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You are here: Home > Corrosionsource/2000 > Session 01 > Paper 0104

ELECTROCHEMICAL NOISE - THE FIRST TWO OCTAVES

PART II

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D.A.Eden
Integriti Solutions Ltd
7 Queens Gardens
Aberdeen, Scotland AB15 4YB

ABSTRACT

Electrochemical noise techniques have been used to study corrosion related processes since the early 1980's. Preliminary studies of the electrochemical characteristics of localised corrosion phenomena, in particular pitting and cavitation attack, established the sensitivity of the technique for the detection of spontaneous changes in corrosion processes. Throughout the last sixteen years, the fundamental principles and methodology behind the measurements has changed little, but with the advent of the computer age, improved data acquisition, signal processing, and fast analysis techniques have enabled the technique to be routinely used in the field. The evolution of electrochemical noise monitoring techniques is reviewed with relation to the development of electrochemical noise measurement for metallic corrosion, and the analysis and interpretation of the observed noise response. Practical site applications have been an intrinsic part of the evolutionary process, and the development of the technology is discussed with relation to the database obtained for a wide variety of corrosion circumstance.

Keywords: Electrochemical noise, localised corrosion, general corrosion, corrosion monitoring.

II. A GENERAL MODEL FOR ELECTROCHEMICAL NOISE

The following is a general model for electrochemical noise after Donald Halford who originally published his work in 1968. Halford was working at the National Bureau of Standards at the time he published his article in the Proceedings of the IEEE in March 1968, and his interests were not in the field of electrochemical noise signals, but rather in improving precision in a slave oscillator which was to be used with the atomic maser frequency standard.

Halford's paper entitled "A General Mechanical Model for Spectral Density Random Noise with Special Reference to Flicker Noise 1/|f|", has been useful in providing the author with an insight into the fundamental processes which produce electrochemical noise, and it is considered both relevant and useful to acknowledge Halford's contribution to the understanding of noise signals by reproducing some of his ideas in this chapter. It is hoped to show how electrochemical noise characteristics in the frequency domain relate to particular types of processes, and in addition help us to derive impedance information from the raw noise data.

The chapter on probabilistic modelling of electrochemical noise sources should be considered in conjunction with this chapter.

1. Flicker Noise.

The term "Flicker Effect" was originally use to describe a particular noise observed in vacuum tubes in the 1920's. There are many different name for this type of effect viz; "1/f noise", "excess noise", "semiconductor noise", "low frequency noise", "contact noise", and "pink noise". The spectral density of this type of noise is seen to increase as its frequency decreases, and a typical behaviour is as , with a being constant and equal to -1. The value of a may vary from system to system, and is not always constant, values of -0.8 to -1.3 are common. In many cases this behaviour is found to hold over many decades of frequency.

This type of noise is found in many systems. According to Halford, it is found for example in quartz crystal oscillators, vacuum tubes, field effect and bipolar transistors, semiconductor diodes, resistors, thermistors, carbon microphones, thin films, light sources, membrane potentials in biological systems, the frequency of rotation of the earth, the flow of traffic in Tokyo, classical music & etc. Most importantly for our purposes, this type of noise is found in electrochemical systems.

The case where a » -1, is common, but certain processes exist which have values of a more negative than -1. For example the fluctuations of the frequency of rotation of the earth are described by a » -2, and the power spectral density of galactic radiation by a » -2.7.

Frequency domain transforms of electrochemical potential and current noise time record data, obtained from a wide variety of corroding systems, has indicated that values of a are typically between 0 and -3. It is therefore of particular interest as to how certain types of spectral characteristic may be related to fundamental corrosion mechanisms.

Halford suggested that it would be useful to be able to produce models which can generate noise having the appropriate spectral density. These models should be physically plausible, and preferably be chosen to correspond as closely as possible to the physical process being measured. With these factors in mind, Halford described a rather general model which can be used to generate noise with a spectral density of , any a, for a very broad range of physically plausible processes. The following describes his approach:

"We consider a system in which some process of interest is occurring, and in which the process is suffering many time-dependent perturbations in a random manner due to some unspecified agent or agents. The uniform portion of the process constitutes a signal, and the random fluctuations are the associated noise. We wish to answer at least two questions.

  1. Can such a superposition of time-dependent perturbations of a specified shape, occurring at random, give rise to an dependence of the noise spectral density with a constant over an arbitrarily large range of spectral frequency, f?
  2. What conditions must be satisfied to obtain the law?

To answer these questions, the discussion needs to be concerned only with the mathematical description of the time-dependent perturbations. Hence there is no reference to specific physical models. To avoid the possibility of the model thereby synthesised being non-physical in principle some constraints are imposed, e.g. certain infinities are excluded from consideration. We use the term mechanical model for a model which is physical in principle, although not necessarily encountered in reality."

Synthesis of a Mechanical Model of

A. Definitions

Let H be the representation in the time domain (t) of a perturbation of the class H . The representation of H(a,t ) has a lifetime t and squared amplitude a2. These quantities will be defined in this part. A class is the set of perturbations which are equivalent under some individual independent scaling of amplitude a, scaling of time, and translation of time. Special consideration is given to reasonable perturbations. By definition a reasonable perturbation 1) is everywhere finite, 2) has a finite time integral, 3) has finite, non-zero energy, 4) has finite non-zero lifetime and 5) is a real function of time. These may be stated symbolically as follows;

............(37a )

............(37b)

............(37c)

............(37d)

and

............(37e)

Throughout the following, the time t need not appear explicitly as an argument of H, and it will not be shown. Under scaling of amplitude, the representation has the following property

............(38)

Let F(w,t) denote the Fourier transform of a-1H(a,t)

............(39)

............(40)

where f is cyclic frequency. Under scaling of frequency and time, the Fourier transform has the property

............(41)

The energy q of a perturbation is defined as

............(42)

Under scaling, q has the property

............(43)

The lifetime of a perturbation is defined implicitly by

............(44)

This definition of t is chosen so that | w|m = 2p |f|m = t -1 , where |f|m is the median absolute frequency of the energy distribution. The utility of this definition may be seen later when we consider the frequency range over which a particular noise law is valid.

The square of the amplitude is defined as

............(45)

For simplicity we set ao2 and t0 to unity. Hence q( ao,t0 ) equals unity, and we note

............(46)

............(47)

Suppose that a process is perturbed by a large number of time dependent perturbations which form a subclass of the class H. We define A2(t) as the mean square amplitude of perturbations in the subclass having the same lifetime t. We further suppose the perturbations occur randomly (as a Poisson process) with the finite average total rate of R perturbations per unit interval of time. Hence the rate at which perturbations of lifetime t occur is given by the product RP(t).

The definitions given above establish a mathematical description of a general mechanical model for the generation of random noise. Using these concepts in the situation described in the preceding paragraph, the equation for the two-sided spectral density S(f) of the noise is defined as

............(48)

This definition of the spectral density is consistent with that of Blackman and Tukey. The dimensionality of s(f) is the same as the dimensionality of the ratio H2/f. For pure real perturbations, S(f) is symmetrical about zero frequency.

By way of example, consider the class of all perturbations each of which is represented in the time domain by a step change followed by an exponential decay back to the origin (Figure 11) represents such a system, according to (49)

............(49)

and derived from

(............(50)

............(51)

............(52)

............(53)

............(54)

............(55)

............(56)

............(57)

Figure 11. A reasonable perturbation from the class having, in the time domain, a step change followed by exponential decay back to the origin.

n.b. In the frequency domain, the power spectral density of the process can be shown to have a value of a of 0 at the low frequency limit, and -2 at higher frequencies due to the exponential decay time constant.

For the generation of flicker noise having a = -1, equation 48 for the spectral density is put in the form

............(58)

The dependence on t of P(t)A2(t) is expressed as

............(59)

In general, B and d may be functions of t, but our interest will focus on those situations in which B and d are independent of t over some finite range. Consider the case where, in the range ,

............(60)

............(61)

............(62)

and for t outside of the range e to z. For the spectral range ,

............(63)

............(64)

Hence

............(65)

for frequencies in the arbitrarily large but finite range .

This result shows that a spectral density law of can be obtained over an arbitrarily large frequency range from a subclass chosen from any class of reasonable perturbations. The sufficient condition is that such subclass have the property within a suitable range of t, with outside that range. It is concluded that this is also the necessary condition for obtaining the noise law from a subclass chosen from any class of reasonable perturbations.

The extension of the law can be achieved for any a , using equation (48) as the starting point, which is exact. However, for any process suffering from reasonable perturbations, the exponents must satisfy the constraints

............(66)

............(67)

Some conclusions are summarised in the following statements;

1) To generate random noise having an spectral density over an arbitrarily large range of f from a subclass of reasonable perturbations occurring at random, chosen from any class characterised by and , it is necessary that .

2) To generate random noise having an spectral density over the arbitrarily large range

............(68)

from a subclass of reasonable perturbations occurring at random, chosen from any class characterised by and , for a in the more restricted interval , it is necessary and sufficient that such subclass satisfy the condition

............(69)

with B constant, over the range , and that , for t outside the range e to z.

3) Any reasonable perturbation has , and . At least one class of reasonable perturbations exists which has and . Indeed an unlimited number of such classes exist.

4) It follows from statements 1), 2), 3) that the only values for a for which noise over an arbitrarily large range of f, can be generated by a subclass chosen from any class of reasonable perturbations are in the interval . This interval of a is centred on the flicker law, .

5) For the smoothed random noise spectral density due to a subclass of reasonable perturbations occurring at random, chosen from any class characterised by and , the law holds at sufficiently high frequencies. The law also holds for the spectral density in the frequency range

if, for ,

and also if, for . Similarly, for such a subclass, the smoothed law holds at sufficiently low frequencies. The law also holds for the spectral density in the frequency range if, for ,

and also if, for .

Discussion.

This general method of generating an spectral density gives special attention to the factor of (48). A second method exists, in which the special attention is given instead to the shape of each of the time dependent perturbations. This second method is severely restricted in its choice of classes of perturbations which can generate noise for any specific value of a . In this second method, a physical explanation of a flicker noise spectrum extending over more than a couple of decades of frequency requires postulating the existence of specially shaped, time dependent perturbations, which are rarely, or never, found. On the other hand, the random perturbations found to be affecting physical processes often do have broad distributions of their lifetime square-amplitude product, one of the necessary conditions for the proper application of the first method. The diffusion process is a prime example of a physical process which gives rise to broad distributions of lifetimes. The first person to point out that a distribution of t might be important appears to have been Bernamount in 1937. Since then, many investigators have invoked particular distributions of t in attempts to explain flicker noise.

The above extraction of Halford’s publication needs to be put into perspective regarding observed electrochemical noise phenomena, i.e. how electrochemical noise spectra may be related to particular types of mechanistic processes.

Early studies of electrochemical noise were focused particularly on the naturally occurring fluctuations of potential. Spectral analysis of the signals generated in a wide range of corrosion circumstance showed that the values of a were variable over a wide range and were in the range typically of 0 to -4. Halford's analysis of the expectation for particular values of a, suggests that values for a more negative than -2, would probably arise due to some additional filtering process. In the case of corroding systems, this is probably associated with our understanding of the fundamental corrosion mechanisms. In the case of corrosion, and indeed of electrochemical systems in general, the driving force of a process is often envisaged as a potential. This is perhaps due to the manner in which electrochemists traditionally observe, and interpret, the behaviour of electrochemical interfaces. In particular, the deterministic method of applying a potential and observing the current response of a system. Whereas this manner of experimentation can be used at controlled potentials, it is inappropriate in the study of the fluctuations of the free corrosion potential.

One could argue that in the case of freely corroding systems, fluctuations in the corrosion current give rise to the observed fluctuations in the free corrosion potential, through the interfacial impedance. This would be consistent with values of a more negative than -2. It is impossible, in practice, to monitor the corrosion current directly, and therefore, in studies of electrochemical current noise, advantage has been taken of the fact that the instantaneous corrosion current, and potential, of any two specimens of material, have virtually zero probability of being identical.

By coupling together two nominally identical specimens of material through sensitive zero resistance ammeters (ZRA's), current flow is observed. The current flow arises as a consequence of the instantaneous differences in the corrosion currents and potentials of the two specimens. The two electrodes in this configuration are effectively held at the same potential by the ZRA, but the composite potential of the specimen is essentially the free corrosion potential. It is therefore possible to monitor fluctuations in both current and potential of a system arising from fluctuations in corrosion current.

The spectral characteristics of the current noise observed in these cases have a values of between 0 and -2, of which the two limit values are the most common. Some systems have been observed where a equals -1. For the purposes of the interpretation of the spectral characteristics of the current fluctuations, the following three cases are identified;

1)a values of 0 correspond to stochastic processes (equivalent to shot noise), where the spontaneous fluctuations in current are uncorrelated and do not exhibit time dependent characteristics. This type of process has a Poisson distribution.

2)a values of -2 correspond to an exponential-type law where the current exhibits distinct time dependence, this type of behaviour may be observed with systems having exponential or Gaussian distributions.

3)a values of -1 are most probably related with diffusion processes, which typically have a broad distribution of lifetimes.

The reader is reminded that the above is based upon random events and does not take into account periodicity of any processes which may occur. In practical situations the occurrence of peaks within the frequency domain is an indicator that certain of the processes observed have a periodicity which arise due to particular conditions, certain types of localised corrosion have been observed to exhibit this type of behaviour.

With regard to the potential noise spectra for freely corroding systems, it has been postulated that the potential signals arise from the interaction of the fluctuations in corrosion current and the interfacial impedance. It is possible to compare the estimate of the transfer function, or impedance |Z|, obtained from the current and potential signals, with that obtained by more conventional methods, i.e. electrochemical impedance spectroscopy. However, due to limitations in the high frequency range over which it is possible to measure the spontaneous fluctuations of potential and current, this is more appropriate for slow corrosion processes. For fast corrosion processes the low frequency transfer function is usually almost purely resistive. By way of example, the power spectrum of a potential noise signal, arising from a current noise source having a = -2, would depend upon the interfacial time constant for the system. If the interfacial impedance were purely resistive then the potential noise power spectrum would exhibit a = -2. On the other hand, if the system behaves as a parallel RC network within the frequency range of the measurements, the potential noise power spectrum would exhibit a = -4. In this latter case the interfacial impedance is effectively acting as a low pass filter to the current fluctuations.

CONCLUSIONS  Top

Electrochemical noise techniques have developed radically over the last sixteen years, with improved data acquisition and analysis routines the data presented to the user of the systems offered today provide a rich source of information which can be used in a wide variety of ways.

The future holds the challenge of providing automated correlation with process plant operational information.

The use of expert systems and neural network technologies will be used to give the operator not only cause and effect of the corrosion regimes, but also guidelines as to methodologies for the avoidance of particular corrosion regimes.

Whereas these expert systems will often be able to advise about corrosion preventative measures, it is unlikely (except for the simplest systems), that control will be automated. Rather that they will be used to help to provide a pro-active approach to corrosion control and maintenance strategies, with concomitant savings in downtime, materials, and maintenance costs.

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  57. C.A.C.Sequeira, "Electrochemical Techniques for Studying Microbial Corrosion," Microbial Corrosion. 1, Sintra, Portugal, 7-9 Mar. 1988, (Elsevier Applied Science, Crown House, Linton Road, Barking, Essex IG11 8JU, UK, 1988, 99-118)
  58. L.Tomosanyi, A.Csanady, F.Molnar, "Passivity of Aluminium and Its Alloys; Investigation and Technology of Passive Layer," Corrosion Week. Lectures 1/Korrosionswoche. Vortrage 1, Budapest, Hungary, 11-15 Apr. 1988, (Scientific Society of Mechanical Engineers, P.O. Box 451, H-1372 Budapest, Hungary", 1988, 78-82)
  59. I.Garz, J.Gollner, "Corrosion Investigations With the Aid of Electrochemical Noise," Corrosion Week. Lectures 2/Korrosionswoche. Vortrage 2, Budapest, Hungary, 11-15 Apr. 1988, (Scientific Society of Mechanical Engineers, P.O. Box 451, H-1372 Budapest, Hungary, 1988, 528-534)
  60. P.R.Roberge, R.Beaudoin, V.S.Sastri, "Electrochemical Noise Measurements for Field Applications," CORROS. SCI. 29, (10), 1231-1233 1989.
  61. M.Metikos-Hukovic, M.Loncar, C.Zevnik, " Monitoring the Electrochemical Potential Noise Produced by Coated Metal Electrodes," WERKST. KORROS. 40, (8), 494-499 Aug. 1989
  62. R.A.Cottis, C.A.Loto, "Electrochemical Noise Generation During SCC of a High-Strength Carbon Steel," CORROSION 46, (1), 12-19 Jan. 1990
  63. F.Carassiti, R.Cigna, G.Gusmano, R.Goolamallee, "Detection of Localised Corrosion by Means of Statistic and Harmonic Analysis of Spontaneous Potential Noise," MATER. SCI. FORUM 44-45, 271-278 1989
  64. C.Gabrielli, F.Huet, M.Keddam, R.Oltra, "A Review of the Probabilistic Aspects of Localized Corrosion," CORROSION 46, (4), 266-278 Apr. 1990
  65. T.Shibata, J.Horikawa, S.Fujimoto, "Noise Analysis of Corrosion Potential of Type 304 Stainless Steel in MgCl2 Solution," BOSHOKU GIJUTSU (CORROS. ENG.) 38, (3), 155-160
  66. D.Liu, F.Wang, C.Cao, H.Lou, "Influence of Phase Composition on Pitting Corrosion Resistance of Sputtered Layer of 1Cr18Ni9Ti Stainless Steel," ACTA METALL. SIN. (CHINA) 25, (5), B299-B302 Oct. 1989
  67. J.A.Richardson, "Monitoring Corrosion in Process Plant," Step Into the 90's. Vol. 1, Queensland, Australia, 27-31 Aug. 1989, (Australasian Institute of Metal Finishing, 191 Royal Parade, Parkville, Victoria 3052, Australia, 1989, 1-11)
  68. T.Shibata, "Stochastic Studies of Passivity Breakdown," CORROS. SCI. 31, 413-423 1990
  69. K.E.Heusler, "Growth and Dissolution of Passivating Films," CORROS. SCI. 31, 597-606 1990
  70. J.L.Dawson, D.G.John, M.I.Jafar, K.Hladky, L.Sherwood, "Electrochemical Methods for the Inspection and Monitoring of Corrosion of Reinforcing Steel in Concrete," Corrosion of Reinforcement in Concrete, Wishaw, Warwickshire, UK, 21-24 May 1990, (Elsevier Applied Science, Crown House, Linton Road, Barking, Essex IG11, 8JU, UK, 1990, 358-371)
  71. S.Sathlyanarayanan, S.P.Manoharan, G.Rajagopal, K.Balakrishnan, "Evaluation of Semiconductive Properties of the Oxide Films on Copper," BULL. ELECTROCHEM. 6, (1), 18-19 Jan. 1990
  72. J.M.Bastidas, S.Feliu Jr, M.Morcillo, S.Feliu, "Study of the Electrochemical Noise Generated by the Mild Steel/Zinc-Rich Paint/NaCl Solution System," PROG. ORG. COATINGS 18, (3), 265-273 23 July 1990
  73. G.Gao, F.H.Stott, J.L.Dawson, D.M.Farrell, "Electrochemical Monitoring of High-Temperature Molten-Salt Corrosion," OXIDATION OF METALS 33, (1-2), 79-94 Feb. 1990
  74. N.Celati, "Characteristics of Pitting Corrosion in Aluminum--Lithium Alloys," Final Report Etablissement Technique Central de l'Armement Pp 61 22 Dec. 1989, Report No. PB91-110932/XAB
  75. N.Celati, "Characteristics of Pitting Corrosion in Aluminum--Lithium Alloys," Final Report Etablissement Technique Central de l'Armement, NASA Pp 56 22 Dec. 1989, Report No. N90-27903/5/XAB
  76. S.Smith, R.Francis, "Use of Electrochemical Current Noise to Detect Initiation of Pitting Conditions on Copper Tubes," BRITISH CORROSION JOURNAL 25, (4), 285-291 1990
  77. D.Liu, F.Wang, Ch.Cao, H.Lou, L.Zhang, H.Lin, "The Pitting Corrosion Resistance of Microcrystalline Coatings of Sputtered 321 Stainless Steel," CORROSION 46, (12), 957-977 Dec. 1990
  78. F.Mansfeld, B.Little, "A Technical Review of Electrochemical Techniques Applied to Microbiologically Influenced Corrosion," CORROSION SCIENCE 32, (3), 247-272 Mar. 1991
  79. N.Celati, "Characteristics of Pitting Corrosion in Aluminum--Lithium Alloys," Final Report, Etablissement Technique Central de l'Armement Pp 61 22 Dec. 1989 Report No.: PB91-110932/XAB
  80. N.Celati, "Characteristics of the Pitting Corrosion in Aluminum--Lithium Alloys," Final Report, Etablissement Technique Central de l'Armement, NASA Pp 56 22 Dec. 1989, Report No.: N90-27903/5/XAB
  81. T.Okada, "A Theoretical Analysis of the Electrochemical Noise During the Induction Period of Pitting Corrosion in Passive Metals. I. The Current Noise Associated With the Adsorption/Desorption Processes of Halide Ions on the Passive Film Surface," JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY 297, (2), 349-359 25 Jan. 1991
  82. T.Okada, "A Theoretical Analysis of the Electrochemical Noise During the Induction Period of Pitting Corrosion in Passive Metals. II. The Current Noise Associated With Halide Nucleus Formation in the Passive Film," JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY, 297, (2), 361-375 25 Jan. 1991
  83. C –N.Cao, Q.Shi, H.Lin, "Features of Electrochemical Noise Generated From Fluctuation of Current for Passivated Metals Below Pitting Corrosion Potential," BULLETIN OF ELECTROCHEMISTRY 6, (8), 710-713 Aug. 1990
  84. J.Flis, J.L.Dawson, J.Gill, G.C.Wood, "Impedance and Electrochemical Noise Measurements on Iron and Iron--Carbon Alloys in Hot Caustic Soda," CORROSION SCIENCE 32, (8), 877-892 Aug. 1991
  85. S.Magaino, R.Yamazaki, N.Kobayashi, "Application of Electrochemical Noise Analysis to Chemical Etching of Steel," JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY, 305, (1), 141-145 25 Apr. 1991
  86. S.C.Dexter, D.J.Duquette, O.W.Siebert, H.A.Videla, "Use and Limitations of Electrochemical Techniques for Investigating Microbiological Corrosion," CORROSION 47, (4), 308-318 Apr. 1991
  87. C.Gabrielli, F.Huet, M.Keddam, R.Oltra, "Localized Corrosion as a Stochastic Process: a Review," Advances in Localized Corrosion, Orlando, Florida, USA, 1-5 June 1987 (National Association of Corrosion Engineers, 1440 South Creek Dr., Houston, Texas 77084, USA, 1990, 93-108)
  88. J.Uruchurtu, "Transient Behavior of Pure Aluminum During Noise Analysis," ibid. 141-144
  89. A.M.P.Simoes, "Passivation and Crevice Corrosion on Stainless Steel. (Thesis)," Technical University of Lisbon Pp 284, 1989, Report No.: PB91-177741/XAB
  90. M.Metikis-Hukovic, E.Stupnisek-Lisac, M.Loncar, "Electrochemical Noise Measurements for the Evaluation of the Protective Properties of Organic Coatings in Marine Atmospheric Environments," BULLETIN OF ELECTROCHEMISTRY 7, (3), 128-132 Mar. 1991
  91. J.U.Chavarin, "Electrochemical Investigations of the Activation Mechanism of Aluminum," CORROSION 47, (6), 472-479 June 1991
  92. C-T.Chen, B.S.Skerry, "Assessing the Corrosion Resistance of Painted Steel by AC Impedance and Electrochemical Noise Techniques," CORROSION 47, (8), 598-611 Aug. 1991
  93. J.Gollner, I.Garz, "Noise Diagnosis in Hole Corrosion," WISSENSCHAFTLICHE ZEITSCHRIFT DER TECHNISCHEN UNIVERSITAT OTTO VON GUERICKE, MAGDEBURG 34, (7), 20-26 1990
  94. J.Stewart, P.M.Scott, D.E.Williams, D.B.Wells, "Electrochemical Noise Measurements of Stress Corrosion Cracking of Sensitised Austenitic Stainless Steel in High-Purity Oxygenated Water at 288 deg C," CORROSION SCIENCE 33, (1), 73-87 Jan. 1992
  95. C.Gabrielli, F.Huet, M.Keddam, "Investigation of Metallic Corrosion by Electrochemical Noise Techniques," Electrochemical and Optical Techniques for the Study and Monitoring of Metallic Corrosion, Vienna do Castelo, Portugal, 9-21 July 1989, (Kluwer Academic Publishers, P.O. Box 17, 3300 AA Dordrecht, The Netherlands, 1991 135-190)
  96. M.G.S.Ferreira, A.M.P.Simoes, "Passivation and Localized Corrosion," ibid. 485-520
  97. Y.J.Qian, X.F.Mai, Z.Chen, "Investigation of Harmonic Analysis and Potential Noise on Detection of Pitting Corrosion and Inhibition," Corrosion Control--7th APCCC. Vol. 1, China, 1991 (International Academic Publishers, Xizhimenwai Dajie, Beijing Exhibition Centre, Beijing 100044, People's Republic of China, 1991, 215-217)
  98. J.Stewart, P.M.Scott, D.E.Williams, D.B.Wells, "Electrochemical Noise Measurements of Stress Corrosion Cracking of Sensitised Austenitic Stainless Steel in High-Purity Oxygenated Water at 288 deg C," CORROSION SCIENCE 33, (1), 73-88, Jan. 1992
  99. C.Monticelli, G.Brunoro, A.Arignani, G.Trabanelli, "Evaluation of Corrosion Inhibitors by Electrochemical Noise Analysis," JOURNAL OF THE ELECTROCHEMICAL SOCIETY 139, (3), 706-711, Mar. 1992
  100. T.Okda, "Electrochemical Noise Considered by Two-Step Initiation Hypothesis of Pitting Corrosion," Critical Factors in Localized Corrosion, Phoenix, Arizona, USA, 14-16 Oct. 1991, (The Electrochemical Society, Inc., 10 South Main St., Pennington, New Jersey 08534-2896, USA, 1992, 65-80, Report No.: PV 92-9
  101. M.S.Sherratt, F.P.A.Robinson, M.Tullmin, A.N.Rothwell, "Electrochemical Noise Measurements on Mild and 12% Chromium Steel in a Chloride Solution," CORROSION AND COATINGS, SOUTH AFRICA 19, (2), 6-12 Apr.-May 1992
  102. B.S.Skerry, C-T.Chen, C.J.Ray, "Pigment Volume Concentration and Its Effect on the Corrosion Resistance Properties of Organic Paint Films," JOURNAL OF COATINGS TECHNOLOGY 64, (806), 77-86 Mar. 1992
  103. H.Scholl, M.M.Davila Jimenez, "The Application of 1-Hydroxyimidazole-3-N-Oxides as Aluminium Corrosion Inhibitors in Alkaline Solutions," CORROSION SCIENCE 33, (12), 1967-1978 Dec. 1992
  104. C.Gabrielli, M.Keddam, "Review of Applications of Impedance and Noise Analysis to Uniform and Localized Corrosion," CORROSION 48, (10), 794-811 Oct. 1992
  105. V.S.Sastri, P.R.Roberge, "Monitoring Corrosion in Sour Media," Materials Performance: Sulphur and Energy, Edmonton, Alberta, Canada, 23-27 Aug. 1992, (Canadian Institute of Mining, Metallurgy and Petroleum, Xerox Tower, 1210-3400 de Maisonneuve Blvd. W., Montreal, Quebec H3Z 3B8, Canada, 1992, 57-69)
  106. S.T.Hirozawa, D.E.Turcotte, "Use of Electrochemical Noise in the Study of Inhibitor Systems for Aluminum," Materials Performance Maintenance, Ottawa, Ontario, Canada, 18-21 Aug. 1991, (Pergamon Press, Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, USA, 1991, 207-222)
  107. M.Tullmin, D.A.Eden, A.N.Rothwell, "A PC Based Corrosion Monitoring System Using Advanced Electrochemical Techniques," CORROSION AND COATINGS, SOUTH AFRICA 20, (1), 4-6, 8 Feb. 1993
  108. T.Okada, "A Theoretical Analysis of the Electrochemical Noise During the Induction Period of Pitting Corrosion in Passive Metals," JOURNAL OF THE ELECTROCHEMICAL SOCIETY 140, (5), 1261-1268 May 1993
  109. U.Cano, J.M.Malo, J.Uruchurtu, "Is It Chaos or Is It Electrochemical Noise? Aluminium Corrosion in Chloride Media," REVISTA DE METALURGIA 28, (6), 348-352 Nov.-Dec. 1992
  110. D.E.Turcotte, S.T.Hirozawa, M.C.Welch, "Gem-Diphosphonates as Corrosion Inhibitors on Aluminum," Light Metals Processing and Applications, Quebec City, Quebec, Canada, 29 Aug.-1 Sept. 1993, (Canadian Institute of Mining, Metallurgy and Petroleum, Xerox Tower, 1210-3400 Maisonneuve Blvd. W., Montreal, Quebec H3Z 3B8, Canada, 1993, 867-874)
  111. E.Benzaid, F.Huet, C.Gabrielli, M.Jerome, F.Wenger, J.Galland, "Investigation of Electrochemical Noise in the Study of Hydrogen Embrittlement of a 42CD4 Carbon Steel Electrode," Progress in the Understanding and Prevention of Corrosion. Vol. II, Barcelona, Spain, July 1993, (The Institute of Materials, 1 Carlton House Terrace, London SW1Y 5DB, UK, 1993,1304-1311)
  112. N.J.E.Dowling, C.Thual-Duret, G.Auclair, J.P.Audouard, P.Combrade, "Assessment of the Pitting Susceptibility of AISI 303 and 304 Stainless Steels as a Function of Sulphur Content Using Electrochemical Noise," ibid. 1328-1339
  113. P.R.Roberge, "Analysis of Spontaneous Electrochemical Noise With a Stochastic Pattern Detector Method," ibid. 1345-1351
  114. B.S.Skerry, D.A.Eden, "Characterisation of Coatings Performance Using Electrochemical Noise Analysis," PROGRESS IN ORGANIC COATINGS 19, (4), 379-396 11 Nov. 1991
  115. A.Legat, V.Dolecek, "Corrosion Monitoring System Based on Measurements and Analysis of Electrochemical Noise," NACE International, P.O. Box 218340, Houston, Texas 77218, USA, 1994, Pp 5, Paper No. 319
  116. S.T.Hirozawa, D.E.Turcotte, "Use of Electrochemical Noise in the Study of Inhibitor Systems. I. The Effect of Silicate Polymerization on the Inhibition of Aluminum," Electrochemical Impedance: Analysis and Interpretation, San Diego, California, United States, 4-5 Nov. 1991 (ASTM, 1916 Race St., Philadelphia, Pennsylvania 19103, United States, 1993, 205-219, Report No.: STP 1188
  117. P.C.Pistorius, T.von Moltke, "Pitting Corrosion of Heat-Tinted Stainless Steel," Modifications of Passive Films, Paris, France, 15-17 Feb. 1993, (The Institute of Materials, 1 Carlton House Terrace, London, SW1Y 5DB, UK, 1994, 316-321, Book No. 577)
  118. P.R.Roberge, E.Halliop, D.R.Lenard, J.G.Moores, "Electrochemical Characterization of the Corrosion Resistance of Aluminum-Lithium Alloys," CORROS. SCI. 35, (1-4), 213-221 1993
  119. A.M.Brennenstuhl, T.S.Gendron, R.Cleland, "Mechanisms of Underdeposit Corrosion in Freshwater Cooled Austenitic Alloy Heat Exchangers," CORROS. SCI. 35, (1-4), 699-711 1993
  120. A.M.Brennenstuhl, T.S.Gendron, "The Use of Field Tests and Electrochemical Noise to Define Conditions for Accelerated Microbiologically Influenced Corrosion (MIC) Testing," Microbiologically Influenced Corrosion Testing, Miami, Florida, United States, 16-17 Nov. 1992, (ASTM, 1916 Race St., Philadelphia, PA 19103-1187, United States, 1994, 15-27, STP 1232)
  121. F.Mansfield, H.Xiao, "Electrochemical Techniques for Detection of Localized Corrosion Phenomena," ibid. 42-60.
  122. I.B.Singh, G.Venkatachari, K.Balakrishnan, "Electrochemical Studies on the Oxidation Behaviour of Iron in NaNO3 - NaNO2 Melt," CORROS. SCI. 36, (10), 1777-1788 Oct. 1994
  123. H.Xiao, F.Mansfield, "Evaluation of Coating Degradation With Electrochemical Impedance Spectroscopy and Electrochemical Noise Analysis," J. ELECTROCHEM. SOC. 141, (9), 2332-2337 Sept. 1994
  124. B.Little, P.Wagner, F.Mansfeld, "Test Methods for Microbiologically Influenced Corrosion (MIC) in Marine Environments," MATER. SCI. FORUM 111-112, 1-23 1992
  125. A.Benzaid, C.Gabrielli, F.Huet, M.Jerome, F.Wenger, "Investigation of the Electrochemical Noise Generated During the Stress Corrosion Cracking of a 42CD4 Steel Electrode," MATER. SCI. FORUM 111-112, 167-175 1992
  126. M.S.Sherratt, F.P.A.Robinson, M.Tullmin, A.N.Rothwell, "Electrochemical noise measurements on mild and 12% chromium steel in chloride solution," BR. CORROS. J. 29, (1), 33-37 1994
  127. M.Moon, B.S.Skerry, "Evaluation of corrosion protection by organic coatings from fractal analysis of electrochemical noise data," POLYM. PREPR. 35, (2), 303-304 Aug. 1994
  128. C.Monticelli, F.Zucchi, F.Bonollo, G.Brunoro, A.Frignani, G.Trabanelli, "Application of electrochemical noise analysis to study the corrosion behavior of aluminum composites," J. ELECTROCHEM. SOC. 142, (2), 405-410 Feb. 1995
  129. P.R.Roberge, "Analysis of electrochemical noise by the stochastic process detector method," CORROSION 50, (7), 502-512 July 1994
  130. N.Celati, C.Bataillon, "Characterization of pitting corrosion on aluminium alloys by electrochemical noise analysis," Eurocorr '91. Vol. 2, Budapest, Hungary, 21-25 Oct. 1991, (GTE Rendezveny Iroda gondozasaban, 1055 Budapest, Kossuth L. ter 6-8, Budapest, Hungary, 1991, 701-706)
  131. K.R.Trethewey, P.R.Roberge, "The characterization of surface profiles created by localized corrosion with stochastic and fractal analysis techniques," Localized Damage III. Computer-Aided Assessment and Control, Udine, Italy, 21-23 June 1994, (Computational Mechanics Publications, 25 Bridge St., Billerica, MA, 01821, 323-330, 1994)
  132. G.P.Bierwagen, V.Balbyshev, D.Mills, D.Tallman, "Fundamental considerations on electrochemical noise methods to examine corrosion under organic coatings," Advances in Corrosion Protection by Organic Coatings II, Cambridge, UK, 1994, (Electrochemical Society, Inc., 10 S. Main St., Pennington, NJ 08534, USA, 1995, 69-81)
  133. D.J.Mills, S.Berg, G.P.Bierwagen, "Characterization of the corrosion control properties of organic electrodeposition coatings," ibid. 82-97
  134. D.J.Mills, G.P.Bierwagen, B.S.Skerry, D.Tallman, "Investigation of anticorrosive coatings by the electrochemical noise method," MATER. PERFORM. 34, (5), 33-38 May 1995
  135. M.Moon, B.S.Skerry, "Interpretation of corrosion resistance properties of organic paint films from fractal analysis of electrochemical noise data," J. COATINGS TECHNOL. 67, (843), 35-44 Apr. 1995
  136. A.Legat, V.Delecek, "Chaotic analysis of electrochemical noise measured on stainless steel," J. ELECTROCHEM. SOC. 142, (6), 1851-1858 June 1995
  137. P.R.Roberge, "Analysis of spontaneous electrochemical noise for corrosion studies," JOURNAL OF APPLIED ELECTROCHEMISTRY 23, (12), 1223-1231 Dec. 1993
  138. G.Gusmano, G.Montesperelli, S.Pacetti, "A study of the factors affecting electrochemical noise of carbon steel in natural waters," TEKHNOLOGIYA LEGKIKH SPLAVOV 561-568 1995
  139. S.T.Hirozawa, "Use of electrochemical noise in the study of corrosion inhibition of aluminum by gem-diphosphonates," TEKHNOLOGIYA LEGKIKH SPLAVOV 25-33 1995
  140. C.Monticelli, M.C.Boggiani, F.Zucchi, "Monitoring of DHP copper corrosion and inhibition by electrochemical noise analysis," TEKHNOLOGIYA LEGKIKH SPLAVOV 45-55 1995
  141. O.E.Garcia, J.Uruchurtu, J.Genesca, "Electrochemical response of copper during pitting corrosion phenomena in chloride solutions," REVISTA DE METALURGIA 31, (6), 361-367 Nov.-Dec. 1995
  142. J.W.Isaac, M-H.Wang, K.R.Hebert, "Electrochemical noise measurements on aluminum microelectrodes," Critical Factors in Localized Corrosion II, Chicago, Illinois, USA, 9-11 Oct. 1995, (Electrochemical Society, Inc., 10 South Main St., Pennington, NJ 08534-2896, USA, 1996, 380-390)
  143. B.Malki, A.Legris, J.L.Pastol, D.Gorse, "A study of dealloying of Cu-Au in aqueous solution by electrochemical noise measurements," ibid. 391-402
  144. J.R.Scully, S.T.Pride, H.S.Scully, J.L.Hudson, "Some correlations between metastable pitting and pit stabilization in metals," ibid. 15-29
  145. H.Mayet, B.Baroux, "A chaotic behavior in pitting corrosion processes," ibid. 368-379
  146. G.Venkatachari, C.Marikkannu, S.Muralidharan, K.Balakrishnan, "Voltage noise measurements during staining of 6061 aluminium alloy exposed to humid atmospheres," BULLETIN OF ELECTROCHEMISTRY 12, (1-2), 77-79 Jan.-Feb. 1996
  147. J.Swarup, P.C.Sharma, "Electrochemical techniques for the monitoring of corrosion of reinforcement in concrete structures," BULLETIN OF ELECTROCHEMISTRY 12, (1-2), 103-108 Jan.-Feb. 1996
  148. M.Slemnik, A.Petek, V.Dolecek, "Measurements of electrochemical noise on the passive layer of differently heat treated stainless steels," WERKSTOFFE UND KORROSION 46, (1), 13-17 Jan. 1995
  149. C.Boulleret, J-L.Pastol, J.Bigot, B.Baroux, D.Gorse, "Pitting resistance of pure Fe-17% Cr alloys: consequences for localized corrosion modeling," JOURNAL DE PHYSIQUE (FRANCE) IV 5, (7), 415-422 Nov. 1995
  150. F.Mansfield, H.Xiao, Y.Wang, "Evaluation of localized corrosion phenomena with electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ENA)," WERKSTOFFE UND KORROSION 46, (1), 3-12 Jan. 1995
  151. F.Mansfeld, H.Xiao, L.T.Han, C.C.Lee, "The impact of microorganisms on corrosion protection by polymer coatings," Polymeric Materials Science and Engineering Spring Meeting 1996. Vol. 74, New Orleans, Louisiana, USA, 24-28 Mar. 1996, (American Chemical Society, 1155 16th St. N.W., Washington, DC 20036, USA, 1996, 75-76)
  152. V.N.Balbyshev, G.P.Bierwagen, "Electrochemical studies of vinyl ester coatings for fuel tanks," ibid. 121-122
  153. R.L.Twite, G.P.Bierwagen, "Defect area calculated from electrochemical noise and impedance measurements," ibid. 123-124
  154. C.Boulleret, D.Gorse, B.Baroux, "The pitting susceptibility of stainless steels after a stay at open circuit in acidified chloride containing solution," CORROSION SCIENCE 38, (6), 999-1002 June 1996
  155. J.G.Gonzalez-Rodriguez, V.M.Salinas-Bravo, J.M.Ramirez-Montano, "A study of the stress corrosion cracking susceptibility of AISI 410 steel in steam turbine environments using electrochemical noise," CORROSION REVIEWS 14, (3-4), 309-321 1996
  156. U.Cano, J.M.Malo, J.Uruchurtu, "Aluminium corrosion in chloride solution. Is it chaos or is it electrochemical noise?" CORROSAO E PROTECCAO DE MATERIAIS 13, (1), 6-12 Jan.-Mar. 1994
  157. W.Morgner, "New possibilities of nondestructive pipe corrosion monitoring," WERKSTOFFE UND KORROSION 46, (7), 398-404 July 1995
  158. J.R.Kearns, J.R.Scully, "Electrochemical Noise Measurement for Corrosion Applications," (ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, USA, 1996)
  159. Z.Szklarska-Smialowska, "Electrochemical methods in stress corrosion cracking," MATERIALS SCIENCE FORUM 192-194, (1), 11-24, 1995
  160. R.A.Cottis, S.Turgoose, "Electrochemical noise measurements--a theoretical basis," MATERIALS SCIENCE FORUM 192-194, (2), 663-672 1995
  161. M.E.M.D.Almeida, L.Mariaca, J.U.Chavarin, M.A.Veloz, "Electrochemical measurements of prerusted steels pretreated in H3PO4 solutions," MATERIALS SCIENCE FORUM 192-194, (2), 723-732 1995
  162. P.R.Roberge, S.Wang, R.Roberge, "Stainless steel pitting in thiosulfate solutions with electrochemical noise," CORROSION 52, (10), 733-737 Oct. 1996
  163. J.F.Chen, W.F.Bogaerts, "Electrochemical emission spectroscopy for monitoring uniform and localized corrosion," CORROSION 52, (10), 753-759 Oct. 1996
  164. A.M.Etheridge, J.M.Sykes, J.D.B.Sharman, E.McAlpine, "Electrochemical measurements during the formation of thin film conversion coatings," MATERIALS SCIENCE FORUM 192-194, (1), 345-356 1995
  165. F.Mansfeld, H.Xiao, Y.Wang, "Evaluation of localized corrosion phenomena with electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ENA)," MATERIALS SCIENCE FORUM 192-194, (2), 673-692 1995
  166. M.Schneider, K.Nocke, H.Pohl, E.Kock, "In situ investigation of crevice corrosion by electrochemical noise analysis," MATERIALS SCIENCE FORUM 217-222, (3), 1547-1552, 1996
  167. M.C.Reboul, T.J.Warner, H.Mayet, B.Baroux, "A ten-step mechanism for the pitting corrosion of aluminium," MATERIALS SCIENCE FORUM 217-222, (3), 1553-1556 1996
  168. J.Fahey, D.Holmes, T-L.Yau, "Evaluation of localized corrosion of zirconium in acidic chloride solutions," CORROSION 53, (1), 54-61 Jan. 1997
  169. P.C.Pistorius, "Design aspects of electrochemical noise measurements for uncoated metals: electrode size and sampling rate," CORROSION 53, (4), 273-283 Apr. 1997
  170. F.Mansfeld, L.T.Han, C.C.Lee, C.Chen, G.Zhang, H.Xiao, "Analysis of electrochemical impedance and noise data for polymer coated metals," CORROSION SCIENCE 39, (2), 255-279 Feb. 1997
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