Corrosion Monitoring Techniques for

Industrial Cooling Water and Process

Systems Reprint R-815

By: Tzu-Yu Chen, Rodney H. Banks, Jeffrey Breshears, Steven N. Nicolich and
Daniel M. Cicero, Nalco, an Ecolab Company

Nalco, an Ecolab Company

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Ecolab, NALCO and the logos are Trademarks of Ecolab USA Inc.
©2002, 2015 Ecolab USA Inc. All Rights Reserved 4-15

First presented at the International Water Conference, October 20-24, 2002

 ABSTRACT Corrosion monitoring can be used as a diagnostic
tool to provide information for solving corrosion
Corrosion-related failures often result in expensive problems. The data obtained can help plant
system shutdowns and excessive maintenance costs. engineers identify system parameters affecting
Too often, corrosion-related problems are only corrosion and implement solutions to a specific water
detected after a failure has occurred, after it is too treatment problem. A variety of monitoring techniques
late to take action to prevent it. has been employed for corrosion monitoring in
industrial cooling water and process systems. This
Various monitoring techniques have been used in includes wet chemistry, x-ray radiography, ultrasonic
industrial cooling water and process systems to scans, coupon weight loss, electrical resistance
routinely measure and report corrosion rates. This probes and various electrochemical techniques.
paper reviews a variety of corrosion monitoring
techniques - including wet chemistry, x-ray WET CHEMISTRY ANALYSES – This usually
radiography, ultrasonic scans, coupon weight loss involves collecting water samples to determine the
method, electrical resistance and electrochemical corrosivity or quality of the water. This method does
measurements - points out the advantages and not provide information on the corrosion rates (mils
disadvantages of each, and describes technological per year or mm per year) of metals present in the
trends that may point to new developments in this system. Typically, the following parameters are
area. monitored: pH, alkalinity, conductivity, total dissolved
solids, total hardness, calcium, magnesium, chloride,
This paper also presents some data collected in the sulfate, inhibitor dosages, total and dissolved metal
laboratory and in field applications, and points out species, such as iron, copper and aluminum. A “well
obstacles to effective corrosion rate measurements, check” analysis is recommended. This consists of a
including low conductivity waters, the challenges complete water analysis when the plant is operating
found in once-through cooling water and the technical properly and the system corrosion is under control.
limitations of the various corrosion measurement The “well check” result can be used as the baseline
techniques. A number of Best Practices for data. Analyses are then performed to determine the
monitoring corrosion rates in cooling water systems is causes when the corrosion rates are outside the
also included. norm.

KEYWORDS: Cooling Water, Once-Through, Open X-Ray RADIOGRAPHY & ULTRASONIC SCANS -
Recirculating, Corrosion Coupon, Corrosion X-ray radiography can detect major flaws and severe
Monitoring, Linear Polarization Resistance, Solution corrosion attacks by providing two-dimensional views
Resistance, Polarization Resistance, Electrical of a system component. But it is not accurate enough
Resistance Probe, Electrochemical Impedance to determine small changes in wall thickness to
Spectroscopy, On-line Real-Time Corrosion determine corrosion rates. Ultrasonic scans typically
Monitoring, Corrosion Monitor, Corrosion Probe. provide depth measurements from the external
surface of a pipe or vessel to the internal surface that
INTRODUCTION reflects sound waves. Unfortunately, the ultrasonic
depth measurements are very often interfered by
Corrosion monitoring is an integral part of any defects in the materials.
industrial water treatment program. It can be used to
determine the effectiveness of the chemical treatment Both the x-ray radiography and ultrasonic scans are
program and establish a correlation between employed almost exclusively for measurements
treatment level and corrosion control. It provides rather than for monitoring. They require special
information on equipment conditions and relates this training and complicated equipment and may not be
information to operational parameters, such as pH, suitable for on-line real-time corrosion monitoring.
temperature, water quality, chemical treatment levels,
etc. Proper corrosion monitoring provides the COUPON WEIGHT LOSS - Coupon weight loss
following benefits: measurement is commonly used for monitoring
corrosion in various industrial plants. The ASTM
1-3
1. Increases equipment life recommended practices listed below should be
2. Reduces operating and maintenance costs followed.
3. Predicts maintenance needs
4. Improves the finished product quality 1. ASTM D2688-94, “Standard Test Methods for
Corrosivity of Water in the Absence of Heat
Transfer (Weight Loss Method).”

2
2. ASTM G4-95, “Standard Guide for Conducting high corrosion because the metal surface is in an
Corrosion Coupon Tests in Field Applications.” “active” state due to the surface preparation prior to
immersion. For this reason, coupon corrosion rates
3. ASTM G1-90, “Standard Practice for Preparing, obtained with short exposure times can be
Cleaning, and Evaluating Corrosion Test misleading. Normally, the longer the exposure period,
Specimens.” the lower the measured average corrosion rate, and
the more closely the coupon tests will approximate
Metal specimens are typically installed in a corrosion the system conditions. Frequently, longer-term tests,
rack for a certain time period ranging from 30 to 180 up to 180 days of immersion, are required. The
days. They are then retrieved and examined to coupon weight loss measurements should follow the
determine the type and the extent of corrosion. The empirically derived minimum exposure time
5,6
weight loss data can be converted to a corrosion rate requirement:
in units of mm/year (millimeters per year) or mpy
4
(mils per year): Minimum Exposure Time (Days) = 85/mpy (3)

mm/year = 13.6 W/(rAt) or (1) The coupon weight loss method is relatively simple
mpy = 534W/(rAt) (2) and inexpensive. However, it only provides the
average corrosion rate over an extended period of
where W = the weight loss (mg), r = the density of time. System upsets causing variations in corrosion
3
the specimen (g/cm ), A = the area of the specimen rates cannot be detected and corrective actions can
2
(in ), and t = the exposure time (hour). not be taken in a timely manner.

The metal coupons should be electrically isolated ELECTRICAL RESISTANCE (ER) PROBE - The
from other metallic components to avoid galvanic conventional electrical resistance probes for
corrosion. Hydrodynamic effects should also be taken corrosion rate measurements consist of a metal wire
into consideration in selecting the test location, for element of known length and diameter embedded in
example, elbows versus straight pipe. a water-resistant material. The value of the electrical
resistance, r, is related to the cross-sectional area of
Figure 1 shows the variation of corrosion rate with the wire element:
time curve for metals immersed in typical industrial
cooling waters. The initial corrosion rate is usually r = s (L / A) (4)
very high. The corrosion rate then decreases and
reaches a steady state value after certain exposure where r = electrical resistance (ohm), s = resistivity of
times ranging from several hours to several days. metal (ohm/cm), L = length of wire element (cm), and
2
Corrosion coupons are highly susceptible to initial A = cross-sectional area of the wire element (cm ).
The electrical resistance is inversely proportional to
the cross-sectional area of the metal wire. As
corrosion proceeds, the cross-sectional area of the
metal wire element decreases. This will result in an
increase in the electrical resistance. By measuring
the change in the electrical resistance, r, one can
determine the change in the cross-sectional area and
13
the corrosion rate. The electrical resistance
technique can be used for corrosion rate
measurements in liquids or vapor phase. The liquid
does not have to be conductive or have a minimum
conductivity required by many electrochemical
techniques. The major disadvantage is that it does
not measure instantaneous corrosion rates. Usually,
it takes a long time to obtain a significant change in
the electrical resistance, especially in well-treated
Figure 1. Typical corrosion rate versus time cooling water systems. The ER method cannot detect
curve. localized corrosion, such as pitting.

ELECTROCHEMICAL TECHNIQUES - Various dc

and ac electrochemical techniques have been

3
successfully employed for on-line, real-time corrosion However, for high purity or low-conductivity waters,
monitoring in industrial cooling water and process such as once-through cooling water, soft cooling
systems. Most electrochemical methods for corrosion water and boiler condensate, the value of the solution
rate measurements, such as linear polarization resistance Rs is not negligible and LPR, which
resistance (LPR) technique and electrochemical measures (Rs+Rp), will underestimate the corrosion
impedance spectroscopy (EIS), are based on the rates. For this reason, many corrosion monitors
7
Stern-Geary equation: based on LPR technique without the capability of
compensating for the solution resistance are not
icorr = (1/2.303) {(babc)/(ba+bc)} (1/Rp) (5) suitable for corrosion rate measurements in low-
conductivity solutions.
2
where icorr = corrosion current density (mA/cm ),
ba = anodic Tafel slope (mV), bc = cathodic Tafel Electrochemical Impedance Spectroscopy (EIS) -
10-12
slope (mV), and Rp = polarization resistance (ohm x In EIS measurements, a small ac potential
2
cm ). The corrosion current density, icorr, can further excitation of different frequencies is applied to the
be converted to corrosion rates in units of mm/year electrode at the free corrosion potential to determine
(millimeters per year) and mpy (mils per year) based Rs as the high frequency limit and (Rs+Rp) as the low
on Faraday’s Law: frequency limit. The polarization resistance, Rp, and
the corrosion rate can then be calculated. EIS
5
mm/year = 3.15x10 {M/(nFd)} x icorr measurements can also provide some mechanistic
5
= 1.37x10 {M/(nFd)} x (B/Rp) (6) insights of the corrosion process, but data
interpretation often requires skill and experience. A
7
mpy = 1.24x10 {M/(nFd)} x icorr disadvantage of EIS is that the system being
6
= 5.39x10 {M/(nFd)} x (B/Rp) (7) measured has to be very stable to obtain meaningful
data due to the long measuring time. The instruments
where M = molecular weight of metal (g/mole), n = involved in EIS are also very expensive and
number of electrons involved in the corrosion reaction complicated and may not be suitable for long-term
(mole), F = Faraday’s constant, d = density of metal field corrosion monitoring.
3
(g/cm ), and B = (babc)/(ba+bc) (mV).
Electrochemical Noise Measurement (ECN) - The
Substituting the values of M, n, and d for iron (M = corrosion reaction on electrodes consists of a series
55.85 g/mole Fe, n = 2 moles e-/mole Fe, d = 7.86 of discrete or stochastic steps on local anodes and
3
g/cm ), Faraday's constant (96,500 coulombs/mole of cathodes. This causes fluctuations, at frequencies
-
e ), and assuming that ba = bc = 120 mV, Eq. (6) and typically below 1 Hz, in the corrosion potential
Eq. (7) become (potential noise) and in the coupling current (current
noise) between electrodes. These fluctuations,
2
mm/year = (3.03x10 )/Rp (for iron/steel) (8) commonly known as electrochemical noise, have
4
mpy = (1.19x10 )/Rp (for iron/steel) (9) been suggested to be due to (1) the difference in
charge consumption and generation between the
Similar equations can be derived for copper and cathodic and anodic reactions present at any small
other metals. interval of time and (2) the transient changes in
cathodic or anodic areas.
Linear Polarization Resistance (LPR) Technique
The linear polarization resistance (LPR) technique The electrochemical current noise is typically
involves applying a small potential signal (for measured with a zero resistance ammeter (ZRA)
example, ±10 mV) to the metal surface at a very slow between two identical electrodes. The
potential scan rate, typically 0.1 mV/second, to electrochemical potential noise is usually measured
measure (Rs+Rp) (sum of solution resistance, Rs, and with a high input impedance voltmeter. Various time
8,9
polarization resistance, Rp). In solutions of high domain or frequency domain techniques, including
conductivities, such as seawater and cooling water visual, statistical, Fast Fourier Transform and
environments, the value of Rs is very small or Maximum Entropy Spectral Analysis, have been used
13, 14
negligible. Therefore, (Rs+Rp) @ Rp and we can for data analyses. It has been reported that the
determine the corrosion rates with LPR based on Eq. electrochemical noise can be employed to monitor
(8) or (9). The LPR technique measures the various types of localized corrosion, such as
instantaneous corrosion rates since a complete scan pitting corrosion and crevice corrosion. But they are
takes only a few minutes. usually qualitative and can only be used as
indications of the severity of localized attack. They do
not provide quantitative localized corrosion rates.

4
 easy task. First, the small O-rings have to be
Electrochemical Harmonic Analysis (EHA) – removed from the threaded rods on the probe. The
15
EHA can be viewed as an extension of EIS probe tips are then screwed onto the probe by hands.
technique. It measures the non-linear distortion, Very often the electrodes are contaminated by
which is a function of the Tafel constants, at the dirt/oils, causing erroneous mpy readings. The
corrosion potential. EHA data is analyzed based on crevice at the O-ring/electrode interface presents
digital signal analysis using a frequency response another concern. Localized corrosion occurring
analyzer or a spectrum analyzer to provide a preferentially at the crevice area may cause
measure of the corrosion current and an estimation of significant errors in the corrosion rate measurements.
Tafel constants in the same measurement. This
technique can be used in low-conductivity waters. NCM100 - Advancements have been made in LPR
The disadvantage of the technique is that the technology. Newer units, such as the NCM100
instrument involved is very expensive and data developed by Ondeo Nalco Company, are smaller
interpretation is very difficult. EHS measurements and easier to use than previous devices. These units
also tend to become unstable when the system is can automatically identify the probe metallurgy,
under localized corrosion attack. making possible true “plug and play”, saving time and
avoiding human errors. The probes are disposable,
GENERAL CORROSION MONITORS/PROBES which eliminates the need for field installation of
replaceable tips/electrodes and O-rings. The
Most commercially available corrosion monitors and electrodes are embedded in an epoxy mounting
probes for field applications are based on material to minimize crevice corrosion and improve
16-20
electrochemical techniques. The simpler units the accuracy of measurements. Using an ac
measure the general corrosion rates with the LPR technique, NCM100 has the capability of
technique. Systems capable of measuring corrosion compensating for the solution resistance for corrosion
rates of metals in low-conductivity solutions also rate measurements in low-conductivity solutions,
determine the solution resistance. Methods for such as once-through cooling water, soft water and
compensating the solution resistance vary among boiler condensate. The units have lower power
these systems. This includes a high frequency EIS requirements, which translates into low maintenance,
18 19
measurement , a current interrupt method and a battery-powered operation. NCLM100 couples data
20
potential step/peak detector technology. logging capabilities with the ubiquity of hand-held
devices such as the Palm Pilot to allow easy retrieval
®
CORRATER - The Corrator Model 9030+ made by and analysis of corrosion data. These units are small,
18
the Rohrback Cosasco Systems is one of the most portable and easy for the operators to carry around
popular corrosion monitors today. It determines the the plant to determine corrosion rates at various
general corrosion rates based on the LPR technique locations. It can also be used as a permanently
with a high frequency EIS measurement to installed instrument for on-line, real-time corrosion
compensate for the solution resistance. It is powered monitoring.
by AC and comes with a 4-20 mA output for external
data logging. Due to its size and weight, it is typically Laboratory Evaluations of NCM100 - The
used as a permanently installed unit for corrosion performance of NCM100 was first evaluated in
monitoring at a certain location. There are other simulated soft cooling water environments in the
portable corrosion monitors powered by dc batteries laboratory. Figure 2 shows the variation of corrosion
available. But almost none of them have Rs rate with time curve obtained on a mild steel
compensation and internal/external data storage corrosion probe measured with NCM100 and EIS
capability. The Corrater technology has some under different test conditions (Phase 1 to Phase 6).
drawbacks in the area of user-friendliness and A Gamry CMS100 system was employed for the EIS
convenience of use. Before starting the tests, the measurements and for comparisons with NCM100. In
operator has to go through several menus to set Phase 1, 100 ppm of a cooling water corrosion
various parameters, such as measurement time and inhibitor was fed to the system. Increasing the
the conversion factor for the specific probe inhibitor dosage from 100 ppm (Phase 1) to 200 ppm
metallurgy. Replacement of the probe tips is not an (Phase 2) caused a decrease in the corrosion rate.
The pH was subsequently increased from 7.0 (Phase
2) to 8.0 (Phase 3) by adding a small amount of
NaHCO3. A reduction in corrosion rate

5
 Field Evaluations of NCM100 – The performance of
Figure 2. Corrosion rates measured by NCM100. NCM100 was further evaluated in a field trial
conducted at a Midwestern hospital. Figure 3
compares the mild steel corrosion rates measured by
NCM100 with that measured by Corrater 9030+. The
cooling water system consists of an 18,000 gallon 3
• - NCM100
cell tower. Water is pumped and recirculated to two
LiBr adsorption chillers. The corrosion monitors and
mild steel corrosion probes were installed in a
corrosion rack in a side stream. As shown in Figure
3, good agreement was observed between NCM100
TM
- Corrater 9030+ and Corrater 9030+ for measuring the mild steel
corrosion rates.

Another field trial was conducted at the utility plant in

a Midwestern institute. Pond water was circulated
through heat exchangers for cooling. Due to an
Figure 3. Comparisons in mild steel corrosion rates environmental concern, the water was not treated for
between NCM100 and Corrater 9030+. corrosion control. NCM100 and Corrater 9030+ with
copper corrosion probes were installed in a corrosion
was observed due to the increase in pH. In Phase 4, rack for corrosion monitoring. Figure 4 compares the
the test water temperature was lowered from 95°F copper corrosion rates measured by NCM100 with
(Phase 3) to 77°F (Phase 4) and a decrease in that measured by Corrater 9030+. The corrosion
corrosion rate was recorded as expected. The test rates measured by NCM100 are in general accord
water temperature was then increased to 122°F in with that measured by Corrater 9030+. The slight
Phase 5 and the corrosion rate of mild steel differences in the measured corrosion rates between
increased accordingly. Finally in Phase 6, a biocide NCM100 and Corrater 9030+ are believed to be due
(3.4 ppm) was added to the test water. This resulted to the difference in the degree of turbulence at the
in a dramatic increase in corrosion rate. As shown, test sections. The NCM100 probe was inserted in a
the NCM100 was capable of detecting the changes in 1” PVC tee while the Corrater probe was inserted in a
mild steel corrosion rate as a result of changes in 2” PVC tee. The 2” PVC was subsequently replaced
inhibitor dosage, pH, temperature and biocide feed. with a 1” tee. Good agreement was found between
EIS measurements were carried out at various time NCM100 and Corrater 9030+ in measuring the
intervals during each phase of the experiment. The copper corrosion rates when 1” PVC tees were used
results obtained by EIS are included in Figure 2 for for NCM100 probe and Corrater probe.
comparisons. Good agreement was found between
EIS and NCM100 in measuring the mild steel
corrosion rates under various simulated soft water
conditions demonstrating performance of NCM100.

6
 The Corrater 9030+ measures the imbalance current
and provides a “Pitting Index” as an indication of the
• - NCM100 Same size severity of localized corrosion. This is essentially a
PVC tee form of electrochemical noise measurement. The
imbalance current is determined by measuring the
galvanic current flowing between two short-circuited
electrodes with a zero resistance ammeter. This
reading is then converted to a “Pitting Index” based
2
TM on an arbitrary scale of 0.5 A/cm per pitting index
- Corrater 9030+
unit. It was suggested that when the imbalance
current exceeds the general corrosion current, pitting
corrosion may be a major problem. Another
TM
technology, SmartCET , measures the “Pitting
Factor” to indicate the risk of local attack on metal
29
Figure 4. Comparisons in copper corrosion rates surface . The “Pitting Factor” is a factor between 0
between NCM100 and Corrater 9030+. and 1 calculated based on electrochemical noise
data. When the pitting factor is greater than or equal
to 0.1, then pitting may occur on the metal surface.
LOCALIZED CORROSION MONITORING Both the “Pitting Index” and the “Pitting Factor” are
qualitative measurements; a large uncertainty
At present, most commercially available corrosion associated with the readings’ interpretation has
monitors only measure general corrosion rates. limited its application. It is often observed in practice
Localized corrosion, such as pitting, crevice corrosion that the localized attack can still be quite severe even
and underdeposit attack, is a more serious concern with a small imbalance current or pitting index
because it is very difficult to control and predict. Many reading.
system upsets, such as changes in pH, an increase
in chloride concentration, a raise in the temperature CONCLUSIONS
and a decrease in the inhibitor level, can initiate
localized corrosion. Because of its autocatalytic Corrosion monitoring tools are often employed to
nature, localized corrosion will propagate or grow evaluate and ensure the performance of various
very rapidly once it’s initiated. Without proper industrial water treatment programs. A good chemical
monitoring tools, localized corrosion often results in treatment program should be one that also provides
unexpected failures, plant shutdowns, loss of good monitoring instrumentation. This is essential to
production and, sometimes, environmental pollution. optimizing the dosage of the chemicals to obtain the
best performance. The particular corrosion
There is currently no industrial standard or test monitoring technique selected depends on its
method for monitoring localized corrosion in cooling applicability to the system and the type of information
22
water and process systems. Turnbull et al. reviewed being sought. Some techniques provide
and evaluated various techniques for monitoring the measurements of average corrosion rates over a
growth or propagation of localized corrosion in certain period of time. Others provide instantaneous
simulated cooling water environments. This included corrosion rate information and are more effective.
23 24
differential flow method , galvanostatic pre-pitting , Most corrosion monitoring techniques are best suited
25 26, 27
pencil type artificial pit , occluded cell , for situations where the corrosion is of a general or
22
artificial/sandwich crevice , and artificial/slot uniform nature, but some techniques provide at least
28
crevice . Most of the techniques involve the some information on the degree or severity of
measurements of the galvanic current flowing localized attack, such as pitting and underdeposit
between a cathode and an anode. However, they can corrosion. More than one monitoring technique may
only be used as indications of the severity of be needed to obtain the necessary information to
localized corrosion. They do not provide direct evaluate the effectiveness of the treatment program.
measurements of localized corrosion rates. In There is a need to develop a corrosion monitor or
22
addition, as reported by Turnbull et al., many of sensor for quantitative localized corrosion rate
these techniques have reproducibility problems due measurements in industrial cooling water and
to (1) interference caused by the unintentional process systems.
crevice corrosion occurring on the electrodes and/or
(2) difficulties in controlling the geometry/dimension,
number and distribution of pits/crevice.

7
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