallized condition as indicated by values for E_pit and E_rp that were similar to those of high purity, polycrystalline aluminum.     

A study of corrosion behavior of Ni-22Cr-13Mo-3W alloy under hygroscopic salt deposits on hot surface

Alloy 22, a nickel base Ni-22Cr-13Mo-3W alloy has an excellent corrosion resistance in oxidizing and reducing environments. Most of the corrosion studies on Alloy 22 have been conducted using conventional chemical or electrochemical methods. In the present investigation, the specimen was directly heated instead of heating the electrolyte, thereby simulating the nuclear waste package container temperature profile. Corrosion behavior of Alloy 22 and evaporation conditions of water diffusing on the container were evaluated using the newly devised heated electrode corrosion test (HECT) method in simulated acidified water (SAW) and simulated concentrated water (SCW) environments. In this method, the concentration of the environment varied with test duration. The corrosion rate of Alloy 22 was not affected by the continuous increase in ionic strength of the SAW (pH 3) environment. Passivation kinetics was faster with increase in concentration of the electrolytes. The major difference between the conventional test and HECT was the aging characteristics of the passive film of Alloy 22. The heated electrode corrosion test can be used for evaluating materials for construction of heat transfer equipments such as evaporators.     

Uniform and pitting corrosion events induced by SCN anions on Al alloys surfaces and the effect of UV light

The influence of the alloying elements on the uniform and pitting corrosion processes of Al-6061, Al–4.5%Cu, Al–7.5%Cu, Al–6%Si and Al–12%Si alloys was studied in 0.50 M KSCN solution at 25 °C. Open-circuit potential, Tafel polarization, linear polarization resistance (LPR) and ICP-AES measurements were used to study the uniform corrosion process on the surfaces of the tested alloys. Cyclic polarization, potentiostatic current-time transients and impedance techniques were employed for pitting corrosion studies. Obtained results were compared with pure Al. Passivation kinetics of the tested Al samples were also studied as a function of applied potential, [SCN⁻] and sample composition by means of potentiostatic current transients. The induction time, after which the growth of stable pits occurs, decreased with increasing applied potential and [SCN⁻]. Regarding to uniform corrosion, alloyed Cu was found to enhance the corrosion rate, while alloyed Si suppressed it. Alloying elements of the tested samples diminished pitting attack to an extent depending on the percentage of the alloying element in the sample. Among the investigated materials, Al–Si alloys exhibited the highest corrosion resistance towards uniform and pitting corrosion processes in KSCN solutions. The passive and dissolution behaviour of Al was also studied under the conditions of continuous illumination (300–450 nm) based on cyclic polarization and potentiostatic techniques. The incident photons had a little influence on pit initiation and a marked effect on pit growth. These explained in terms of a photo-induced modification of the passive film formed on the anode surface, which render it more resistant to pitting. The effects of UV photons energy and period of illumination on the morphology of the pitted surfaces were also studied.     

Electrochemical hydrogen storage behaviors of ultrafine Co-P particles prepared by direct ball-milling method

Ultrafine particles of Co-P were synthesized by direct ball milling of Co and P powders and also investigated as a reversible hydrogen storage electrode material. The electrochemical results demonstrated that the reversible charge-discharge capacity of the Co-P electrode can reach more than 300 mA h/g. In addition, the cycling ability and high rate capability of the Co-P electrode are excellent with only 5% capacity decay after 100 cycles at a high rate of 300 mA/g. The temperature-programmed desorption measurements (TPD) of the Co-P electrode revealed that the charge and discharge reactions of the Co-P electrode proceeds predominantly through electrochemical hydrogen storage mechanism and the electrooxidation of cobalt contributes only a negligible part to the reversible electrochemical capacity.     

Electrochemical behavior of palladium-gold alloys

The behavior of Pd-Au alloys, prepared by electrochemical codeposition, has been studied in acidic solutions (1 M H₂SO₄) using mainly the cyclic voltammetry technique. Morphology of the alloy surface and bulk compositions were examined by SEM/EDAX method. Various types of voltametric behavior during potential cycling in the oxygen region are presented. The influence of hydrogen absorption on electrochemical properties of surface oxides is demonstrated. The problem of the nature of oxygen electrochemisorbed on Pd-Au alloys is discussed.     

Pitting corrosion of Al and Al–Cu alloys by ClO4 ions in neutral sulphate solutions

The influence of various concentrations of NaClO₄, as a pitting corrosion agent, on the corrosion behaviour of pure Al, and two Al–Cu alloys, namely (Al + 2.5 wt% Cu) and (Al + 7 wt% Cu) alloys in 1.0 M Na₂SO₄ solution was investigated by potentiodynamic polarization and potentiostatic techniques at 25 °C. Measurements were conducted under the influence of various experimental conditions, complemented by ex situ energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) examinations of the electrode surface. In free perchlorate sulphate solutions, for the three Al samples, the anodic polarization exhibits an active/passive transition. The active dissolution region involves an anodic peak (peak A) which is assigned to the formation of Al₂O₃ passive film on the electrode surface. The passive region extends up to 1500 mV with almost constant current density (j_pass) without exhibiting a critical breakdown potential or showing any evidence of pitting attack. For the three Al samples, addition of ClO₄⁻ ions to the sulphate solution stimulates their active anodic dissolution and tends to induce pitting corrosion within the oxide passive region. Pitting corrosion was confirmed by SEM examination of the electrode surface. The pitting potential decreases with increasing ClO₄⁻ ion concentration indicating a decrease in pitting corrosion resistance. The susceptibility of the three Al samples towards pitting corrosion decreases in the order: Al > (Al + 2.5 wt% Cu) alloy > (Al + 7 wt% Cu) alloy. Potentiostatic measurements showed that the rate of pitting initiation increases with increasing ClO₄⁻ ion concentration and applied step anodic potential, while it decreases with increasing %Cu in the Al samples. The inhibitive effect of SO₄²⁻ ions was also discussed.     

Investigations of pitting corrosion of magnesium by means of DEIS and acoustic emission

The paper presents methodology and results of electrochemical examination of magnesium in 0.1 M NaCl solution with different pH. The measurements were conducted under potentiodynamic conditions using Dynamic Electrochemical Impedance Spectroscopy (DEIS). Analysis of DEIS results was performed based on electrical equivalent circuit. As the result of analysis changes of separate parameters of the equivalent circuit vs. potential for different pH values of the environment were obtained. Simultaneously with DEIS measurements an investigation using acoustic emission was conducted. The results showed that for pH higher than 12.50 the properties of layers on the surface of magnesium change significantly. One can observe a stable passive state that has properties considerably different from those of the layers that form in solutions with lower alkalinity. In such conditions the beginning of pitting corrosion process can be unequivocally determined by the level of acoustic emission and the values of electrochemical parameters.     

Electrochemical deposition and characterization of ZnCo alloys and corrosion protection by electrodeposited epoxy coating on ZnCo alloy

ZnCo alloys electrochemically deposited on steel under various deposition conditions were investigated. The influence of deposition current density, temperature and composition of deposition solution on the phase structure and corrosion properties of ZnCo alloys were studied. It was found that ZnCo alloy obtained from chloride solution at 5 A dm⁻² showed the best corrosion properties, so this alloy was chosen for further examination. Epoxy coating was electrodeposited on steel and steel modified by ZnCo alloy using constant voltage method. The effect of ZnCo alloy on the corrosion behavior of the protective system based on epoxy coating is interpreted in terms of electrochemical and transport properties, as well as of thermal stability.     

Protection of copper corrosion by modification of dodecanethiol self-assembled monolayers prepared in aqueous micellar solution

A novel method of preparing 1-dodecanethiol (DT) self-assembled monolayers (SAMs) on copper in aqueous micellar solution is explored. The resulting SAMs are characterized by XPS, contact angle tests and electrochemical measurements. It is found that DT dissolved in aqueous micellar solution can adsorb rapidly to the copper surface through strong thiolate bonds to form well-organized SAMs, which have properties comparable to those formed in ethanol solution. The electrochemical measurements show that the inhibition efficiency (IE) increases with an increase in the immersion time of copper in the aqueous micellar solution. After self-assembly for 1 h, the SAMs are able to effectively protect the underlying copper against corrosion in chloride-containing solution by hindering the cathodic process. Overall, the inhibition efficiency can reach 98.94%.     

Passivation and pitting corrosion of nanostructured Sn-Ni alloy in NaCl solutions

The passivation and pitting corrosion of tin-nickel alloy (34% Ni-66% Sn) in NaCl solution was studied using potentiodynamic, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques complemented by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of concentration of the chloride ion, the switching potential, scans rate and pH on the electrochemical behavior of Sn-Ni alloy is discussed. The data indicate that the corrosion rate and the pitting corrosion of Sn-Ni alloy increases by the increasing of chloride ion concentration. The observed corrosion resistance of electrodeposited Sn-Ni alloy is due to the formation of a thin passive film from tin and nickel oxides.     

Electrochemical corrosion behavior of nickel coating with high density nano-scale twins (NT) in solution with Cl

In this work, a nickel coating with high density nano-scale twins (NT) was synthesized on Q235 steel by using pulsed electrodeposition technique. The effects of NT structure on pitting corrosion resistance and semi-conducting properties of passive films formed on pure Ni in borate buffer solution with chloride ions were investigated by the potentiodynamic polarization measurements and capacitance measurements. The results indicated that the passive films formed on NT coatings showed higher pitting corrosion resistance and a bi-layer semi-conducting structure distribution, comparing with those formed on industrial electrodeposited (IE) nickel. The passive films are p-type semi-conductors at low potentials, but they show an n-type semi-conductor behavior at high potentials. It demonstrated that NT structure decreased vacancy diffusion velocity and slowed down the growth of passive films consequently. This led to the enhancement of pitting resistance for NT nickel.     

Pitting and stress corrosion cracking behavior in welded austenitic stainless steel

The effect of microstructural changes in 304 austenitic stainless steel induced by the processes of gas tungsten arc welding (GTAW) and laser-beam welding (LBW) on the pitting and stress corrosion cracking (SCC) behaviors was investigated. According to the in situ observations with scanning reference electrode technique (SRET) and the breakdown potentials of the test material with various microstructures, the GTAW process made the weld metal (WM) and heat-affected zone (HAZ) more sensitive to pitting corrosion than base metal (BM), but the LBW process improved the pitting resistance of the WM. In the initiation stage of SCC, the cracks in the BM and HAZ propagated in a transgranular mode. Then, the crack growth mechanism changed gradually into a mixed transgranular + intergranular mode. The cracks in the WM were likely to propagate along the dendritic boundaries. The crack initiation rate, crack initiation lifetime and crack propagation rate indicated that the high-to-low order of SCC resistance is almost the same as that for pitting resistance. High heat-input (and low cooling rate) was likely to induce the segregation of alloying elements and formation of Cr-depleted zones, resulting in the degradation in the corrosion resistance.