This paper describes the corrosion behavior of aluminum, copper, and mild steel when exposed to chloride media using both electrochemical noise analysis (ENA) and electrochemical impedance spectroscopy (EIS). Analysis...This paper describes the corrosion behavior of aluminum, copper, and mild steel when exposed to chloride media using both electrochemical noise analysis (ENA) and electrochemical impedance spectroscopy (EIS). Analysis of electrochemical noise (EN) data demonstrated the need for removal of drifts in both potential and current fluctuations. Statistical analysis such as noise resistance, localization index, skewness and kurtosis has been evaluated. Noise resistance showed a good agreement with polarization resistance. Fast Fourier transformation (FFT) has been applied to convert EN data from the time domain to the frequency domain. Spectral noise plots showed a good agreement with impedance spectra for the different alloys determined at the same exposure time. Spectral and statistical analysis can extract useful information from EN data.展开更多
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 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.展开更多
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 microscop...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.展开更多
The potential noise during corrosion of pure aluminum in sodium chloride solution was recorded and analyzed with wavelet transform technique. The typical results show that the electrochemical noise (EN) signal is comp...The potential noise during corrosion of pure aluminum in sodium chloride solution was recorded and analyzed with wavelet transform technique. The typical results show that the electrochemical noise (EN) signal is composed of distinct type of events, which can be classified according to their scales, i.e. time constants. And the process underlying the rapid fluctuations of EN, which is characterized by a small scaling value, i.e. high frequency components and which is usually used for local analysis, is not consistant with time; whilst those associated with slower processes or characterized by a large scaling value, which are usually used for global analysis, are continuous.展开更多
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 ...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.展开更多
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 analy...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.展开更多
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 alu...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-.展开更多
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/...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.展开更多
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) var...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.展开更多
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 g...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.展开更多
The corrosion process of AZ91D magnesium alloy in neutral 1%(mass fraction) sodium chloride aqueous solution was investigated by electrochemical noise(EN),SEM and EDX. Fractal theory was primarily used to depict the c...The corrosion process of AZ91D magnesium alloy in neutral 1%(mass fraction) sodium chloride aqueous solution was investigated by electrochemical noise(EN),SEM and EDX. Fractal theory was primarily used to depict the corrosion process of the alloy. The fast wavelet transform(FWT),as well as the fast Fourier transform(FFT),was employed to analyze the EN data. The results show that the overall corrosion process can be described by three stages. The first stage corresponds to the pit nucleation and growth; the second stage involves the growth of a passive oxide layer; and the third stage involves reactivation. With increasing immersion time,fractal dimension increases fast initially,fluctuates in the medium and increases again at last. Pitting corrosion and fractal dimension increase due to the initiation and formation of pits in the initial and the end of immersion,while depresses due to the passivation in the medium period. The results of SEM and EDX support the above conclusions.展开更多
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),fl...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.展开更多
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 cu...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.展开更多
The nickel electroplating process was investigated by means of electrochemical noise(EN), cyclic voltammetry in conjunction with the scanning electron microscopy(SEM) technique. The results show that, in the experimen...The nickel electroplating process was investigated by means of electrochemical noise(EN), cyclic voltammetry in conjunction with the scanning electron microscopy(SEM) technique. The results show that, in the experimental conditions and with the increase of current density, the growth mechanism of nickel crystallites changes from 2-D to 3-D with the potential turning point of about -1.15 V, and the potential for the onset of diffusion control of the ensemble nickel electroplating process was about -1.4 V. In the case of activation-control, the two-dimensional (2-D) nucleation / growth process of nickel often results in the electrocrystallization EN features of only slowly small positive potential drift and the corresponding compact layer-by-layer deposit structure, and the maximum relative energy of the RP-EDP (re-plotted relative energy distribution plot), which is obtained from wavelet analysis, defined in the region with smaller scales. While under the diffusion-control, the three-dimensional (3-D) nucleation / growth process of nickel, often results in the electrocrystallization EN features of both the fast positive potential drift and subsequent remarkable negative potential drift and the corresponding dentritic/large conglomerate structure of nickel deposit, and the maximum relative energy of the RP-EDP defined in the region with larger scales. The electroplating time affects the nickel deposit structure mainly through its influence on the growth rate of crystallites and the Ni2+ ions diffusion process around each crystallite.展开更多
The manuscript presents the results from the electrochemical noise (EN) monitoring of Inconel 82 weld overlay on Type 304L stainless steel (SS) weld in 0.01M FeCl3. The microstructure of the weld overlay obtained from...The manuscript presents the results from the electrochemical noise (EN) monitoring of Inconel 82 weld overlay on Type 304L stainless steel (SS) weld in 0.01M FeCl3. The microstructure of the weld overlay obtained from optical and scanning electron microscopy (SEM) showed an austenite structure, containing equiaxed dendrites and secondary phases at the interdendritic region. Energy dispersive spectroscopy (EDS) attached to SEM revealed the secondary phases to be Nb rich Laves phase. The electrochemical potential noise was monitored using a three identical electrode configuration. The acquired signals were detrended, and wavelet analysis was employed to encode useful information from the noise transients. Visual examination of the potential noise-time record contained distinct high amplitude transients typical of localized corrosion attack. The energy distribution plots (EDP) of the potential noise derived from wavelet analysis depicted maximum relative energy on D6-D8 crystals, which represent large time scale events such as those occurring from localized attacks. Also, repassivation events too could be divulged from the potential EDP. The micrographs of the post electrochemical noise experimented specimens revealed the occurrence of localized attacks along the interdendritic region and none inside the dendritic cores. The presence of secondary phases along the interdendritic regions was found to be detrimental in chloride medium, imparting inferior localized corrosion resistance to the weld overlay.展开更多
Stainless steel(SS)is one of the most widely used engineering materials in marine engineering.However,its corrosion in the marine atmospheric environment due to the high concentration of Cl-is a problem.The SS corrosi...Stainless steel(SS)is one of the most widely used engineering materials in marine engineering.However,its corrosion in the marine atmospheric environment due to the high concentration of Cl-is a problem.The SS corrosion is a threat to the development and security of marine industry;therefore,evaluating the corrosion resistance of SSs is necessary.In this work,atmospheric corrosion detection probes based on a symmetrical electrode system were used to study the corrosion behaviors of 304 SS and 2205 duplex stainless steel(DSS)in a simulated marine atmosphere.A theoretical model for electrochemical noise(EN)data analysis based on the Thevenin electrochemical equivalent circuit(EEC)model was established.The relationship between the EN characteristic parameters and the corrosion rate was obtained.The Thevenin EEC model analysis showed that the relationship between the noise resistance(Rn),the noise impedance[Rsn(f)],and the impedance modulus(|Z(f)|)was Rn≈Rsn=■.Thus,Rn and Rsn can be used as indicators for quantitative corrosion evaluation.The results of EN detection for the 304 SS and 2205 DSS showed that in a simulated marine atmospheric environment,the passive fi lms on the two SSs were relatively intact at the initial exposure stage,and their dissolution rates were slow.The corrosion resistance of the 2205 DSS was higher than that of the 304 SS.With the deposition of Cl-on the SS surface,pitting was initiated and the dissolution rate increased.The pitting initiation process on the SS surface was random,and part of the active pores could be repassivated.展开更多
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 e...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.展开更多
In view of the limitations of a Rn-Gn model in the low frequency range and the defects of an En-In model in common use now, this paper builds a complete En-In model according to the theory of random harmonic. The para...In view of the limitations of a Rn-Gn model in the low frequency range and the defects of an En-In model in common use now, this paper builds a complete En-In model according to the theory of random harmonic. The parameters for the low-noise design such as the equivalent input noisy voltage Ens, the optimum source impedance Zsopt and the minimum noise figure Fmin can be calculated accurately by using this En-In model because it considers the coherence between the noise sources fully. Moreover, this paper points out that it will cause the maximum 30% miscalculation when neglecting the effects of the correlation coefficient 7. Using the series-series circuits as an example, this paper discusses the methods for the En-In noise analysis of electronic circuits preliminarily and demonstrates its correctness through the comparison between the simulated and measured results of the minimum noise figure Fmin of a single current series negative feedback circuit.展开更多
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...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.展开更多
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 no...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.展开更多
文摘This paper describes the corrosion behavior of aluminum, copper, and mild steel when exposed to chloride media using both electrochemical noise analysis (ENA) and electrochemical impedance spectroscopy (EIS). Analysis of electrochemical noise (EN) data demonstrated the need for removal of drifts in both potential and current fluctuations. Statistical analysis such as noise resistance, localization index, skewness and kurtosis has been evaluated. Noise resistance showed a good agreement with polarization resistance. Fast Fourier transformation (FFT) has been applied to convert EN data from the time domain to the frequency domain. Spectral noise plots showed a good agreement with impedance spectra for the different alloys determined at the same exposure time. Spectral and statistical analysis can extract useful information from EN data.
基金supported by the National Natural Science Foundation of China(Grant No.20203015).
文摘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.
基金This work was supported by the National Natural Science Foundation of China(No.20203015 and No.50499335).
文摘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.
文摘The potential noise during corrosion of pure aluminum in sodium chloride solution was recorded and analyzed with wavelet transform technique. The typical results show that the electrochemical noise (EN) signal is composed of distinct type of events, which can be classified according to their scales, i.e. time constants. And the process underlying the rapid fluctuations of EN, which is characterized by a small scaling value, i.e. high frequency components and which is usually used for local analysis, is not consistant with time; whilst those associated with slower processes or characterized by a large scaling value, which are usually used for global analysis, are continuous.
基金Acknowledgements - The authors wish to acknowledge the financial support of the National Key Basic Research Foundation of China
文摘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.
基金the financial support of the National Key Basic Research Foundation of China (Project G19990650), the National Natural Science Foundation of China (Project 50071054) and the financial support of State Key
文摘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.
基金The authors wish to acknowledge the financial support of the national key basic research foundation of China (Grant No. G19990650), the National Natural Science Foundation of China (Grant No. 50071054) and State key Laboratory for Corrosion and Protecti
文摘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-.
基金Project(2006CB605004) supported by the National Basic Research Program of China
文摘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.
文摘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.
文摘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.
基金Projects(50471043, 50771092) supported by the National Natural Science Foundation of ChinaProject(2005DKA10400-Z15) supported by the National R&D Infrastructure and Facility Development Program of ChinaProject supported by Key Laboratory for Ultra-light Materials and Surface-treatment Technology of Education Ministry of China
文摘The corrosion process of AZ91D magnesium alloy in neutral 1%(mass fraction) sodium chloride aqueous solution was investigated by electrochemical noise(EN),SEM and EDX. Fractal theory was primarily used to depict the corrosion process of the alloy. The fast wavelet transform(FWT),as well as the fast Fourier transform(FFT),was employed to analyze the EN data. The results show that the overall corrosion process can be described by three stages. The first stage corresponds to the pit nucleation and growth; the second stage involves the growth of a passive oxide layer; and the third stage involves reactivation. With increasing immersion time,fractal dimension increases fast initially,fluctuates in the medium and increases again at last. Pitting corrosion and fractal dimension increase due to the initiation and formation of pits in the initial and the end of immersion,while depresses due to the passivation in the medium period. The results of SEM and EDX support the above conclusions.
基金Supported by the National Basic Research Program of China("973"Program,No.2011CB610505)National Natural Science Foundation of China(No.61240038)
文摘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.
基金supported by the National Natural Science Foundation of China (Nos. 51304047 and 51374066)the Ph.D. Programs Foundation of the Ministry of Education of China (No.20130042120040)
文摘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.
基金Project(20203015) supported by the National Natural Science Foundation of China Project supported by the State Key Laboratory for Corrosion and Protection of China
文摘The nickel electroplating process was investigated by means of electrochemical noise(EN), cyclic voltammetry in conjunction with the scanning electron microscopy(SEM) technique. The results show that, in the experimental conditions and with the increase of current density, the growth mechanism of nickel crystallites changes from 2-D to 3-D with the potential turning point of about -1.15 V, and the potential for the onset of diffusion control of the ensemble nickel electroplating process was about -1.4 V. In the case of activation-control, the two-dimensional (2-D) nucleation / growth process of nickel often results in the electrocrystallization EN features of only slowly small positive potential drift and the corresponding compact layer-by-layer deposit structure, and the maximum relative energy of the RP-EDP (re-plotted relative energy distribution plot), which is obtained from wavelet analysis, defined in the region with smaller scales. While under the diffusion-control, the three-dimensional (3-D) nucleation / growth process of nickel, often results in the electrocrystallization EN features of both the fast positive potential drift and subsequent remarkable negative potential drift and the corresponding dentritic/large conglomerate structure of nickel deposit, and the maximum relative energy of the RP-EDP defined in the region with larger scales. The electroplating time affects the nickel deposit structure mainly through its influence on the growth rate of crystallites and the Ni2+ ions diffusion process around each crystallite.
文摘The manuscript presents the results from the electrochemical noise (EN) monitoring of Inconel 82 weld overlay on Type 304L stainless steel (SS) weld in 0.01M FeCl3. The microstructure of the weld overlay obtained from optical and scanning electron microscopy (SEM) showed an austenite structure, containing equiaxed dendrites and secondary phases at the interdendritic region. Energy dispersive spectroscopy (EDS) attached to SEM revealed the secondary phases to be Nb rich Laves phase. The electrochemical potential noise was monitored using a three identical electrode configuration. The acquired signals were detrended, and wavelet analysis was employed to encode useful information from the noise transients. Visual examination of the potential noise-time record contained distinct high amplitude transients typical of localized corrosion attack. The energy distribution plots (EDP) of the potential noise derived from wavelet analysis depicted maximum relative energy on D6-D8 crystals, which represent large time scale events such as those occurring from localized attacks. Also, repassivation events too could be divulged from the potential EDP. The micrographs of the post electrochemical noise experimented specimens revealed the occurrence of localized attacks along the interdendritic region and none inside the dendritic cores. The presence of secondary phases along the interdendritic regions was found to be detrimental in chloride medium, imparting inferior localized corrosion resistance to the weld overlay.
基金the National Natural Science Foundation of China(No.51701140)。
文摘Stainless steel(SS)is one of the most widely used engineering materials in marine engineering.However,its corrosion in the marine atmospheric environment due to the high concentration of Cl-is a problem.The SS corrosion is a threat to the development and security of marine industry;therefore,evaluating the corrosion resistance of SSs is necessary.In this work,atmospheric corrosion detection probes based on a symmetrical electrode system were used to study the corrosion behaviors of 304 SS and 2205 duplex stainless steel(DSS)in a simulated marine atmosphere.A theoretical model for electrochemical noise(EN)data analysis based on the Thevenin electrochemical equivalent circuit(EEC)model was established.The relationship between the EN characteristic parameters and the corrosion rate was obtained.The Thevenin EEC model analysis showed that the relationship between the noise resistance(Rn),the noise impedance[Rsn(f)],and the impedance modulus(|Z(f)|)was Rn≈Rsn=■.Thus,Rn and Rsn can be used as indicators for quantitative corrosion evaluation.The results of EN detection for the 304 SS and 2205 DSS showed that in a simulated marine atmospheric environment,the passive fi lms on the two SSs were relatively intact at the initial exposure stage,and their dissolution rates were slow.The corrosion resistance of the 2205 DSS was higher than that of the 304 SS.With the deposition of Cl-on the SS surface,pitting was initiated and the dissolution rate increased.The pitting initiation process on the SS surface was random,and part of the active pores could be repassivated.
基金Funded by the National Natural Science Foundation of China(Nos.51701140 and 51371124)the Major State Basic Research Development Program(973 Program)(No.2014CB046805)
文摘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.
文摘In view of the limitations of a Rn-Gn model in the low frequency range and the defects of an En-In model in common use now, this paper builds a complete En-In model according to the theory of random harmonic. The parameters for the low-noise design such as the equivalent input noisy voltage Ens, the optimum source impedance Zsopt and the minimum noise figure Fmin can be calculated accurately by using this En-In model because it considers the coherence between the noise sources fully. Moreover, this paper points out that it will cause the maximum 30% miscalculation when neglecting the effects of the correlation coefficient 7. Using the series-series circuits as an example, this paper discusses the methods for the En-In noise analysis of electronic circuits preliminarily and demonstrates its correctness through the comparison between the simulated and measured results of the minimum noise figure Fmin of a single current series negative feedback circuit.
基金supported by the National Key R&D Program of China(2022YFB3705300)the National Natural Science Foundation of China(Nos.52034004,52271111 and 52171123).
文摘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.
基金Projects (51131005, 51171172, J0830413) supported by the National Natural Science Foundation of ChinaProject (Y4110074) supported by Zhejiang Provincial Natural Science Foundation, China
文摘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.
