CORROSION MONITORING OF LY12 IN SODIUM CHLORIDE SOLUTION WITH ELECTROCHEMICAL NOISE TECHNIQUE

Spontaneous electrochemical noise (EN) can be a rich source of information concerning the processes simultaneously occurring on a corroding interface. But the noise signal is often difficult to be analyzed due to the complicated nature of the specific systems being investigated. In this paper, the potential noise fluctuations during the free corrosion of commercial aluminum alloy LY12 in sodium chloride solution was recorded and analyzed with different techniques. The typical results showed that the fractal dimension (D,n) obtained from spectral power density (SPD) is mainly directly proportional to the intensity of pitting corrosion and to the value of pitting parameter (SE) derived from dimensional analysis, while the fractal dimension (DE) obtained from EIS is mainly related to the uniform corrosion.

Characterization of stress corrosion crack growth of 304 stainless steel by electrochemical noise and scanning Kelvin probe

The fatigue pre-cracking 304 stainless steel （SS） specimens with lengths of 1.002 mm （L-crack） and 0.575 mm （S-crack） were prepared. Their corrosion behavior was studied by electrochemical noise （EN） in 4 mol/L NaC1 ＋ 0.01 mol/L Na2S203 solution under slow-strain-rate-testing （SSRT） conditions. Moreover, the characteristics of L-crack＇s surface morphology and potential distribution with scanning Kelvin probe （SKP） before and after SSRT were also discussed. Compared with S-crack, L-crack is propagated and the features of crack propagation can be obtained. After propagation, the noise amplitudes increase with increasing stress and accelerating corrosion, the white noises at low and high frequencies （WE and WH） of the later stage are one order of magnitude larger than that at early stage in the current power spectral densities （PSDs）. The potential PSDs also increase, but WH disappears. In addition, the crack propagation can be demonstrated according to variation of probability distribution, surface morphology and potential distribution.

ELECTROCHEMICAL NOISE ANALYSIS OF PURE ALUMINUM IN SODIUM CHLORIDE SOLUTION WITH WAVELET TRANSFORM TECHNIQUE

Wavelet transforms (WT) are proposed as an alternative tool to overcome the limitations of Fourier transforms (FFT) in the analysis of electrochemical noise (EN) data. The most relevant feature of this method of analysis is its capability of decomposing electrochemical noise records into different sets of wavelet coefficients, which contain information about the time scale characteristic of the associated corrosion event. In this context, the potential noise fluctuations during the free corrosion of pure aluminum in sodium chloride solution was recorded and analyzed with wavelet transform technique. The typical results showed that the EN signal is composed of distinct type of events, which can be classified according to their scales, i.e. their time constants. Meanwhile, the energy distribution plot (EDP) can be used as 'fingerprints' of EN signals and can be very useful for analyzing EN data in the future.

Online evaluation of electroless deposition rate by electrochemical noise method

Continuous noise resistance calculation(CNRC)technique was used for online determination of the electroless nickel deposition rate on zirconium pretreated magnesium alloy.For this purpose,the noise resistance(R_n) variation with time was calculated for the pretreated alloy surface in the electroless plating solution.The CNRC results were described by energy dispersive X-ray spectroscopy(EDS)and scanning electron microscopy(SEM)techniques.Also,potentiodynamic polarization and gravimetric measurements were used for determination of the electroless deposition rate at the same time period and the results were compared with the CNRC results.The Rn variation with plating time shows that the electroless plating consists of different stages with various deposition rates.The results of the CNRC and polarization methods were not in acceptable agreement due to the limitations of the polarization method for online monitoring of the deposition rate.However,the results of the gravimetric measurements were in complete agreement with the CNRC technique and so,the CNRC can be considered as suitable tool for online evaluation of the electroless deposition rate.

ELECTROCHEMICAL NOISE FEATURES OF PURE ALUMINUM DURING PITTING CORROSION IN NEUTRAL NaCl SOLUTION

Spontaneous electrochemical noise (EN) can be a rich source of information concerning the processes simultaneously occurring at a corroding interface. Potential noise fluctuations during the free corrosion of pure aluminum in different concentration of neutral sodium chloride solution are investigated, and the breakdown and restoration of passive metal's film are studied using potentiodynamic scanning (PDS) measurements and electrochemical impedance spectroscopy (EIS) technique. Two capacitance loops are observed in the Nyquist plots in two kinds of concentration, and the corrosion process is under activation control at first, then become diffusion control within the oxide film and corrosion products of (Al(OH)p-mCl-m) accumulated on the surface of the corroding electrode. It is suggested that the pitting corrosion is much easier to occur for pure aluminum in 7.0wt% than in 2.0wt% NaCl solution, and the high concentration of chloride ion in solution inhibits the repassivation of a metastable pit. The corrosion rate deterministic step does not involve Cl-.

Galvanic corrosion behavior of plain carbon steel-B_4C composite in 3.5% NaCl solution with electrochemical noise

The galvanic corrosion behavior of metal-matrix composite plain carbon steel/boron carbide （B4C） in 3.5% NaCl solution was studied. The composite was locally produced as a weld band on carbon steel by means of the gas tungsten arc welding process and using nickel as the wetting agent. Samples from the weld band, heat-affected zone and parent metal region were extracted precisely and DC/AC electrochemical tests in combination with techniques such as scanning electron microcopy and energy dispersive spectrometry were conducted. The results of the electrochemical tests show that the corrosion resistance of the parent metal sample is higher than that of the welded composite and the HAZ samples. However, as the corrosion potential （Eco^r） of the parent metal is more positive than other two samples, this becomes the cathode in galvanic couples with two other samples. On the other hand, the weld composite sample is also cathodic due to its more positive Ecorr compared to HAZ sample. This means that the HAZ can be particularly at risk of preferential dissolution. The approach can be used in specific areas on plain carbon steel to locally increase hardness and resistance to abrasion and reduce manufacturing costs.

Portable 4-Channel Electrochemical Noise Test System

A portable 4-channel electrochemical noise(EN) test system with high precision was developed.The modular instrument cRIO was used as its core and the signal conditioning module included zero resistance ammeter(ZRA),fly line,screening box and shielded wire.The EN data were acquired from two Q235 carbon steel specimens placed in 0.5 mol/L H2SO4 solution and 0.1 mol/L NaCl solution.The experimental result shows that this system can achieve an accuracy of 10 pA and 10 μV,and it can be applied to on-site multi-channel EN test.

In situ characterization of natural pyrite bioleaching using electrochemical noise technique

An in situ characterization technique called electrochemical noise（ECN） was used to investigate the bioleaching of natural pyrite.ECN experiments were conducted in four active systems（sulfuric acid,ferric-ion,9k culture medium,and bioleaching solutions）.The ECN data were analyzed in both the time and frequency domains.Spectral noise impedance spectra obtained from power spectral density（PSD）plots for different systems were compared.A reaction mechanism was also proposed on the basis of the experimental data analysis.The bioleaching system exhibits the lowest noise resistance of 0.101 MΩ The bioleaching of natural pyrite is considered to be a bio-battery reaction,which distinguishes it from chemical oxidation reactions in ferric-ion and culture-medium（9k） solutions.The corrosion of pyrite becomes more severe over time after the long-term testing of bioleaching.

ELECTROCHEMICAL NOISE ANALYSIS OF THE INFLUENCE OF THE Zn^(2+)IONS CONCENTRATION ON ZINC ELECTROPLATING

The influence of the concentration of Zn2+ ions on zinc electroplating process was investigated by means of electrochemical noise (EN) and cyclic voltammetry methods in conjunction with the scanning electron microscopy (SEM) technique. It was found that the EN generated during the electroplating of dentritic or large polymeric zinc deposit has large potential oscillation amplitude and positive potential drift while the compact zinc deposit possesses small noise amplitude and little potential drift. With the change of rate determining step from diffusion-control through mixed-control to activation-control, the maximum relative energy obtained from wavelet analysis defined from the region with larger scales to those with smaller scales, and the EDP (relative energy distribution plot) can be us, as 'fingerprints' of EN to characterize the electroplating process and the deposit structure. The results also showed that electrochemical noise technique can give more information about the electrodeposit structure than other normal electrochemical measurements, such as linear potential sweep method and cyclic voltammetry technique.

STUDY THE INFLUENCE OF H_(3)BO_(3)ON THE ZINC ELECTROPLATING USING ELECTROCHEMICAL NOISE TECHNIQUE

The influence of H3BO3 on the zinc electroplating was studied using electrochemical noise technique, cyclic voltammetry and steady-state polarization method. The results showed that, under the experimental conditions, the deposition of zinc followed the mechanism of two-dimensional nucleation and subsequent grain growth. The addition of H3BO3 into the electroplating solution prominently changes the nucleation and growth kinetics of zinc deposits, which is directly related to the features of electrocrystallization noise and the corresponding structure of the electrodeposits. The results also shown that the electrochemical noise (EN) technique can give more information about the electrodeposits structure and electroplating mechanism than other normal electrochemical measurements can give, such as steady-state polarization method and cyclic voltammetry technique.

Effect of pH and applied stress on hydrogen sulfide stress corrosion behavior of HSLA steel based on electrochemical noise analysis

The influence mechanism of pH and the externally applied stress on sulfide stress corrosion cracking behavior based on the joint analysis of the in situ electrochemical noise and microstructure was studied.The results showed that{\mathrm{H}}^{+}in solution changes the composition and structure of corrosion product film by affecting the concentration of{\mathrm{S}}^{2-}and{\mathrm{Fe}}^{2+}near the anode surface.When the pH increased from 2.6 to 3.6 and 4.6,the corrosion product film changed from porous Mackinawite to dense and stable FeS.The change in corrosion product type delayed the crack initiation time by 10.5 and 45.5 h,while the uniform corrosion time was prolonged by 6.1 and 46 h,respectively,delaying SSC behavior.After increasing the applied stress,the local plastic deformation on the material surface increases the porosity and crack rate of the corrosion product film and becomes a fast propagation channel for SSC cracks.When the applied stress is 110%of the actual yield strength of the material,the initiation time of stress corrosion cracking is 6 and 18.1 h earlier than that of 90%and 100%,respectively.The local corrosion time was extended by 23.5 and 8.2 h,respectively,accelerating SSC behavior.

Electrochemical noise analysis on the pit corrosion susceptibility of biodegradable AZ31 magnesium alloy in four types of simulated body solutions

Magnesium alloys have been investigated as biodegradable implant materials since the last century. Non-uniform degradation caused by local corrosion limits their application, and no appropriate technology has been used in the research. In this study, electrochemical noise has been used to study the pit corrosion on magnesium alloy AZ31 in four types of simulated body solutions, and the data have been analyzed using wavelet analysis and stochastic theory. Combining these with the conventional polarization curves, mass loss tests and scanning electron microscopy, the electrochemical noise results implied that AZ31 alloy in normal saline has the fastest corrosion rate, a high pit initiation rate, and maximum pit growth probability. In Hanks＇ balanced salt solution and phosphate-buffered saline, AZ31 alloy has a high pit initiation rate and larger pit growth probability, while in simulated body fluid, AZ31 alloy has the slowest corrosion rate, lowest pit initiation rate and smallest pit growth probability.

Analysis of cracks origin behaviors during sulfide stress corrosion (SSC) in HSLA steel at different temperatures by electrochemical noise

The sulfide stress corrosion(SSC)behaviors of the high strength low alloy steel at the different temperatures were investigated by the microstructural observation and electrochemical noise(EN)analysis.With the corrosion temperature increasing from 20 to 40℃,SSC ruptured time is prolonged.The increase in corrosion temperature results in the decrease of the saturation solubility of H_(2)S in the solution and thus increases pH value of solution.The increase in corrosion temperature decreases the size of the holes and cracks in the corrosion product film on the surface of the sample,which is due to the formation of the dense FeS corrosion product film.The current kurtosis results indicate that the time for the first occurrence of crack initiation is postponed by the increase in the corrosion temperature.The standard deviation of current noise signals,current kurtosis,power spectral density and energy distribution plot results shows a great consistency,which suggests that EN analysis method can reflect SSC behaviors in real time.

Potentiostatic Electrochemical Noise Analysis of 2101 Lean Duplex Stainless Steel in 1mol/L NaCl

The critical pitting temperature （CPT） of 2101 lean duplex stainless steel （DSS） in 1 mol/L NaCl was investigated.Potentiostatic electrochemical noise （EN） technique coupled with scanning electron microscopy （SEM） was used to study the corrosion process of 2101 DSS at different temperatures （15,25,28,and 35 C） from below CPT to above CPT.The EN data were analyzed by wavelet technique based on orthogonal db4 wavelet.The results showed that,the patterns of current noises were different at different temperatures.The characteristics of energy distribution plot （EDP） obtained from wavelet analysis technique can be used as ＂fingerprints＂ of EN signal and can be used to interpret the corrosion process.With increasing solution temperature,the maximum relative energy defined in EDP changed from the region of crystal series coefficients with smaller scales through middle scales to larger scales,which indicated the process of initiation,propagation and growth into stable pitting of metastable pitting.The results were well confirmed by the corresponding morphologies.

Shot noise analysis on corrosion behavior of zinc alloy (ZnAl4Cul) under dry-wet cycles

The corrosion behaviors of zinc alloy （ZnAl4Cul） in 3.5% （mass fraction） NaCl, 7.3% （mass fraction） Na2SO4 and simulated acid rain solutions were investigated using electrochemical measurements. The potential noise during dry-wet cycle was monitored and analyzed by fast Fourier transform （FFT）, fast wavelet transform （FWT）, shot noise theory and stochastic theory. Cumulative probability curves of event frequency fn indicate that the corrosion events in the dry cycles are greater than those in the wet cycles. Uniform corrosion was observed in the NaCl solution compared with more localized corrosion in the Na2SO4 solution, which is evidenced by FWT and SEM. Conditional events generation rate r（t） for diffusion controlled reactions decreases with increasing the time. r（t） values for uniform corrosion and diffusion controlled process are the largest in the wet cycle in 3.5% NaCl solution. The values of r（t） for pitting corrosion in Na2SO4 solution are observed to become large during spraying periods, and r（t） for pitting corrosion has the largest value in the Na2SO4 solution. The intergranular corrosion of zinc is serious in simulated acid rain solution.

Atmospheric Corrosion Monitoring of Field-exposed Q235B and T91 Steels in Zhoushan Offshore Environment Using Electrochemical Probes

This work aimed to in-situ monitor the atmospheric corrosion of steels exposed to Zhoushan offshore environment by using electrochemical noise（EN） technique. A portable EN monitoring system was established and two electrochemical probes（named as Q235 B and T91） were designed. Experimental results indicated that the noise resistance of T91 steel was higher than that of Q235 B steel, revealing that the corrosion resistance of T91 was higher than that of Q235 B. A 60-day monitoring result indicated that the noise resistance was well correlated with the weight loss data. Wavelet analyses results of EN data indicated that Q235 B underwent uniform corrosion and T91 suffered from localized corrosion, which was further confirmed by the surface observation. It is concluded that EN can be used as a new method to identify the corrosion form and corrosion resistance in atmospheric conditions.

Effect of surface damage induced by cavitation erosion on pitting and passive behaviors of 304L stainless steel

The corrosion behavior of 304L stainless steel(SS)in 3.5wt%NaCl solution after different cavitation erosion(CE)times was mainly evaluated using electrochemical noise and potentiostatic polarization techniques.It was found that the antagonism effect resulting in the passivation and depassivation of 304L SS had significant distinctions at different CE periods.The passive behavior was predominant during the incubation period of CE where the metastable pitting initiated at the surface of 304L SS.Over the rising period of CE,the 304L SS experienced a transition from passivation to depassivation,leading to the massive growth of metastable pitting and stable pitting.The depassivation of304L SS was found to be dominant at the stable period of CE where serious localized corrosion occurred.

Galvanic corrosion behavior of copper/titanium galvanic couple in artificial seawater

The corrosion behaviors of copper and copper/titanium galvanic couple （GC） in seawater were studied by electrochemical impedance spectroscopy （EIS） and electrochemical noise （EN） techniques in conjunction with scanning electron microscopy （SEM） method. The results show that the corrosion process of copper in seawater can be divided into two stages, in which corrosion resistance and SE show the same evolution trend of initial increase and subsequent decrease, while SG changes oppositely. However, the ensemble corrosion process of copper/titanium GC in seawater includes three stages, in which corrosion resistance and SE show the evolution features of initial decrease with a subsequently increase, and the final decrease again;while SG changes oppositely. The potential difference between copper and titanium in their galvanic couple can accelerate the initiation of pitting corrosion of copper, and both the minimum and maximum corrosion potentials of copper/titanium GC are much more positive than those of pure copper.

Characterization of pitting corrosion of 7A60 aluminum alloy by EN and EIS techniques

The pitting corrosion behaviors of 7A60 aluminum alloy in the retrogression and re-aging （RRA） temper were investigated by electrochemical impedance spectroscopy （EIS） and electrochemical noise （EN） techniques, and the microstructure and the second phase content of the alloy were observed and determined by scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS）. The results show that there exist two different corrosion stages for 7A60 alloy in 3.5%NaCl solution, and the corrosion process can be detected by the appearance of EIS spectrum with two capacitive time constants and the wavelet fractal dimension D extracted from EN. SEM and EDS results also demonstrate that severe pitting corrosion in 7A60 alloy is mainly caused by electrochemical active MgZn2 particles, secondly by Al2MgCu and Mg2Si. Al7Cu2Fe particles make little contribution to the pitting corrosion of 7A60 alloy.

Contrasting initial events of localized corrosion on surfaces of 2219-T42 and 6061-T6 aluminum alloys exposed in Caribbean seawater

Aluminum alloy samples, 6061-T6 and 2219-T42, were exposed to Caribbean seawater for 90 d. The fluctuations of open circuit potential, considered as electrochemical noise (EN), were used to characterize and compare initial pitting events, which appeared on their surfaces. EN analysis was carried out using the power spectral density (PSD) vs frequency. The decrease of the β exponent in PSD graphs indicated a release of spontaneous energy with the progress of pit formation in seawater. The fluctuations were associated with the breakdown and formation of new corrosion layers. The values of β exponent in PSD graphs suggest that corrosion process of AA2219-T42 alloy occurs as a persistent non-stationary process, the dynamics of which is controlled by fractional Brownian motion (fBm), while on AA6061-T6 alloy the corrosion process was dominated by stationary and weakly persistent features, with the contribution of fractional Gaussian noise (fGn). After the exposure in seawater, SEM-EDX analysis revealed insoluble intermetallic particles on the alloys, rich in Cu or Fe and irregularly distributed. The preferential dissolution of Mg and Al occurs from the S-phase (Al2CuMg) of AA2219-T42 alloy.