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www.elsevier.com/locate/corsci

electrochemical noise with wavelet transform

X.F. Liu

a,b,*

State Key Laboratory for Mechanical Behavior of Materials, Xian Jiaotong University,

Xian 710049, PR China

Received 23 June 2004; accepted 1 June 2005

Available online 15 August 2005

Abstract

In the study, the fractal parameters were introduced to describe the irregular characteristic

of electrochemical noise, which were calculated with wavelet transform to overcome some

defects of other methods. Compared with other fractal parameters, wavelet standard deviation

(STD) exponent (Hws) had smaller deviation and could describe the fractal characteristics of

electrochemical noises in a wide range, therefore Hws was chosen to evaluate general and local

irregularity of potential signals generated from 7075-T76 aluminum alloy in 3.5% NaCl solution without and with dierent inhibitors respectively. The results showed that the smaller general Hws value, the more frequently potential uctuated on the electrode surface, and the less

eect of inhibitor in the solution. The dierence between general Hws and 1 reected the condition of surface passivity. Local Hws could eectively extract the local feature of electrochemical noise and quantitatively describe the change of its fractal characteristic with time, which

was a promising index to analyze electrochemical noise in practice.

2005 Elsevier Ltd. All rights reserved.

Keywords: Electrochemical noise; Wavelet transform; Fractal; Standard deviation of wavelet coecient;

General and local feature

*

Corresponding author. Address: State Key Laboratory for Mechanical Behavior of Materials, Xian

Jiaotong University, Xian 710049, PR China. Fax: +86 029 323 7910.

E-mail address: xiaofang_liu@263.net (X.F. Liu).

0010-938X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.

doi:10.1016/j.corsci.2005.06.001

1338

1. Introduction

Mandelbrot introduced the concept of fractals in terms of statistical self-similarity, the idea that the shape of an object did not dene its size [1]. The original example was the length of a rocky coastline, a map of a rocky coastline gave no indication

of its scale. Many natural phenomena have since been shown to exhibit statistical

self-similarity. Examples include earthquakes, fragments, river networks, and mineral deposits [2].

Fractals are mathematical sets with a high degree of geometrical complexity,

which can model many kinds of time series. So Mandelbrot and Van Ness extended

the concept of statistical self-similarity to time series, and the classic example is a

fractal Brownian motion (fBm) [3]. The fractal dimension is an important characteristic of fractals because it contains information about their geometric structure. It

has become an eective tool to study complex sets. There are many denitions for

the fractal dimensions of a fractal set [4,5], but their calculation is not so easy [6].

For simplication, some parameters were proposed to describe fractal characteristic,

for example, Hurster index (Hu) and Hausdor exponent (Ha), whose relationships

with fractal dimension were also discussed.

The estimation of fractal parameter as a constant has been extensively studied

[7,8]. In certain modeling applications, treating the self-similarity parameter as a constant seemed justiable. However for many phenomena with self-similar behavior,

the natures of the self-similarity change as these phenomena evolve. To model such

these data suciently, the fractal parameter must be allowed to vary as a function of

time. For such processes, the local fractal parameter function (H(t)) delivers important, even decisive, information regarding their behavior. Therefore it is desirable to

develop a procedure for H(t) estimation.

Recently electrochemical noise has been researched widely for the detection and

evaluation of localized and general corrosion behavior [9,10]. For electrochemical

noise technique, one of its principal advantages is that it can be used without disturbing of the system under investigation. In addition, it is more sensitive to localized

corrosion processes than some traditional techniques, which produce little information. In the literatures, two main methods for the mathematical treatment of electrochemical noise have been implemented: the statistical method in time domain and the

spectral method in frequency domain [1116]. Although these techniques were useful

for analyzing stationary phenomena and some information was obtained, they were

limited in analyzing non-stationary signals. Some electrochemical noises originating

from corrosion processes were generally considered to be non-stationary in character, for example large amplitude localized transients.

Wavelet analysis is a relatively new mathematical tool used to supplement conventional Fourier analysis, and does not have some of the inherent inadequacies related

to Fourier approach [17,18]. Previous wavelet analysis of electrochemical noise has

included monitoring corrosion process with wavelet transform to distinguish corrosion mechanisms such as pitting and crevice corrosion [19,20]. Another study used

wavelet transform methods to analyze current noise data from dierent electrochemical systems using the energy distribution at dierent scales to measure the activity of

1339

the corrosion events at dierent scale values [21]. The noise resistance was calculated

as a ratio of the standard derivation of the reconstructed potential noise to the reconstructed current noise [22]. The eect of some inhibitors on aluminum alloy was analyzed with the standard deviation of wavelet coecients [23].

For an electrochemical noise signal originating from corrosion process, wavelet

transform could decompose it into a series of components at dierent scales and

locations. Each component was dened by a set of wavelet coecients, which was

the similarity between the noise signal and a wavelet function, and then contained

information about the time scale characteristic of the associated corrosion event.

Therefore, wavelet transform was suitable to analyze the self-similarity of a time series [24], that is, fractal characteristic, although some fractal characteristics were analyzed with chaotic theory [25], whose computation was complex and dicult to

understand.

For a time series of electrochemical noise originating from corrosion process in

practical engineering, it is usually non-stationary and its feature changes frequently

as environmental media and surface condition of electrode material vary with time,

therefore its fractal characteristic should also change. Although general fractal

parameter could give the useful information about electrochemical noise, local fractal parameter describing the characteristic at a certain interval is more interesting,

from which the local information about electrochemical noise is valuable in practice,

and helpful to evaluate and understand corrosion process.

In this study, it demonstrated that wavelet transform could be used to evaluate

general and localized fractal characteristic of electrochemical noises, and a series

of simulating signals with known features were presented to check the eectiveness

of the evaluating procedure, furthermore with which general and localized fractal

characteristic were analyzed about potential noises resulting from 7075-T76 aluminum alloy in 3.5% NaCl solution without and with dierent inhibitors, which were

related to corrosion behaviors of the material and the eect of inhibitors, so as to

illustrate that the fractal parameters representing the characteristic of electrochemical noise were useful in practical engineering.

2. Fractal-wavelet background

2.1. Fractal and its parameter

Until today, there is no common denition of what is a fractal, but it is clear that

a fractal has many dierences from Euclidean shapes [26]. Mandelbort gave a mathematical denition of a fractal as a set for which the Hausdor Brsicovich dimension

strictly exceeded the topological dimension. However, he was not satised with this

denition as it excluded sets that one would consider fractals. The fractal dimension

is an important characteristic of the fractals because it contains information about

their geometric structures.

In practice, electrochemical noise could be divided into two kinds of time series:

fractional Gaussian noise (fGn) and fractional Brownian motion (fBm). The analysis

1340

of their fractal characteristic, that is, self-similarity, is often related to their persistence and stationary. The persistence measures the correlations between adjacent

values within a time series and can be strong, weak, or non-existent (a white noise).

Values of a time series can aect other values in the time series that are not only nearby in time (short range) but also far away in time (long range). Stationary is also one

of the most important aspects of a time series. A time series is said to be strictly stationary if all moments are independent of the length of the time series considered

[27]. Quantifying the persistence and stationary of electrochemical noise signal could

provide information about the nature of corrosion processes.

In order to describe these fractal characteristics, some parameters were dened,

such as fractal dimension (D), Hausdor exponent (Ha), Hurst exponent (Hu), spectral-power exponents (b), and so on. The relationships among them and their application ranges were also discussed [2729].

The classic example of a stationary, discontinuous time series is a Gaussian white

noise. Consider a variable en, n = 1, 2, . . . , N, with a Gaussian distribution of values

that are uncorrelated and random; the distribution has zero mean and a standard

deviation re. A white noise is a time series constructed with yn(wn) = en. The classic

example of a non-stationary time series is a BrownianPmotion, which is obtained by

n

summing a Gaussian white-noise sequence, y n Bm i1 ei . The standard deviation

of a Brownian motion is given by

rn Bm re n1=2

A time series of electrochemical noise can be prescribed either in the time domain

or in the frequency domain in terms of discrete Fourier transform, and its powerspectral density, Sm, usually has a power-law dependence on frequency

S m fmb ;

m 1; 2; . . . ; N =2

where fm = m/N. The value of b is a measure of the persistence strength about the

time series, which is the slope in its power-spectral density periodogram with the

loglog scaling. The Brownian motion has b = 2 and a white noise has b = 0. It

has been concluded [27] that the relationships among b, the persistence strength,

and stationary of a time series are as following:

b>1

Strong persistence

Non-stationary

b0

Uncorrelated

Stationary

Stationary

b<0

Stationary

Anti-persistence

Hausdor is the oldest and probably the most important. Hausdor dimension has

the advantage of being dened for any set, and is mathematically convenient, because it is based on measures, which are relatively easy to manipulate. A major disadvantage is that in many cases it is hard to calculate or estimate with computation

methods. However, in order to understand the mathematics of fractals, familiarity

with Hausdor measure and dimension is essential.

1341

Hausdor exponent, Ha, is one of persistence measures for a time series, which is

associated the standard deviation, rn, with the y-coordinate of the time series, and

the variable n with the x-coordinate, and results in [3]:

rn nHa

A white noise, rn, is independent of n, thus Ha = 0. Any stationary time series, rn, by

denition, must be independent of n, thus again Ha = 0. From the above equation, it

was found Ha = 0.5 for a Brownian motion. 0 < Ha < 0.5 corresponds to shortrange strong persistence, and 0.5 < Ha < 1 to long-range strong persistence.

Voss has used the box-counting method to obtain the general relation between the

Hausdor exponent, Ha, and the fractal dimension, D, with the result [28]:

Ha 2 D

Ha can also be calculated with the semi-variogram method [30]. For a Brownian motion, Ha = 0.5 and D = 1.5. For the time series, Ha is dened between 0 and 1, and D

between 1 and 2.

According to Vosss theory [31], a relationship between the power b, the Hausdor exponent Ha, and the fractal dimension D is given by

b 2Ha 1 5 2D

Therefore, the Hausdor exponent Ha is only applicable for the time series with

1 6 b 6 3, because Ha is dened from 0 to 1 while 1 6 D 6 2. However, the spectral-power exponent b could be a measure of the persistence strength to all time

series, not just 1 6 b 6 3.

An alternative approach to quantify the correlations in time series was developed

by Hurst [32], who considered a river ow as a time series and determined the storage

limits in an idealized reservoir. Basing on these studies he introduced empirically the

concept rescaled-range (R/S) analysis, from which Hurst exponent (Hu) was

obtained.

It was found [27] that Hurst exponent provided a quantitative measure of the

persistence strength and anti-persistence for fractional Gaussian noises (fGn, 1 6

b 6 1), the relation between the Hurst exponent Hu and the power b was expressed

as

b 2Hu 1

Since a white noise (b = 0) is a random process that has adjacent values which are

uncorrelated, it is appropriate to conclude that Hu = 0.5 implies a uncorrelated time

series. It follows that 0.5 < Hu 6 1.0 implies persistence and that 0 6 Hu < 0.5

implies anti-persistence.

2.2. Fractal calculation with wavelet transform

For a time series of electrochemical noise originated from corrosion process, its

power b in the frequency domain is usually in the range of 03. So, Ha and Hu

are just suitable to analyze some parts of electrochemical noises respectively, and

1342

their calculations are also complex. Although the power b obtained with fast Fourier

transform (FFT) could be applied to all the time series of electrochemical noise, Fourier transform has some inherent disadvantages, for example, the transform results

do not provide time resolution, and de-trending and windowing often have an inuence on the transform results. Especially, spectral analysis requires the signal to be

stationary, i.e. the statistical properties do not change with time. However, typical

potential noise drifts with time and therefore it is common to remove this drift, usually by subtracting a linear regression line from the data, and some errors may be

induced in the power spectrum. Likewise, windowing is another pre-analysis procedure to induce errors associated with the ends of the data sequence. Further more,

Fourier transformation is suitable to analyze the periodic time series, however

electrochemical noise from corrosion process always does not exhibit periodic

characteristic.

To overcome these disadvantages of the above fractal parameters and nd a

suitable parameter representing the fractal characteristic of all electrochemical

noises, wavelet transform was introduced, which provided information on both

the time and frequency dependence of a time series. Wavelet transform has a fractal

basis and is particularly useful when applied to non-periodic multi-scaled time series,

and the method could not only be applied to stationary process but also to non-stationary process [33,34].

In wavelet transform process, Mallat pyramidal algorithm [35] was used and the

original time series passed through two complementary lters and emerged as two

components: the approximation and the detail. The decomposition process could

be iterated with successive approximations being decomposed in turn, so that one

signal was broken down into many higher-resolution components, which were the

approximations A2j f and details D2j f of the signal at dierent scales 2j, here j was

the level of decomposition hierarchy, j 2 Z. Fig. 1 shows two-level signal decompoe

sition (analysis) and reconstruction (synthesis) using wavelet, where GG

represents

e

an analysis (synthesis) low pass lter and QQ represents an analysis (synthesis)

high pass lter, Ad2j f denotes an input signal and Ad2j1 f D2j1 f signies the low(high)

frequency component of input signal, where 2j, 1 < j < J, denotes the scale. In the

decomposition stage, a signal was ltered and convolved, and then downsampled

by a factor of 2. In the reconstruction stage, two components were combined by inverse processes of the analysis stage.

When wavelet transform was applied to analyze fractal characteristic of a time

series, there were two kinds of useful data. One was the reconstructed detail signal,

whose energy could be used to calculate Hausdor exponent (Ha). Other was the

wavelet coecient at dierent scales, which were similarity between wavelet function

and the time series at dierent scales, and should be able to represent the self-similarity of the time series.

The power spectrum P(x) of a fractal time signal was represented by

P x axb ax2H a 1

^ j x was expressed as

the high pass lter w

2

1343

a

b

Fig. 1. Two-band signal decomposition and reconstruction by wavelet: (a) decomposition; (b)

reconstruction.

^ j 2

P 2j x P xw

2 x

^ j x w2

where w

2

d

spectrum P 2j x of a discrete signal, sampled by a factor of 2j, was written as

P d2j x 2j

1

X

P 2j x 2j 2mp

m1

Z j

2j 2 p d

E 2j

P j xdx

2p 2j p 2

10

By putting Eqs. (8) and (9) into (10), the following relationship was obtained:

E2j1 22Ha E2j

11

1

E j1

Ha log2 2

2

E2j

12

1344

For the wavelet coecients at dierent scales, their variance were calculated as

j

N =2

X

2

1

Vj

d j;k dj

j

N =2 1 n1

13

where N was the number of potential noise data, dj,k was the wavelet coecient at

the scale 2j and location k2j, and dj was the mean value of dj,k at the scale 2j.

It has also been shown [27] that if the original data series obeys a power law distribution (and therefore a fractal), the variance function can be expressed as a power

law relation with the form:

V j 2j 2j

Hw

14

Hw b

15

The authors of this paper have introduced calculating the standard deviation of

the wavelet coecient at dierent scale so as to compare with the uctuation level

of every detail signal quantitatively [23,36], as following:

s

s

PN =2j

PN =2j

PN =2j

j 2

2

k1 d j;k d j

k1 d j;k

k1 d j;k =N =2

STDj

N =2j 1

N =2j 1

j 1; 2; . . . ; J

16

According to the above equation, in log2 STDj log2 2j plot, the inuences of

inhibitors on electrochemical noise of 7075 aluminum alloy were discussed in detail.

Although the authors realized the self-similarity of electrochemical noises in the

paper, the fractal problem was not discussed deeply [23,36]. In fact,

STDj V j 2j

1=2

1Hw

2j 2

17

Therefore, in log2 STDj log2 2j plot, the slope of log2 STDj values, Hws,

estimated with least-squares regression, should be related to Hw and b as following:

Hws 0.5Hw 0.5b

18

In the following, a set of simulating signals with arbitrary values of b (b = 1,

0.5, 0, 0.5, 1, 1.5, 2, and 2.5) were generated to calculate Ha, Hw, and Hws with

wavelet transform for comparison so as to choose the best parameter describing

the fractal characteristic of electrochemical noise.

Fractional Gaussian noise (fGn, 1 6 b 6 1) could be generated synthetically

from Gaussian white noise function (b = 0) [27]. A discrete Fourier transform was

taken of a Gaussian white noise, the resulting Fourier spectrum would be at.

The resulting Fourier coecients Ym were ltered using the relation:

Y 0m

mb=2

N

Ym

1345

19

An inverse discrete Fourier transform was taken of the ltered Fourier coecients,

and the result was a fractional Gaussian noise. To remove edge eects, only the central portion was retained. Fractional Gaussian noises could be summed to give

fractional Brownian motions, bfBm = 2 + bfGn. Fractional Brownian motion are

associated with b values greater than 1, and the classic example of Brownian motion

is b = 2, which is simply the integral of white noise. Several examples of fGn and

fBm are shown in Fig. 2 with b = 1, 0.5, 0.5, 1, 1.5, 2, and 2.5. Fig. 2 shows

the change in behavior of a time series with regard to the power spectral exponent.

These simulating signals were decomposed with wavelet transform, using the simplest wavelet function, Haar, and then fractal dimension parameters, that is, Ha,

Fig. 2. Simulating signals with arbitrary values of b: (a) 1; (b) 0.5; (c) 0; (d) 0.5; (e) 1; (f) 1.5; (g) 2; and

(h) 2.5.

1346

Table 1

Hausdor exponent (Ha), wavelet variance exponent (Hw), and wavelet STD exponent (Hws) of

simulating signals with arbitrary values of b in Fig. 2

Serial number

Ha

Hw

Hws

a

b

c

d

e

f

g

h

1.0

0.5

0.0

0.5

1.0

1.5

2.0

2.5

0.8686

0.6951

0.4828

0.2511

0.0128

0.2252

0.4540

0.6568

0.7689

0.4234

0.0052

0.4374

0.9559

1.4369

1.8982

2.3061

0.3761

0.2034

0.0109

0.2451

0.4863

0.7268

0.9574

1.1614

Hw, and Hws, were calculated. The number of data points N and the used wavelet

limit the maximum value for decomposition level, J. Using the Haar wavelet with

N = 1024, it is possible to compute up to J = 9. Considering the calculation of STDj,

J was chosen as 6 in the process of simulating signals in Fig. 2.

After the decomposition of the noise signals, the detail signals at each level need

reconstruct so as to calculate Ha, and then the energy of each detail signal was calculated, so Ha was half of the slope obtained with least-squares regression from

log2 Energy log2 2j plot according to Eq. (12), shown in Table 1. Wavelet variance and STD of wavelet coecients at each level were calculated with Eqs. (13) and

(16), then Hw and Hws could be obtained with the similar method to Ha calculation

from log2 V j log2 2j and log2 STDj log2 2j respectively, shown in Table 1.

From Table 1, it was found with least-squares regression method that the relationships among Ha, Hw, Hws, and b were as following:

Ha b 1=2;

deviation r 0.0677

Hws 0.5Hw; deviation r 0.0064

Hws 0.5b; deviation r 0.0633

Hw b; deviation r 0.1266

The results showed that Ha was clearly unsuitable to describe the fractal characteristic of all simulating signals because its values were minus for the signals with

b < 1, which were out of its denition, and the STD of its residuals from the regression line was bigger than Hwss. Hw and Hws could be used to describe all the simulating signals. However compared with Hw, Hws had smaller residuals with the

relationship of b except b = 0, shown in Fig. 3(a), even if Hws was multiplied by 2

to be at the same level as Hw, its residuals from b would also be smaller than

Hws in the range of b > 0 (Fig. 3(b)). In practice, b value of electrochemical noise

is usually between 0 and 3. Therefore, Hws was chosen as the best parameter to evaluate the fractal characteristic of electrochemical noise. According to the fractal definition of b and Ha, the relationships among Hws, the persistence strength, and

stationary of a time series were as following:

1347

Fig. 3. Absolute dierences between b and corresponding Hw (+), between b/2 and corresponding Hws (*)

(a), and between b and corresponding 2 Hws (*) (b) of the simulating signals in Fig. 2.

Hws > 1

Non-stationary

Hws 1

1 > Hws > 0.5

Brownian motion

Short-range strong persistence

Non-stationary

Hws 0

Uncorrelated

Stationary

Stationary

Hws < 0

Stationary

Anti-persistence

In practice, a time series of electrochemical noise originating from corrosion process, f(t), is often measured at discrete, equally spaced time points. Because of the

1348

change of environmental factors such as temperature, solution concentration, inhibitor, and so on, the characteristic of electrochemical noise would vary with time. So

the fractal parameter need not only describe its general characteristic, but also evaluate the change trend of its characteristic. It is necessary to estimate its local fractal

parameter.

The time series could be partitioned into 2l non-overlapping subintervals of equal

length, where l was an integer chosen such that 0 6 l 6 J. The 2l subintervals were of

the form:

I m m 12J l ; m2J l ; m 1; . . . ; 2l

20

b wst was constructed, which could be regarded as

For each Im, an estimation H

estimating the average value of the scaling function Hws(t) over the corresponding

b wst associated with Im might be

subinterval Im. The appropriate time index of H

regarded as the midpoint of Im, namely (2m 1)2Jl1.

At rst, the full 2J observation of the time series was transformed with Haar wavelet, and a series of dj,k, the wavelet coecients at the scale 2j and location k2j, were

obtained. Then for each Im, the STD of corresponding dj,k values was calculated at

each level j respectively, where the level j was no more than some positive integer

J 0 (J 0 6 J)chosen as wavelet decomposition space, and the location k2j was within

the subinterval Im. For each m = 1, . . . , 2l, the bivariate collections of data was dened as

X m ; Y m flog2 2j ; log2 STDd j;k g; k2j 2 I m ; 1 6 k 6 2J j ; 1 6 j 6 J 0

21

Then a least-squares line was tted to (Xm, Ym), treating the Xm as the regressor meab wst was the

surements and the Ym as the response measurements. The estimate H

slope in the least-squares t.

As a nal and optional stage in the procedure, a curve was constructed from the

b wst by employing local polynomial smoothing. This curve

collection of estimates H

then served to approximate the shape of the wavelet STD exponent function Hws(t).

In practical engineering, the sample size of electrochemical noise is not usually a

power of two, the data can be augmented with repeating a part of original noise in

order to make the sample size become a power of two, and the results are adjusted to

delete these corresponding to the repeating data. If such the sample of electrochemical noise is processed with FFT, the data are often augmented with zero values, thus

a large error will be induced in analysis results. So wavelet analysis is more suitable

to practical application.

The performance of the above algorithm for local fractal parameter, Hws(t), was

tested with time series simulating ve kinds of ideal electrochemical noise generated

from corrosion process, which were shown in Fig. 4. The characteristics of ve noise

signals were as following:

S1stochastic white noise, simulating general corrosion process on the surface.

S2no uctuation, simulating ideal passivity on the surface.

1349

Fig. 4. Simulating potential noise signals for calculation of local fractal parameter, Hws.

S3there were ve break/heal events with short time, whose position, amplitude,

and transient time were (100, 10, 8), (300, 5, 8), (500, 15, 8), (715, 20, 8), and (900,

30, 8) respectively, simulating pitting occurrence on the inorganic passive surface.

S4there were ve break/heal events with long time, whose position, amplitude,

and transient time were (97, 10, 32), (300, 6, 16), (500, 15, 32), (705, 20, 32), and

(900, 10, 16) respectively, simulating pitting occurrence on the organic passive

surface.

S5there were two slow uctuations, whose position, amplitude, and decay time

were (100, 10, 170) and (500, 6, 185), simulating slow varying trend of potential

under the passive condition.

For each signal, the sample size was N = 1024 (210, J = 10) and the sample frequency was 1 Hz.

In the estimation algorithm, each sample was partitioned into 32 = 25 (l = 5) subintervals, which resulted in 32 estimation of Hws(t) corresponding to the time

(2m 1) * 24, m = 1, . . . , 25. Each signal was rstly transformed with Haar wavelet

and the decomposition space (J 0 ) was 4. Then, the STD of dj,k corresponding to each

subinterval was calculated at each level and its Hws was estimated according to Eq.

(21). In constructing the estimated curves of Hws(t), the points were just connected

directly, not smoothed over the discontinuity. The calculation results of the local

Hws(t) for the simulating noises are shown in Fig. 5, and their general Hws values

were also calculated in the same decomposition space, J 0 = 4 so as to compare with

each other, shown in Table 2.

1350

Fig. 5. Estimation of local wavelet STD exponent (Hws) for simulating potential noises in Fig. 4.

With comparison of simulating signals and the corresponding general and local

Hws values, some interesting information could be obtained. For stochastic signal,

S1, its general Hws was near zero, so its adjacent data was uncorrelated. Its local

Hws values were near or below zero except for two points around 528 s and 784 s,

which indeed exhibited weak persistence from its shape in Fig. 4 although the signal

was produced with random function in Matlab software, thus the conclusions about

S1 fractal characteristic from its general and local Hws values respectively were basically the same. For the simulating passivity, S2, its general Hws indicated that it was

near Brownian motion, but its local Hws did not exist because there were some zero

values of the STD of dj,k at some scale levels. In fact, for S2, S3, S4, and S5, the local

Hws did not exist in all simulating periods of ideal passivity. This fact more further

reected the surface condition: there was no uctuation. For S5, because the partition interval (25 s) was more less than its slow uctuation time (170 s and 185 s),

the uctuations were divided into some parts in the analyzing process, therefore local

Hws values were just obtained at some parts, which could not describe the uctua-

1351

Table 2

General wavelet STD exponent (Hws) of simulating signals in Figs. 4 and 6

Noise signal

General Hws

S1

S2

S3

S4

S5

S6

0.0022

0.8174

0.4186

0.8250

1.0860

0.1801

tion feature. However, its general Hws was enough to represent its fractal

characteristic.

From the general Hws values of the signals, S3 and S4, they belonged to weak persistence and short-range strong persistence respectively. Their local Hws values could

not only show the persistence for each uctuating event, but also indicate its position. The local Hws values also showed that there existed strong persistence uctuation even in weak persistence signal, such as (300, 5, 8) in S3, and so did long-range

strong persistence uctuation in short-range strong persistence signal, such as

(97, 10, 16) in S4. One uctuation event, (500, 15, 32), was divided into two partition

intervals in wavelet transform process, so there were two Hws values.

In order to demonstrate the ability of local fractal parameter to reect the feature

change of a time series and the inuence of interval length on estimation of local

fractal parameter, simulating signal S6 was constructed with four sections of dierent

self-similarity, which were respectively a part [1, 256] of four simulating signals with

known b values, Fig. 2(c) b = 0, (e) b = 1, (f) b = 1.5, and (g) b = 2, that is,

S6 [1, 256] with b = 0, S6 [257, 512] with b = 1, S6 [513, 768] with b = 1.5,

S6 [769, 1024] with b = 2, shown in Fig. 6(a). In J 0 = 4 decomposition space, similar

to the above calculation procedure of local Hws, its local Hws values were estimated

with the interval length 32 and 64 respectively, and the results are shown in Fig. 6(b)

and (c). Its general Hws was also calculated in the same decomposition space so as to

compare with the results of local Hws, shown in Table 4.

According to the above denition of Hws and the relationship between Hws and

b, with comparison of S6, its local Hws curves and its general Hws, it was found that

its general Hws could not represent the signal with varying fractal characteristic, but

its local Hws values were basically able to reect the varying trend of its characteristic although the interval length had some inuence on the calculating results. Local

Hws curve resulting from the interval length of 64 described the change trend of its

characteristic more accurately than from the interval length of 32. For a section with

steady feature, for example S6 [513, 768] and S6 [769, 1024], if the interval length was

too small, local Hws values would concentrate on reecting local feature and might

inuence the judgement of fractal characteristic about the section, however the statistical property of local Hws values still reected its fractal characteristic. Therefore

the interval length should be chosen reasonably so as to reect the change of signal

characteristic with time.

1352

Fig. 6. Simulating signal (a) with varying fractal characteristic and the estimation of its local Hws with the

interval length, 32 (b) and 64 (c), respectively.

From the above discussion about the general and local Hws of the simulating signals in Figs. 4 and 6, it was shown that the local Hws could extract the varying feature of a signal with time and be more suitable to describe the signal uctuating

frequently, however the general Hws was able enough to represent the fractal characteristic of the signal with very slow uctuation. The subinterval partition of a time

series would inuence the result of local Hws calculation, which should be carried

out on the basis of its self-feature and usually avoid separating a local accident with

distinct feature.

3. Experiment

The test material 7075-T76 aluminum alloy had the following analysis of composition: Cu(1.68%), Zn(5.61%), Mg(2.16%), Mn(0.21%), Cr(0.11%), other(0.66%),

1353

is determined by the oxide lm of the surface and the intermetallic phases such as

MgZn2, Al7Cu2Fe and Al2CuMg [3639]. In the test electrolyte, which was 3.5%

NaCl solution made of reagent grade sodium chloride and distilled water, localized

corrosion such as pitting corrosion occurred easily on the surface of 7075-T76 aluminum alloy. In order to investigate the eect of inhibitors on localized corrosion

of aluminum alloy, some inhibitors were added to the test electrolyte, such as phosphate, molybdate, citrate, benzimidazole/benzothiazole (MBTZ), and chromate. The

total amount of inhibitors in all experimental solution was xed at 500 ppm and the

circumambient temperature was 28 2C.

The working electrodes were cuboid, and a hole was drilled on one part of the

specimen to be connected with the wire of the measuring instrument. The exposed

surface was prepared by polishing with 280-, 400-, 600-grit papers in succession

and then cleaning with acetone. All the surfaces including the wire were masked with

wax, then a 1 cm2 circular area of wax was removed and this exposed area of specimen was rinsed with acetone and water, and nally dried in air. A new working electrode was used in each run. A saturated calomel electrode (SCE), brought into close

proximity to the working electrode by a Luggin probe, was used to measure the

potential of the working electrode.

After the specimen was immersed in the test solution for 24 h, its potential noise

signal at open-circuit was sampled with an instrument for measuring and analyzing

electrochemical noise [40]. The sampling interval was 2 s and the length of the measured record was 1024 points.

4.1. Measurement results

The measured potential noise data in the test solutions are shown in Figs. 7 and

8. When the 7075-T76 aluminum alloy was put into the 3.5% NaCl solution for 1 h,

its potential uctuated very frequently (Fig. 7(a)), but after 24 h both the amplitude

and rate of potential uctuation decreased (Fig. 7(b)). When the test solutions contained dierent inhibitors, electrode potential exhibited dierent uctuation phenomena. In phosphate solution, potential uctuation (Fig. 8(b)) was similar to

that in the 3.5% NaCl solution for 1 h, and electrode potential uctuated more

slowly in phosphate/molybdate solution than in phosphate solution (Fig. 8(c)),

and after adding citrate (Fig. 8(d)), it uctuated further more slowly than in phosphate/molybdate solution. In phosphate/citrate solution, the potential changed

very slowly (Fig. 8(e)), and then after MBTZ was added (Fig. 8(f)), the uctuation amplitude decreased more further. In chromate and phosphate/molybdate/

citrate/MBTZ solutions, the electrode potential seldom uctuated (Fig. 8(a)

and (g)).

1354

Fig. 7. Potential noise signals of 7075-T76 aluminum alloy immersed in 3.5% NaCl solution after 1 h (a)

and 24 h (b) respectively.

Just as the same of the calculation procedure for the simulating signals in Fig. 2,

these electrochemical noise signals were decomposed with wavelet transform, using

the simplest wavelet function, Haar, and then their fractal parameters, that is, Ha,

Hw, and Hws, were calculated respectively. The number of decomposition level, J,

together with the sampling interval Dt, determined the scale range studied

(2Dt, 2JDt). It should be noticed that the number of data points N and the used wavelets limit the maximum value of chosen J. Using the Haar wavelet with N = 1024, it

was possible to compute up to J = 9. However, a higher J would imply a shorter window of data to analyze because of the boundary eects, and due to the fact that all

the transients contained in the potential records last less than 300 s, it was determined that J = 6 gave a reasonable scale range to study the transients.

After the decomposition of the noise signals, the detail signals at each level need

reconstruct so as to calculate Ha, and then their energies was calculated respectively,

so according to Eq. (12), Ha was half of the slope obtained with least-squares

regression from log2 Energy log2 2j plot, shown in Fig. 9. The results are in

Table 3. The wavelet variance and STD of coecients at each level were calculated

with Eqs. (13) and (16), then Hw and Hws could be obtained from

log2 V j log2 2j and log2 STDj log2 2j respectively, shown in Fig. 9. From

Fig. 9, it was shown that the residuals of Ha evaluation, which were the vertical

distances between data points and regression line, were clearly bigger than for

Hws value, so Hws value should be more accurate to represent the characteristic

of electrochemical noise. For all the electrochemical noises, their Hws values were

calculated from Fig. 10, and shown in Table 3.

These electrochemical noises also were analyzed with FFT so as to get the spectrum power, b, according to Eq. (2). Because detrending and windowing often

inuence the FFT results, the same pre-treat methods, linear detrending and window = 1024, were applied for all noise signals to compare with each other. The results are also shown in Table 3.

1355

Fig. 8. Potential noise signals of 7075-T76 aluminum alloy immersed in 3.5% NaCl solution containing

chromate (a), phosphate (b), phosphate/molybdate (c), phosphate/molybdate/citrate (d), phosphate/

citrate (e), phosphate/citrate/MBTZ (f), and phosphate/molybdate/citrate/MBTZ (g) respectively.

From Table 3, it was found with least-squares regression method that the relationships among Ha, Hw, Hws, and b were as following:

Ha b 1=2;

deviation r 0.0676

Hws Ha 0.5;

deviation r 0.0073

Hws 0.5b; deviation r 0.0722

Hw b;

deviation r 0.1543

1356

Fig. 9. The energy of detailed signals and the STD of detailed coecients after potential noises were

processed with wavelet transform for 7075-T76 aluminum alloy in 3.5% NaCl solution without inhibitor

(a) and with phosphate (b).

Therefore, the results from the practical noises were consistent with theory analysis

and the results from simulating signals. These results also showed that Ha was

1357

Table 3

Hausdor exponent (Ha), wavelet variance exponent (Hw), wavelet STD exponent (Hws) (J = 6), and

spectrum power (b) of potential noises generated from 7075-T76 aluminum alloy in 3.5% NaCl solution

without and with inhibitors

Serial number

Solution

Ha

Hw

Hws

1#

2#

3#

4#

5#

6#

7#

8#

9#

Blank (1 h)

Blank (24 h)

Chromate

Phosphate

Phosphate/molybdate

Phosphate/citrate

Phosphate/citrate/molybdate

Phosphate/citrate/MBTZ

Phosphate/citrate/molybdate/MBTZ

0.0744

0.1085

0.4834

0.0907

0.0049

0.6438

0.2467

0.5280

0.4904

0.8102

1.2118

1.9664

0.7907

0.9896

2.2853

1.4665

2.0537

1.9779

0.4154

0.6142

0.9915

0.4037

0.5031

1.1510

0.7416

1.0352

0.9973

0.8439

1.4277

2.0580

0.8334

1.1651

2.6280

1.3860

2.0830

2.0070

because of its minus values in some signals and its big dispersion, and that Hw

had larger deviation with the relationship of b in comparison with Hws although

it could be suitable for all the noise signals. Therefore Hws was more suitable to

be as the fractal parameter of electrochemical noise in this paper, and its denition

could be deduced from b, Ha, and Hu meanings, which has been explained in previous theory part.

4.3. Relationships between fractal characteristic and corrosion process

According to Hws denition and the results of Table 3, the studied electrochemical noises could be divided into four kinds as following:

(1)

(2)

(3)

(4)

2#, 5#, and 6#: short-range strong persistence, non-stationary,

3# and 9#: Brownian motion,

7# and 8#: long-range strong persistence, non-stationary.

The characteristics of these potential noises were closely related to the summation

of electrical processes occurring on the electrode surface in the test solutions. The

relationship between fractal characteristic and surface condition would be analyzed

in detail.

Corrosion resistance of 7075-T76 aluminum alloy is not only associated with the

oxide lm of its surface, but also with micro-structural heterogeneity at the surface.

It contains signicant amounts of constituent particles such as Al7Cu2Fe, MgZn2

and Al2CuMg [3639]. Local galvanic cells form easily on the metal surface in aqueous environments because of the dierence in electrochemical activity between these

heterogeneous phases and between the particles and the matrix. These cells lead to

accelerated, localized corrosion (pitting) attack. It has been proved that in 3.5%

NaCl solution, comparison with the matrix, MgZn2 particles act as principal anodes,

1358

-6

-10

Log (STDj )

-8

1#

5#

6#

8#

9#

-12

-14

-16

Log (2 )

-6

-10

Log (STDj )

-8

-12

2#

3#

4#

7#

-14

-16

b

Log (2 )

2

Fig. 10. STD of wavelet detailed coecients of potential noises generated from 7075-T76 aluminum alloy

in 3.5% NaCl solution without and with inhibitors.

and Al7Cu2Fe as cathode to dissolve, and Al2CuMg particles also act as anodic sites,

losing Mg and Al through dissolution in the early stage of corrosion and becoming

more cathodic as Cu is left behind [38,39,41]. In addition to the eects of microstructural heterogeneity, the importance of passive surface lms on pitting must

be considered. In this study, Cl could destabilize the passive lm over the matrix

to promote the occurrence of pitting corrosion [42]. So, in this study, when the sample was put into 3.5% NaCl solution for 1 h, there were a lot of reacting spots on the

surface because of the eect of particles and Cl, and which had little or no inuence

with each other, thus there was a weak correlation between adjacent values, and the

moments were independent of the length of the measure time. After 24 h, because Cu

was deposited on the surface from the solution to form a yellow thin lm, the reacting spots decreased and potential uctuated slowly. As a result, the correlation be-

1359

tween adjacent data increased and the moments were determined by the measure

time, so the fractal characteristic of its potential noise was strong persistence and

non-stationary.

When the inhibitors were added into the test electrolyte, they inuenced the surface corrosion process with dierent mechanism. Because of chromate powerful

oxidizing properties and its adsorbability to the material surface [43], the presence

of chromate in the solution, even in the presence of aggressive anions like Cl,

stimulates the repair of awed regions of the surface lm and oxidizes the active

sites, accommodates on the active sites and cathodic areas, and inhibits active

galvanic couples, leading to the formation of a stable corrosion resistant barrier

lm [44]. So its potential seldom uctuated, just stochastic uctuating, and its

amplitude was very small. Therefore, the potential noise belonged to Brownian

motion.

Because the main protective eect of phosphate is to react with corrosion products such as Al3+, Zn2+, and Mg2+ to deposit on the specimen surface and form

the protective lm [45], which may not be uniform, its inhibiting eects do not occur

quickly. After 24 h immersion, there existed a lot of corrosion and deposition reaction on the surface, which had little inuence on each other. Therefore, the potential

noise in phosphate solution had weak persistence and stationary. After a small

amount of molybdate was added in phosphate solution, the breakdown probability

of the lm decreased in chloride media because molybdate as an oxidizer could reinforce the oxide lm of aluminum alloy surface [44]. However, because of the weaker

oxidizing properties of molybdate compared to chromate and its low concentration

in the test, there were still some aws on the specimen surface, at which break/heal

events and phosphate deposition occurred. So the correlation between adjacent data

strengthened and the moments were related to time.

Carboxylates generally provided the combined action of an easily-reduced cation

and a strongly-adsorbed anion that formed a chemical bond between the carboxyl

ion and the metal substrate [46]. Thus, when the citrate ion with three carboxyls

was added in 3.5% NaCl solution, it could competitively adsorb on the surface of

aluminum alloy instead of chloride ion. When citrate met with phosphate in the solution, they would form a synergistic lm to cover the surface of aluminum alloy [36],

but this lm was not compact and uniform. Some ions could penetrate through it

from the solution to the substrate surface or from the substrate to the solution,

and further could not absorb rmly on the particles such as Al2CuMg [29]. Therefore, corrosion reaction had been occurring although its rate was very low. This process was reected by much slower uctuation on potential noise in phosphate/citrate

solution, which could be described as long-range strong persistence in fractal

characteristic.

In phosphate/molybdate/citrate solution, the adsorption of citrate lowered the

reactivity of the surface and facilitated oxidizing passivation of the remaining surface

by molybdate, resulting in the passive lm on a majority of electrode surface. But the

synergistic eect of adsorption and oxidation could not form the stable lm on some

particles such as Al2CuMg, which easily induced pitting. So its potential noise exhibited the typical pitting characteristic, that is, break/heal events occurred on the

1360

surface lm. In one break/heal event, its potential data were correlated and its transient time was longer than in phosphate/molybdate solution, thus its Hws was bigger

than in phosphate/molybdate solution, and its potential noise had stronger persistence though in short-range.

Because MBTZ containing the elements of sulfur and nitrogen could easily adsorb

on copper and its alloy to form a chemisorbed layer and hinder the corrosion of copper and its alloy [47,48], MBTZ adsorbed easily on the intermetallic phases containing copper such as Al7Cu2Fe and Al2CuMg, thus it could inhibit the corrosion

induced by intermetallic phases, hindered the cathodic process of corrosion on

7075 aluminum alloy and signicantly drove the corrosion potential toward more

negative values. As a result, in phosphate/citrate/MBTZ and phosphate/molybdate/citrate/MBTZ solution, pitting and localized corrosion were inhibited, so

potentials became more stable than in phosphate/citrate and phosphate/molybdate/citrate solution respectively. In phosphate/citrate/MBTZ solution, potential

still uctuated very slowly with lower amplitude, so it exhibited long-range strong

persistence. When molybdate was added into the solution, potential seldom uctuated, similar to that in chromate solution, so its fractal characteristic belonged to

Brownian motion.

With comparison of Hws values of potential noises in dierent solutions, combined with corrosion reaction on the electrode surfaces, it was shown that Hws value

could evaluate the irregularity of electrochemical noise quantitatively at the analysis

scale, that is, as Hws became smaller, the corresponding potential uctuated more

frequently, and the surface was more unstable, thus the eect of the inhibitor on corrosion was weaker. The dierence between Hws and 1 reected the distance to

Brownian motion for potential noise at the analysis scale, the smaller the dierence,

the nearer to Brownian motion, and the more stable the potential at the analysis

scale. In fact, if the comparison was carried out in the Fig. 10, these views were very

clear. Therefore, log2 STDj log2 2j plot could not only be used to compare the

uctuation at dierent scales with each other [23,36], but also calculate the fractal

parameter, Hws, so as to describe the irregularity, or complexity of electrochemical

noise quantitatively.

The above results were coincidence with the previous studies. It has been established that the slope (a) of the potential noise power spectrum on a log vs. log scale

(the parameter a being obtained from the equation PSD(V) f a) can be used as a

signicant parameter to distinguish the types of corrosion [10,14]. A slope shallower

than 20 dB/decade has been related to pitting corrosion process, and a slope steeper than 20 dB/decade has been associated with passivation. The parameter a was

the same meaning with b in this paper, and they were dierent just in expression

form, that is, a = 20 dB/decade was same as b = 2. So according to the previous

study, there formed passive lms on the sample surface in chromate, phosphate/citrate, phosphate/citrate/MBTZ, and phosphate/molybdate/citrate/MBTZ solutions,

and there existed pitting corrosion in other solutions. Although the result was right,

it was rougher qualitatively compared with the result from wavelet analysis, and a lot

of useful information was lost and the dierences among these noise signals were not

discovered.

1361

Table 4

Comparison of wavelet STD exponent (Hws) at dierent scales (J = 4 and 6) of potential noises generated

from 7075-T76 aluminum alloy in 3.5% NaCl solution without and with inhibitors

Serial number

Solution

Hws (J = 4)

Hws (J = 6)

1#

2#

3#

4#

5#

6#

7#

8#

9#

Blank (1 h)

Blank (24 h)

Chromate

Phosphate

Phosphate/molybdate

Phosphate/citrate

Phosphate/citrate/molybdate

Phosphate/citrate/MBTZ

Phosphate/citrate/molybdate/MBTZ

0.3572

0.6666

1.0045

0.3403

0.6924

1.2317

1.0248

1.0400

1.0008

0.4154

0.6142

0.9915

0.4037

0.5031

1.1510

0.7416

1.0352

0.9973

The fractal parameters of all the studied potential noises were calculated at the

scale 256 s (J = 6) level so as to compare with each other. In fact, self-similarity of

a time series exists in a certain scale range, that is, for a time series, if the analysis

scale is in this range, the scale has little or no inuence on the evaluation of fractal

parameter, and if out of this range, the scale would have some inuence on the fractal evaluation. So Hws values of all potential noises were calculated at the scale 64 s

(J = 4) level, shown in Table 4.

Comparing Hws values at J = 4 level with the corresponding values at J = 6 level,

it was found that except in phosphate/molybdate and phosphate/molybdate/citrate

solution, there were no apparent change for Hws properties of potentials in other

solution. In phosphate/molybdate and phosphate/molybdate/citrate solution, potential noises mainly consisted of a series of break/heal events of passive lm, whose

transient time was shorter in phosphate/molybdate solution than in phosphate/

molybdate/citrate solution. When the analysis scale became smaller from 256 s

(J = 6) to 64 s (J = 4), the correlation between adjacent data in a break/heal event

would become strong spontaneously, especially for potential in phosphate/molybdate/citrate solution, its fractal characteristic became long-range strong persistence

from short-range strong persistence because the analysis scale (64 s) was little more

or less than the transient time of a lot of events. In fact, the results were consistent

with that from FFT analysis.

PSD of potential noise in phosphate/molybdate/citrate solution exhibited two

parts: a low-frequency plateau and a high-frequency part which tted the following

relationship: PSD(V) = Kfa, a = 2.2151, and the roll-o frequency, fc, which was

the frequency to separate the two parts of the PSD, shown in Fig. 11. From the literature [49], it could be concluded from a and fc that pitting corrosion occurred with

the frequency fc on the passive surface. Here, fc 1/scale and a 2Hws. Therefore,

the results from FFT and wavelet analysis supported to each other, but the result

from wavelet analysis was clearer than from FFT.

1362

Fig. 11. The power spectrum of potential noises generated from 7075-T76 aluminum alloy in 3.5% NaCl

solution with phosphate/citrate/molybdate.

The discussion in previous theory showed that the local Hws was more suitable to

describe the varying feature of the signal uctuating frequently, and the general Hws

was able enough to represent the fractal characteristic of the signal with very slow

uctuation. So the potential noises, originated from 7075-T76 aluminum alloy in

3.5% NaCl solution containing phosphate, phosphate/molybdate, and phosphate/

molybdate/citrate respectively, were chosen so as to analyze their local fractal

characteristics.

The estimation algorithm was to partition the noise signals into 32 = 25 (l = 5)

subintervals, which resulted in 32 estimates of local Hws. When the STD of dj,k

for each estimate was calculated, the wavelet decomposition level j was restricted

to be no more than 4 (J 0 = 4). In order to compare with each other conveniently,

the results of local Hws was put together with its corresponding original noises,

shown in Figs. 1214.

In phosphate solution, the general Hws of its potential noise is 0.3403 (Table 4),

which indicated that the fractal characteristic of its noise was weak persistence, that

is, corrosion events on the electrode surface were independent because phosphate

could not form a stable and uniform passive lm [50]. From Fig. 12, many of local

Hws were between 0 and 0.5, so in a majority of time, the adjacent potential data

were just correlated weakly, but there were a few of Hws below zero or more than

0.5, which meant that the potentials in the corresponding parts were anti-persistence

1363

Fig. 12. Potential noise (a) generated from 7075-T76 aluminum alloy in 3.5% NaCl solution with

phosphate and the estimation of its local wavelet STD exponent (Hws) (b).

Fig. 13. Potential noise (a) generated from 7075-T76 aluminum alloy in 3.5% NaCl solution with

phosphate/molybdate and the estimation of its local wavelet STD exponent (Hws) (b).

its local Hws values in phosphate solution (Fig. 12(a) and (b)), the local Hws values

1364

Fig. 14. Potential noise (a) generated from 7075-T76 aluminum alloy in 3.5% NaCl solution with

phosphate/molybdate/citrate and the estimation of its local wavelet STD exponent (Hws) (b).

could eectively describe the change of the irregularity about potential uctuation,

for example, the potentials around 2000 s were strongly correlated, so the local

Hws values of two corresponding intervals were 0.4587 and 0.8900.

When both phosphate and molybdate existed in the solution, because of molybdate oxidation, the defects on the passive lm decreased [44] and the potential uctuation became slower, so the correlation between adjacent data was strengthened,

and its general Hws was 0.6924. This change was also reected with a majority of

local Hws values between 0.5 and 1. However, the local Hws also pointed out that

the weak persistence or anti-persistence existed about between 200 s and 300 s,

and between 1800 s and the 1900 s (Fig. 13(b)), in which the corresponding potential

uctuated more frequently than other parts (Fig. 13(a)).

In phosphate/molybdate/citrate solution, because of the synergistic eect of three

inhibitors, the more stable lm was formed on the surface of aluminum alloy [50,51],

but there were a few spots, especially intermetallic particles such as Al7Cu2Fe and

Al2CuMg, which was dicult to form the stable lm [50]. So there were still

break/heal events on the surface, however because of the inuence of citrate on

the capacitive behavior of the metalenvironment interface, the re-passivation time

became longer [52] than the analysis scale level. Thus its general Hws was 1.0248,

which exhibited long-range strong persistence, and most of its local Hws was also

more than 1. But at the beginning and end of noise signal (Fig. 14(a)), potential uctuated more frequently than the middle part. This phenomenon was reected clearly

by the corresponding local Hws values (Fig. 14(b)), which were between 0 and 0.5

and below zero to exhibit weak persistence and anti-persistence respectively.

1365

From the application of local Hws in Figs. 1214, the analysis showed that the

conclusions from the general and local Hws were basically consistent about the fractal characteristics of these electrochemical noises. But the local Hws could quantitatively extract the local feature of electrochemical noise, and accurately display the

fractal characteristics of dierent parts so as to analyze its corrosion process in convenience, and the general Hws just reected the statistical property of the local Hws

values. Therefore, in practice when electrochemical noise is used to measure and

monitor corrosion process, the local Hws could eectively describe the change of

the noise properties, especially when the data sample size is not sucient, it can

be extended with repeating measurement data so as to avoid the inherent defects

of FFT. Therefore, local Hws analysis should be more suitably applied to analyze

electrochemical noise in engineering.

5. Conclusion

On the basis of the introduction to calculate general and local fractal parameters

of simulating signals with wavelet transform, general and local fractal characteristics

were analyzed about electrochemical potential noises generated from 7075-T76 aluminum alloy in 3.5% NaCl solution without and with dierent inhibitors respectively. It was concluded as following:

log2 STDj log2 2j plot could not only be used to compare the uctuation of

electrochemical noise at dierent scales with each other, but also calculate the

fractal parameter, wavelet STD exponent (Hws), so as to describe the irregularity,

or complexity of electrochemical noise quantitatively.

Compared with Hausdor exponent (Ha) and wavelet variance exponent (Hw),

Hws resulting from the standard deviation of wavelet detail coecients, had smaller deviation and could describe the fractal characteristics of electrochemical noises

in a wide range. Compared with the spectral power (b) from FFT analysis,Hws calculation avoids some inherent defects such as detrending and windowing.

For the potential noises in the study, the smaller Hws value, the more frequently

potential uctuated on the electrode surface, and the less eect of inhibitor in the

solution. The dierence between Hws and 1 reected the condition of surface passivity. The smaller the dierence, the more stable surface lm at the analysis scale.

For the studied electrochemical noises, the results from Hws analysis were consistent with that from FFT analysis, but which were more distinct and quantitative

than from FFT.

The results from general and local Hws were basically consistent about the fractal

characteristics of these electrochemical noises. But local Hws could apparently

indicate the change of the fractal characteristics with time for electrochemical

noise so as to analyze its corrosion process in convenience, and the general

Hws reected the statistical property of the local Hws values.

Local Hws was more suitable to describe the varying feature of signal uctuating

frequently, however general Hws was enough to represent the fractal characteristic of the signal with very slow uctuation.

1366

References

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Press, Cambridge, 1997.

[3] B.B. Mandelbrot, J.W. Van Ness, Fractional Brownian motions, fractional noises and applications,

SIAM Rev. 10 (1968) 422437.

[4] A.J. Hurd, D.A. Weitz, B.B. Mandelbrot, Fractal Aspects of Materials: Disordered Systems,

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