This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: G96 − 90 (Reapproved 2018)

Standard Guide for

Online Monitoring of Corrosion in Plant Equipment
(Electrical and Electrochemical Methods)1
This standard is issued under the fixed designation G96; the number immediately following the designation indicates the year of original
adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript
epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope 2. Referenced Documents

1.1 This guide covers the procedure for conducting online 2.1 ASTM Standards:2
corrosion monitoring of metals in plant equipment under D1125 Test Methods for Electrical Conductivity and Resis-
operating conditions by the use of electrical or electrochemical tivity of Water
methods. Within the limitations described, these test methods G1 Practice for Preparing, Cleaning, and Evaluating Corro-
can be used to determine cumulative metal loss or instanta- sion Test Specimens
neous corrosion rate, intermittently or on a continuous basis, G3 Practice for Conventions Applicable to Electrochemical
without removal of the monitoring probes from the plant. Measurements in Corrosion Testing
1.2 The following test methods are included: Test Method A G4 Guide for Conducting Corrosion Tests in Field Applica-
for electrical resistance, and Test Method B for polarization tions
resistance. G15 Terminology Relating to Corrosion and Corrosion Test-
ing (Withdrawn 2010)3
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1.2.1 Test Method A provides information on cumulative
metal loss, and corrosion rate is inferred. This test method G59 Test Method for Conducting Potentiodynamic Polariza-
responds to the remaining metal thickness except as described tion Resistance Measurements
in Section 5.
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1.2.2 Test Method B is based on electrochemical measure-
G102 Practice for Calculation of Corrosion Rates and Re-
lated Information from Electrochemical Measurements

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ments for determination of instantaneous corrosion rate but
may require calibration with other techniques to obtain true
corrosion rates. Its primary value is the rapid detection of
3. Terminology
3.1 Definitions—See Terminology G15 for definitions of
changes in the corrosion rate that may be indicative of terms used in this guide.
undesirable changes in the process environment. ASTM G96-90(2018)
4. Summary of Guide
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1.3 The values stated in SI units are to be considered
4.1 Test Method A–Electrical Resistance—The electrical
standard. The values in parentheses are for information only.
resistance test method operates on the principle that the
1.4 This standard does not purport to address all of the electrical resistance of a measuring element (wire, strip, or tube
safety concerns, if any, associated with its use. It is the of metal) increases as its cross-sectional area decreases:
responsibility of the user of this standard to establish appro-
l
priate safety, health, and environmental practices and deter- R5σ (1)
A
mine the applicability of regulatory limitations prior to use.
Specific precautionary statements are given in 5.6. where:
1.5 This international standard was developed in accor- R = resistance,
dance with internationally recognized principles on standard- σ = resistivity of metal (temperature dependent),
ization established in the Decision on Principles for the l = length, and
Development of International Standards, Guides and Recom- A = cross-section area.
mendations issued by the World Trade Organization Technical In practice, the resistance ratio between the measuring
Barriers to Trade (TBT) Committee. element exposed to corrosion and the resistance of a similar

1 2
This guide is under the jurisdiction of ASTM Committee G01 on Corrosion of For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Metals and is the direct responsibility of ASTM Subcommittee G01.11 on contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Electrochemical Measurements in Corrosion Testing. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved May 1, 2018. Published June 2018. Originally the ASTM website.
3
approved in 1990. Last previous edition approved in 2013 as G96 – 90 (2013). DOI: The last approved version of this historical standard is referenced on
10.1520/G0096-90R18. www.astm.org.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 G96 − 90 (2018)
reference element protected from corrosion is measured, to 4.2.3 The corrosion current density, icorr, can be converted
compensate for resistivity changes due to temperature. Based to corrosion rate of the electrode by Faraday’s law if the
on the initial cross-sectional area of the measurement element, equivalent weight (EW) and density, ρ, of the corroding metal
the cumulative metal loss at the time of reading is determined. are known (see Practice G102):
Metal loss measurements are taken periodically and manually i corr
or automatically recorded against a time base. The slope of the corrosion rate 5 K 1 EW (4)
ρ
curve of metal loss against time at any point is the correction
rate at that point. The more frequently measurements are taken, where:
the better is the resolution of the curve from which the K 1 = a constant.
corrosion rate is derived. 4.2.4 Equivalent weight of an element is the molecular
4.1.1 The electrical resistance of the metal elements being weight divided by the valency of the reaction (that is, the
measured is very low (typically 2 to 10 mΩ). Consequently, number of electrons involved in the electrochemical reaction).
special measurement techniques and cables are required to 4.2.5 In order to obtain an alloy equivalent weight that is in
minimize the effect of cable resistance and electrical noise. proportion with the mass fraction of the elements present and
4.1.2 Various probe element cross-sectional areas are nec- their valence, it must be assumed that the oxidation process is
essary so that a wide range of corrosion rates can be monitored uniform and does not occur selectively; that is, each element of
with acceptable resolution. the alloy corrodes as it would if it were the only element
4.2 Test Method B–Polarization Resistance: present. In some situations these assumptions are not valid.
4.2.1 The polarization resistance test method involves inter- 4.2.6 Effective equivalent weight of an alloy is as follows:
action with the electrochemical corrosion mechanism of metals 1
in electrolytes in order to measure the instantaneous corrosion m (5)
n if i
rate. Its particular advantage is its speed of response to (l Wi
corrosion rate upsets. On a corroding electrode subject to
certain qualifications (see 12.1), it has been shown that the where:
current density associated with a small polarization of the
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fi = mass fraction of ith element in the alloy,
electrode is directly proportional to the corrosion rate of the Wi = atomic weight of the ith element in the alloy,
electrode. ni = exhibited valence of the ith element under the condi-
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4.2.2 The polarization resistance equation is derived in Test
Method G59. See Practice G3 for applicable conventions. For
tions of the corrosion process, and
m = number of component elements in the alloy (normally

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small polarization of the electrode (typically ∆E up to 20 mV), only elements above 1 mass % in the alloy are
the corrosion current density is defined as: considered).
B Alloy equivalent weights have been calculated for many
i corr 5 (2)
engineering metals and alloys and are tabulated in Practice
Rp
ASTM G96-90(2018)
G102.
where:
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4.2.7 Fig. 1 represents an equivalent circuit of polarization
B = a combination of the anodic and cathodic Tafel slopes resistance probe electrodes in a corroding environment. The
(ba, bc), and value of the double layer capacitance, Cdl, determines the
Rp = the polarization resistance with dimensions ohm·cm2. charging time before the current density reaches a constant
ba bc value, i, when a small potential is applied between the test and
B5 (3)
2.303 ~ b a 1b c ! auxiliary electrode. In practice, this can vary from a few

NOTE 1—Rs = Solution Resistance (ohm·cm−2) between test and auxiliary electrodes (increases with electrode spacing and solution resistivity).
Ru = Uncompensated component of solution resistance (between test and reference electrodes) (ohm·cm−2).
Rp = Polarization Resistance Rp (ohm·cm2).
Cdl = Double layer capacitance of liquid/metal interface.
i = Corrosion current density.
FIG. 1 Equivalent Circuit of Polarization Resistance Probe

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 G96 − 90 (2018)
seconds up to hours. When determining the polarization reduced up to approximately ten fold. This extends the oper-
resistance, Rp, correction or compensation for solution ating range over which adequate determination of the polar-
resistance, Rs, is important when Rs becomes significant ization resistance can be made (see Fig. 2).
compared to Rp. Test Methods D1125 describes test methods 4.2.10 A two-electrode probe with electrochemical imped-
for electrical conductivity and resistivity of water. ance measurement technique at high frequency short circuits
4.2.8 Two-electrode probes, and three-electrode probes with the double layer capacitance, Cdl, so that a measurement of
the reference electrode equidistant from the test and auxiliary solution resistance, Rs, can be made for application as a
electrode, do not correct for effects of solution resistance, correction. This also extends the operating range over which
without special electronic solution resistance compensation. adequate determination of polarization resistance can be made
With high to moderate conductivity environments, this effect of (see Fig. 2).
solution resistance is not normally significant (see Fig. 2). 4.2.11 Even with solution resistance compensation, there is
4.2.9 Three-electrode probes compensate for the solution a practical limit to the correction (see Fig. 2). At higher
resistance, Rs, by varying degrees depending on the position solution resistivities the polarization resistance technique can-
and proximity of the reference electrode to the test electrode. not be used, but the electrical resistance technique may be
With a close-spaced reference electrode, the effects of Rs can be used.

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ASTM G96-90(2018)
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NOTE 1—See Appendix X1 for derivation of curves and Table X1.1 for description of points A, B, C and D.
NOTE 2—Operating limits are based on 20 % error in measurement of polarization resistance equivalent circuit (see Fig. 1).
NOTE 3—In the Stern-Geary equations, an empirical value of B = 27.5 mV has been used on the ordinate axis of the graph for “typical corrosion rate
of carbon steel”.
~ µmhos! 1 000 000
NOTE 4—Conductivity 5
cm Resistivity ~ ohm·cm!
NOTE 5—Effects of solution resistance are based on a probe geometry with cylindrical test and auxiliary electrodes of 4.75 mm (0.187 in.) diameter,
31.7 mm (1.25 ft) long with their axes spaced 9.53 mm (0.375 in.) apart. Empirical data shows that solution resistance (ohms·cm2) for this
geometry = 0.55 × resistivity (ohms·cm2).
NOTE 6—A two-electrode probe, or three-electrode probe with the reference electrode equidistant from the test and auxiliary electrode, includes % of
solution resistance between working and auxiliary electrodes in its measurement of Rp.
NOTE 7—A close-space reference electrode on a three electrode probe is assumed to be one that measures 5 % of solution resistance.
NOTE 8—In the method for Curve 1, basic polarization resistance measurement determines 2Rp + Rs (see Fig. 1). High frequency measurement short
circuits Cdl to measure Rs. By subtraction polarization resistance, Rp is determined. The curve is based on high frequency measurement at 834 Hz with
Cdl of 40 µ F/cm2 on above electrodes and 6 1.5 % accuracy of each of the two measurements.
NOTE 9—Curve 1 is limited at high conductivity to approximately 700 mpy by error due to impedance of Cdl at frequency 834 Hz. At low conductivity
it is limited by the error in subtraction of two measurements where difference is small and the measurements large.
NOTE 10—Errors increase rapidly beyond the 20 % error line (see Appendix X1, Table X1.1).
FIG. 2 Guidelines on Operating Range for Polarization Resistance

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 G96 − 90 (2018)
4.2.12 Other methods of compensating for the effects of equipment and cable runs (where applicable) to avoid electri-
solution resistance, such as current interruption, electrochemi- cally noisy sources such as power cables, heavy duty motors,
cal impedance and positive feedback have so far generally been switchgear, and radio transmitters.
confined to controlled laboratory tests. 6.2.1 The electrical resistivity of metals increases with
increased temperature. Although basic temperature compensa-
5. Significance and Use tion is obtained by measuring the resistance ratio of an exposed
5.1 General corrosion is characterized by areas of greater or test element and protected reference element, the exposed
lesser attack, throughout the plant, at a particular location, or element will respond more rapidly to a change in temperature
even on a particular probe. Therefore, the estimation of than does the protected reference element. This is a form of
corrosion rate as with mass loss coupons involves an averaging thermal noise. Various probes have different sensitivities to
across the surface of the probe. Allowance must be made for such thermal noise. Where temperature fluctuations may be
the fact that areas of greater or lesser penetration usually exist significant, preference should be given to probes with the
on the surface. Visual inspection of the probe element, coupon, lowest thermal noise sensitivity.
or electrode is required to determine the degree of interference 6.2.2 If probe elements are flexed due to excessive flow
in the measurement caused by such variability. This variability conditions, a strain gage effect can be produced introducing
is less critical where relative changes in corrosion rate are to be stress noise onto the probe measurement. Suitable probe
detected. element shielding can remove such effects.
5.2 Both electrical test methods described in this guide 6.3 Process fluids, except liquid metals and certain molten
provide a technique for determining corrosion rates without the salts, do not normally have sufficient electrical conductivity to
need to physically enter the system to withdraw coupons as produce a significant shorting effect on the electrical resistance
required by the methods described in Guide G4. of the exposed probe element. Conductive deposits (such as
iron sulfide) can cause some short–circuiting effect on the
5.3 Test Method B has the additional advantage of provid-
element, reducing the measured metal loss, or showing some
ing corrosion rate measurement within minutes.
apparent metal gain. Certain probe configurations are less
5.4 These techniques are useful in systems where process sensitive to this than others, depending on the path length
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upsets or other problems can create corrosive conditions. An
early warning of corrosive attack can permit remedial action
between one end of the exposed probe element and the other.
6.4 When first introduced into a system, initial transient
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before significant damage occurs to process equipment.
5.5 These techniques are also useful where inhibitor addi-
corrosion rates on a probe element may be different from the
longer term corrosion rates.

Document
indication of an increasing corrosion rate can be used to signal Preview
tions are used to control the corrosion of equipment. The 6.4.1 Establishment of a probe element surface typical of
the plant by passivation, oxidation, deposits, or inhibitor film
the need for additional inhibitor. build up may vary from hours to several days.
5.6 Control of corrosion in process equipment requires a
ASTM G96-90(2018) 6.5 Since the corrosion rate is usually temperature
knowledge of the rate of attack on an ongoing basis. These test dependent, results will be comparable only for the alloy at the
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methods can be used to provide such information in digital process temperature to which the probes are exposed. In heat
format easily transferred to computers for analysis. transfer environments actual plant metal temperatures may be
significantly different from that of the test probe.
TEST METHOD A—ELECTRICAL RESISTANCE
(1-6)4 6.6 Electrical resistance probe elements are by their nature
consumable. Hazardous situations may occur if probes are left
6. Limitations and Interferences in service for extended periods beyond their probe life. Crevice
6.1 Results are representative for average metal loss on the corrosion can cause damage or leaks at the element in some
probe element. On wire-form measuring elements, pitting may specimen configurations, that can cause false readings and
be indicated by rapid increases in metal loss reading after 50 % early failure of probe elements. Normally the probe life is
of probe life is passed. The larger cylindrical measuring limited to approximately 50 % of the probe element thickness
elements are much less sensitive to the effect of pitting attack. for safety reasons. Additionally, beyond this point measure-
Where pitting is the only form of attack, probes may yield ments become increasingly erratic due to the irregular corroded
unreliable results. surface of the probe element, and the particularly non-linear
characteristics of wire probe elements.
6.2 It should be recognized that the thermal noise and 6.6.1 Electrical resistance probes should be selected to
stress-induced noise on probe elements, and electrical noise on provide a suitable backup seal, that is compatible with the
these systems, occur in varying degrees due to the process and process environment, in order to contain the process if the
local environment. Care should be exercised in the choice of element seal fails.
the system to minimize these effects. Electrical noise can be
minimized by use of correct cabling, and careful location of 7. Apparatus
7.1 Electrical Resistance Corrosion Probes:
4
The boldface numbers in parentheses refer to a list of references at the end of 7.1.1 A probe is composed of two elements of identical
this standard. material. One is a measuring element and the other is a

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 G96 − 90 (2018)
protected reference element. In addition, a further check provides guidance on proper methods of cleaning various
element is fully incorporated beyond the reference element to materials. Some people do not recommend reusing the probes.
assist in monitoring of any process leakage into the probe. 8.4 Mechanical or chemical cleaning will remove metal
7.1.2 Process monitoring probes are available in both re- from the probe measurement element, increasing its reading.
tractable and non-retractable configurations. The former en- This new reading should be taken immediately after installa-
ables removal of the probe for inspection or probe replacement tion in the new location.
under operating conditions, except where operational safety
precludes this. 9. Probe Installation
7.1.3 There is a trade off between probe sensitivity and
9.1 Install the probe in a position as representative of the
probe life. Care should be taken in selecting a probe suffi-
corrosive environment as possible without causing deleterious
ciently sensitive for the corrosion conditions, particularly when
effects to the probe or the system. Do not mount probe
monitoring for process upsets.
transversely in a high-flow pipeline without shielding (see 6.3).
7.1.4 Systems typically have a resolution of 0.1 % of probe
life. However, for reasons of noise given in 6.2, it is generally 9.2 Do not install the probe in a dead-end section where
recommended that only changes of greater than 1 % of probe temperature or flow conditions, or both, are not representative
life are used for calculation of a corrosion rate or detection of of the system under examination.
an upset. When monitoring steady metal loss rather than
process upsets, probe life is generally more critical than 10. Procedure
response time. For example, a typical probe span suitable for a 10.1 Portable Intermittent Instrument:
six month probe life would have on average a 1 % change 10.1.1 Check correct operation of the instrument with the
approximately every two days. test probe provided according to the manufacturer’s instruc-
7.1.5 For process upset detection, response time to the upset tions.
is much more critical than probe life. A probe sensitivity should 10.1.2 Connect the instrument to the probe and log both the
be chosen such that 1 % of the probe life, at the upset corrosion measure and check readings. Ensure that the check reading is

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rate, corresponds to the desired or maximum permissible within specified limits. Follow the manufacturer’s instructions
response time to the upset condition. This generally will to convert the measured reading to cumulative metal loss.
demand a more sensitive probe. However, since the upset Check that the readings are steady and record the midpoint and
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condition will generally not exist for an extended period, the
probe life will not be severely reduced.
extent of any variation of the reading.
10.2 Automatic Continuous Monitoring Instruments:
terials and seals. Document Preview
7.1.6 Check compatibility of process fluid with probe ma-
10.2.1 These instruments are available in various single or
multi-channel configurations. They may be standalone systems
7.2 Electrical Resistance Probe Monitoring Instruments: or interfaced with process computers, or both. These units
7.2.1 Portable, intermittent instruments, and ASTM provide continuous information on metal loss or corrosion
G96-90(2018)
continuous
single and multi-channel instruments are available. Since the rates, or both.
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10.2.2 The system should be installed and tested according
electrical resistance probe measures cumulative metal loss, the
intermittent measurement permits the determination of the to the manufacturer’s instructions. Test probes are normally
average corrosion rate only between the measurement points. provided to assist the set-up of all channels and cabling of the
With continuous monitoring, corrosion in real time can be system.
determined. 10.2.3 Connect the operational probes into the system.
7.2.2 Automatic continuous monitoring systems may be 10.2.4 Various output forms of information are available,
standalone systems or interfaced to other process computers, or together with alarms. Computerized systems will often allow
both. alarms to be set for excessive corrosion rates to draw attention
to problem areas that may then be analyzed in detail from the
8. Probe Preparation metal loss versus time graph. Generally the most useful form of
data is the graph of metal loss versus time for each monitored
8.1 Commercial probes are generally received in sealed point.
plastic bags to protect prepared surfaces. Care should be taken
during installation to avoid handling the probe measurement 11. Interpretation of Results
element, that can cause additional corrosion.
11.1 Plot the graph of metal loss versus time. Upsets and
8.2 Probe measurement element surfaces should be smooth changes in corrosion rate will be readily observable as changes
and free of indentations or signs of mechanical damage. in the slope of the curve. The average corrosion rate will be the
Grit-blasting with 120 grit is suitable as a surface preparation slope of the line connecting the two points on the curve over
prior to degreasing. the time period under consideration. The maximum corrosion
8.3 If probes are being moved from one system to another, rate will be the slope of the tangent to the curve at the steepest
they must be cleaned mechanically before reuse to ensure point of the curve (see Fig. 3).
complete removal of oxide or inhibitor films. Degreasing is 11.2 Some systems automatically calculate corrosion rates
necessary to complete the cleaning procedure. Practice G1 over various periods.

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 G96 − 90 (2018)

FIG. 3 Typical Plot of Metal Loss Versus Time

11.3 Careful interpretation is necessary in correlating these 12.5 The theoretical polarization resistance equation in
corrosion test results with actual metal corrosion in the plant. 4.2.2 relates only to the corrosion interface. In practical
Comparison with metal coupon results (see Guide G4) or with measurements solution resistance becomes an increasing inter-
actual metal exposed in the plant is recommended. ference in low conductivity environments.
11.3.1 Actual mass loss incurred by the probe elements can 12.5.1 A general indication of limits of use are shown in
be used to establish correlations between the corrosion rate Fig. 2. (For derivation of curves in Fig. 2 and examples of
estimated by the electrical resistance methods and actual errors, see Appendix X1.) The main limitations of each
corrosion losses. Practice G1 provides guidance on methods of technique in plant equipment are as follows:
evaluating mass loss.
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TEST METHOD B—POLARIZATION RESISTANCE
12.5.1.1 Two-Electrode Probes and Three Electrode Probes
With Equidistant Reference Electrode—Limited as solution

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resistance becomes significant compared with polarization
(2, 3, 4, and 6-25) resistance.
12.5.1.2 Three-Electrode Probe With Close-Space Refer-
12. Limitations and Interferences
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12.1 In the case of polarization resistance measurements,
ence Electrode—Compensation for solution resistance limited
by physical proximity of reference electrode to test electrode
interferences derive from both theoretical and practical as- and its position in the potential field between the test and
sumptions and limitations.
ASTM G96-90(2018)
12.1.1 The theoretical polarization resistance equations in
auxiliary electrode.
12.5.1.3 High Frequency Measurement for Compensation of
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4.2.2 on which the measurement is based are derived on the Solution Resistance—Limited by error of small differences
following assumptions: (2, 19) between two large numbers at high solution resistance, and the
12.1.1.1 The corrosion is uniform. frequency of the resistance compensation measurement.
12.1.1.2 The corrosion mechanism consists of only one 12.5.1.4 Current Interruption for Compensation of Solution
anodic and one cathodic reaction. The corrosion potential is not Resistance—Limited by noise on high impedance input at time
near the redox potential of either reaction. of current interruption measurement.
12.1.1.3 Other secondary reactions that are not directly
corrosion related but involve charge transfer are not significant. 12.6 In actual plant measurements, fouling or bridging of
12.1.1.4 Metals or alloys should give Tafel kinetics for both electrodes with conductive deposits may reduce the apparent
anodic and cathodic reactions. value of polarization resistance thereby indicating a higher
12.1.1.5 Measurements are made over a sufficiently small corrosion rate. This will invalidate measurements until the
polarization range that the potential-current plot is essentially probe is cleaned.
linear. 12.7 Probes of pitted metal or metal with sharp edges may
12.2 The polarization resistance technique is restricted to yield unreliable results. General reuse of probe electrodes is
use in sufficiently conductive environments (refer to Fig. 2). not recommended.
12.3 Deposits on the electrodes may affect the results. 12.8 Since the corrosion rate is usually temperature
12.4 When polarization of an electrode is made by the dependent, results will be comparable only for the alloy at the
polarization resistance measurement, time is required to charge process temperature to which the probes are exposed. In heat
the double layer capacitance, Cdl, (see Fig. 1) before a transfer environments actual plant metal temperatures may be
measurement can be taken. The assumption is that the corro- significantly different from that of the test probe.
sion potential has remained constant through this measurement 12.9 The corrosion rates occurring on the probe electrodes
cycle. This assumption can be a limitation if long cycle times during the first few hours or days of exposure may not be
are used, particularly in a dynamic plant environment. typical of corrosion occurring in the system. Establishment of