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Corrosion Science 48 (2006) 13371367

www.elsevier.com/locate/corsci

Fractal characteristic analysis of


electrochemical noise with wavelet transform
X.F. Liu

a,b,*

, H.G. Wang a, H.C. Gu

Xian High-technology Institute, Xian 710025, PR China


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

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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

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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

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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

1 > b > 0 Weak persistence


b0
Uncorrelated

Stationary
Stationary

b<0

Stationary

Anti-persistence

Among the wide variety of fractal dimensions in application, the denition of


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.

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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

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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

where a denoted a constant. The power spectrum P 2j x of a fractal signal ltered by


^ j x was expressed as
the high pass lter w
2

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decimation by a factor of two.


a

interpolation by a factor of two.


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 denoted the wavelet function at the scale 2j. The power


^ 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

Let E2j be the energy of a high frequency signal D2j f , dened as


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

Thus, the Hausdor exponent Ha was computed by


1
E j1
Ha log2 2
2
E2j

12

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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

where Hw is known as the wavelet exponent.


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

Hws was named as wavelet STD exponent.


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:

X.F. Liu et al. / Corrosion Science 48 (2006) 13371367

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.

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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 Ha 0.5; deviation r 0.0050


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:

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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

Long-range strong persistence

Non-stationary

Hws 1
1 > Hws > 0.5

Brownian motion
Short-range strong persistence

Non-stationary

0.5 > Hws > 0 Weak persistence


Hws 0
Uncorrelated

Stationary
Stationary

Hws < 0

Stationary

Anti-persistence

2.3. Estimation of local fractal parameter


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

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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.

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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.

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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-

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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.

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X.F. Liu et al. / Corrosion Science 48 (2006) 13371367

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%),

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Al(balance). The corrosion resistance of 7075-T76 aluminum alloy (AlZnMgCu)


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. Results and discussion


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)).

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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.

4.2. Calculation results of general fractal parameters


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.

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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 0.5Hw; deviation r 0.0086


Hws 0.5b; deviation r 0.0722
Hw b;

deviation r 0.1543

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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

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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

clearly unsuitable to describe the fractal characteristic of all electrochemical noises


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)

1# and 4#: weak persistence, stationary,


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,

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-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-

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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

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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.

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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

4.4. Inuence of the analysis scale on fractal evaluation


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.

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Fig. 11. The power spectrum of potential noises generated from 7075-T76 aluminum alloy in 3.5% NaCl
solution with phosphate/citrate/molybdate.

4.5. Analysis of local fractal characteristic


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

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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).

or short-range strong persistence. With comparison of the potential uctuation and


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

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X.F. Liu et al. / Corrosion Science 48 (2006) 13371367

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.

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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.

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