EPRI Galvanic Corrosion

Predictive Model for Galvanic Corrosion
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Technical Report
Predictive Model for Galvanic
Corrosion
1008184
Final Report, December 2004
EPRI Project Manager

A. Machiels
D. Munson
EPRI 3412 Hillview Avenue, Palo Alto, California 94304 PO Box 10412, Palo Alto, California 94303 USA
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CITATIONS
This report was prepared by
BNFL Nuclear Sciences & Technology Services

168, Harwell International Business Center
Didcot, Oxfordshire OX11 0QJ
United Kingdom
Principal Investigators
W. S. Walters
J. Henshaw
H. E. Sims
This report describes research sponsored by EPRI.
The report is a corporate document that should be cited in the literature in the following manner:
Predictive Model for Galvanic Corrosion, EPRI, Palo Alto, CA: 2004. 1008184.
iii
REPORT SUMMARY
Significant damage caused by galvanic corrosion is occasionally encountered in nuclear power

plants. It occurs where two dissimilar metals are mechanically joined, brazed, or welded and
connected by an electrolyte. If not detected or repaired in time, it can cause loss of the pressure
boundary and/or hinder equipment operability. The problem tends to be most severe in service
water, circulating water, and fire protection systems of plants with high-conductivity waters (for
example, sea water and brackish water). Significant attack also can occur in low-conductivity
waters if the metals are sufficiently dissimilar (for example, copper or brass and carbon steel).
The ability to predict corrosion rates is key to determining the location and frequency of
inspections and component replacement to prevent galvanic failures in power stations.
Background
A model to predict rates of galvanic corrosion in piping systems was developed and included in
the CHECWORKS Cooling Water Application. The model was based on data in the literature,
which were somewhat incomplete, and did not properly account for key variables such as water
conductivity, temperature, flow rate, and dissolved oxygen content. In 2001, EPRI sponsored
development of a mechanistically based model that would account for the key parameters and be
suitable for use in a Corrosion Calculator and/or the CHECWORKS Cooling Water
Application. The 2001 work also identified a significant lack of experimental data to provide
input parameters to the model and long-term rates against which to validate the model.
Objectives
To develop model parameters for materials commonly used in nuclear power plant balance-
of-plant systems.
To determine long-term corrosion rates for six of the most commonly found metallic couples
for benchmarking the long-term corrosion behavior model.
Approach
The project team developed a new galvanic corrosion model based on fundamental principles of
electrochemistry. As part of this development, experimental information on galvanic corrosion
rates was obtained to benchmark the new model. In particular, the following metallic couples
were investigated: carbon steel and Admiralty brass; carbon steel and titanium; carbon steel and
90:10 copper-nickel bronze; carbon steel and 316L stainless steel; carbon steel and AL6XN; and
316L stainless steel and AL6XN. These six couples were studied in a flowing loop, both in saline
solution and in a lower conductivity solution. Potentiodynamic polarization testing also was
conducted on the six materials involved in the galvanic couples, with the addition of 304L
stainless steel, 70:30 copper-nickel bronze, and copper.
v
The polarization cell and the flowing loop were designed, constructed, and tested specifically for
this program. All pipework or containment vessels were made of glass or inert polymer to avoid
complications with other corrodible metals. Measurements were made in real time using
automated systems; results were logged automatically and interpreted as digital datasets.
Polarization studies were completed on all the metals of interest. From these studies, the
following parameters were evaluated: the anodic and cathodic slopes of the Tafel plots and the
magnitude of the residual current density at the cross-over from cathodic to anodic behavior.
Also, the voltage (applied potential) at which behavior changes from cathodic to anodic was
measured; this is equivalent to the corrosion potential of the metal in that solution.
Loop studies were performed in pairs, using a loop with parallel flow lines on the six metallic
couples. For each loop test, the corrosion current was measured over a period of approximately
three to four weeks, with steady state being achieved in approximately 11 days.
Results
Modeling the flowing loop data using the FACSIMILE model developed previously and using
the Tafel constants from the polarization studies indicated the following:
At high conductivity, the corrosion current is close to what would be expected for the carbon
steel couples if the process was controlled by mass transfer of O2 to the cathodic surface.
The Tafel constants derived from the polarization studies are too large to explain the
corrosion currents measured in the loop. At high conductivity, the measured polarization
exchange current density needs to be reduced by a factor of 102 and at low conductivity by a
3
factor of 10 to get reasonable agreement with the measured corrosion rates.
EPRI Perspective
Development of a reliable model to predict galvanic corrosion would provide operating plants
with an additional tool to help focus their inspection program and better interpret inspection
results of degraded components with respect to their remaining service life. The model described
in this report with the Tafel parameters derived from the polarization studies was not able to
predict the loop test results. Modeling of the phenomena needs to be improved before a truly
predictive galvanic corrosion model is available for power plant applications. This report,
therefore, should be considered a milestone toward that end.
Keywords
Galvanic corrosion
Piping degradation
Tafel parameters
Polarization curves
vi
EPRI Licensed Material
ABSTRACT
The prediction of corrosion rates is a key input to determining the location and frequency of
inspections and component replacement in power stations. To quantify the corrosion behavior of
various equipment and piping components containing raw water, EPRI developed the
CHECWORKS Cooling Water Application to address the low-temperature/low-flow-rate
conditions normally experienced in the balance of plant tertiary systems. Within this context,
one of the key issues is galvanic corrosion between dissimilar metals connected in the same run
of piping or in other equipment, such as valves and heat exchangers.
A new galvanic corrosion model was developed, and as part of this development, experimental
information on galvanic corrosion rates was obtained in order to be able to model short-term and
long-term galvanic corrosion rates. Polarization tests were carried out on carbon steel, titanium,
316L stainless steel, 304L stainless steel, AL6XN molybdenum steel, Admiralty brass, copper,
70:30 Cu/Ni bronze and 90:10 Cu/Ni bronze. Flowing loop tests were performed on the galvanic
couples of carbon steel/Admiralty brass, carbon steel/titanium, carbon steel/AL6XN
molybdenum steel, carbon steel/90:10 Cu/Ni bronze, carbon steel/316L stainless steel, and 316L
stainless steel/AL6XN. The results of these tests are reported. The interpretation of these results
and their application in the calculation model are presented.
vii
CONTENTS
1 INTRODUCTION ....................................................................................................................1-1
2 DESCRIPTION OF GALVANIC CORROSIVE MODEL .........................................................2-1

2.1 Physical Basis of the Model ............................................................................................2-1
2.1.1 Transport Along the Pipe.........................................................................................2-1
2.1.2 Corrosion at the Metal Surface................................................................................2-3
3 DESCRIPTION OF EXPERIMENTAL WORK ........................................................................3-1

3.1 Outline of Work Program.................................................................................................3-1
3.2 Experimental Technique..................................................................................................3-3
3.2.1 Polarization Experiments.........................................................................................3-3
3.2.2 Flowing Loop Tests .................................................................................................3-8
4 POLARIZATION EXPERIMENTAL RESULTS ......................................................................4-1

4.1 Preliminary Tests and Method Development ..................................................................4-1
4.2 Polarization Tests in Simulant Sea Water .......................................................................4-6
4.3 Polarization Tests in Simulant Lake Water......................................................................4-7
4.4 Polarization Tests of Additional Metals ...........................................................................4-9
4.5 Polarization Tests at Intermediate Conductivity. ...........................................................4-10
4.6 Polarization Tests of Oxidized Samples........................................................................4-11
4.7 Polarization Tests at Elevated Temperature. ................................................................4-16
4.8 Summary of the Results of Polarization Tests ..............................................................4-18
4.9 Discussion of Polarization Results ................................................................................4-23
5 FLOW LOOP EXPERIMENTAL RESULTS ...........................................................................5-1

5.1 Loop Test #1 ...................................................................................................................5-3
5.2 Loop Test #2 ...................................................................................................................5-6
5.3 Loop Test #3 ...................................................................................................................5-9
5.4 Loop Test #4 .................................................................................................................5-12
ix
5.5 Loop Test #5 .................................................................................................................5-15

5.6 Loop Test #6 .................................................................................................................5-18
5.7 Summary of Flow Loop Test Results ............................................................................5-20
6 INTERPRETATION OF RESULTS.........................................................................................6-1
7 DISCUSSION AND SUMMARY .............................................................................................7-1
8 REFERENCES .......................................................................................................................8-1
A TAFEL PLOTS FROM THE POLARIZATION STUDIES...................................................... A-1

A.1 Polarization Studies in Sea Water Chemistry ................................................................ A-1
A.2 Polarization Studies in Lake Water Chemistry............................................................. A-16
A.3 Polarization Studies in Brackish Water Chemistry....................................................... A-29
x
LIST OF FIGURES
Figure 3-1 Schematic Diagram of Polarization Test Equipment ................................................3-5

Figure 3-2 Polarization Test Equipment.....................................................................................3-6
Figure 3-3 Schematic Diagram of Galvanic Corrosion Test Loop..............................................3-9
Figure 3-4 Galvanic Corrosion Test Loop ................................................................................3-10
Figure 4-1 Polarization Commissioning Carbon Steel in Sea Water Solution (Measured
Results) ..............................................................................................................................4-3
Figure 4-2 Polarization Commissioning Carbon Steel in Sea Water Solution
(Calculated Results)...........................................................................................................4-4
Figure 4-3 Polarization Result Carbon Steel in Sea Water Solution (Tafel Plot) ....................4-5
Figure 4-4 Estimation of the Effect of the IR Drop 70:30 Cu/Ni Bronze in Lake Water
(Tafel Plot)..........................................................................................................................4-8
Figure 4-5 Polarization Equipment with Heated Cell Arrangement..........................................4-17
Figure 5-1 Linear Flow Velocity Depending on Tube Internal Diameter and Bulk Flow
Rate....................................................................................................................................5-2
Figure 5-2 Galvanic Corrosion Loop Test #1 Results ................................................................5-5
Figure 5-3 Galvanic Corrosion Loop Test #2 Results ................................................................5-8
Figure 5-4 Galvanic Corrosion Loop Test #3 Results ..............................................................5-11
Figure 5-8 Galvanic Test Section Clamp Jig............................................................................5-21
Figure 6-1 Plot of Corrosion Rate Against Distance from Metal-Metal Joint for Carbon
Steel (CS) and Admiralty Brass (AB) Galvanic Couple. The Low Conductivity
Corresponds to Lake Water at 1-2 mS/cm, The Intermediate Conductivity to
Brackish Water at 10 mS/cm, and the High Conductivity Is for Sea Water at 7080
mS/cm ................................................................................................................................6-7
Figure 6-2 Plot of Corrosion Rate Against Distance from Metal-Metal Joint for Carbon
Steel (CS) and AL6XN Galvanic Couple. The Low Conductivity Corresponds to
Lake Water at 1-2 mS/cm, the Intermediate Conductivity to Brackish Water at 10
mS/cm, and the High Conductivity Is for Sea Water at 7080 mS/cm ...............................6-8
Equation 6-3 Plot of Corrosion Rate Against Distance from Metal-Metal Joint for a
Carbon Steel (CS)/Admiralty Brass Couple. Calculations Were Carried Out for Sea
Water Conditions................................................................................................................6-9
xi
LIST OF TABLES
Table 3-1 Selection of Galvanic Couples...................................................................................3-2

Table 4-1 Dimensions of Polarization Samples (length 250mm). ..............................................4-6
Table 4-2 Tafel Parameters Taken from Polarization Curves in Sea Water Chemistry .............4-7
Table 4-3 Tafel Parameters Taken from Polarization Curves in Lake Water Chemistry............4-9
Table 4-4 Dimensions of Additional Sample Materials (Length: 250 mm) .................................4-9
Table 4-5 Further Tafel Parameters Taken from Polarization Curves in Sea Water
Chemistry .........................................................................................................................4-10
Table 4-6 Further Tafel Parameters Taken from Polarization Curves in Lake Water
Chemistry. ........................................................................................................................4-10
Table 4-7 Tafel Parameters Taken from Polarization Curves in Brackish Chemistry ..............4-11
Table 4-8 Aging Period of Oxidized Samples ..........................................................................4-12
Table 4-9 Conductivity of Repeat Test Solutions.....................................................................4-13
Table 4-10 Description of Oxidized Samples ...........................................................................4-14
Table 4-11 Tafel Parameters Taken from Polarization Curves from Repeat
Measurements in Sea Water Chemistry ..........................................................................4-15
Measurements in Lake Water Chemistry .........................................................................4-15
Table 4-13 Aging Period for Samples Tested at High Temperature ........................................4-16
Table 4-14 Conductivity of High Temperature Test Solutions .................................................4-17
Table 4-15 Description of Samples Before High Temperature Tests.......................................4-18
Measurements at Elevated Temperatures, in Sea Water Chemistry ...............................4-18
Table 4-17 Summary of Polarization Measurement Results....................................................4-19
Table 5-1 Sample Dimensions...................................................................................................5-1
Table 5-2 Input Parameters and Results for High Conductivity Loop Experiments .................5-22
Table 5-3 Input Parameters and Results for Low Conductivity Loop Experiments ..................5-23
Table 5-4 Free Corrosion Potentials for Metals in the Loop.....................................................5-24
Table 5-5 Summary of Results for Loop Tests ........................................................................5-25
Table 6-1 Estimate of Galvanic Potentials and Currents for Loop Couples Using Simple
Approach............................................................................................................................6-2
Table 6-2 Parameters Used to Estimate the Limiting Cathodic Current ....................................6-4
Table 6-3 Predicted and Measured Currents for Galvanic Couples Using Polarization
Parameters for Fresh Specimens ......................................................................................6-4
xiii
Parameters for Aged Specimens .......................................................................................6-5
2 3
Parameters for Fresh Specimens in Sea Water, but Reduced by 10, 10 and 10 .............6-6
xiv
1
INTRODUCTION
The prediction of corrosion rates is a key input to determining the location and frequency of
inspections and component replacement in the balance of plant of a power station. To quantify
the corrosion susceptibility of various equipment and piping components, EPRI developed the
CHECWORKS Cooling Water Application (CWA) to address the low-temperature/low-flow-
rate conditions normally experienced in raw water balance of plant systems. Within this
context, one of the key issues is galvanic corrosion between dissimilar metals connected in the
same run of piping, or in the same equipment (e.g., valves and heat exchangers).
The galvanic corrosion model currently in the CWA module of CHECWORKS consists of the
following:
1. Examining the two alloys in the galvanic series to determine their galvanic potentials.
2. Calculating the area ratio of the cathode and anode.
3. For the anodic alloy, multiplying the rate of general corrosion by a factor based on the
galvanic potential difference and a factor based on the area ratio of the cathode and anode.
There are a number of implicit assumptions and simplifications in this approach:

1. The galvanic (corrosion) potentials of the two dissimilar metals in the environment under
consideration are the same as in the experimental conditions used to measure these
potentials.
2. The cathodic and anodic surface areas are equivalent to the alloy surface areas.
3. The solution conductivity is such that galvanic corrosion extends for no more and no less
than 10 ft.
Since the general corrosion rates for many of the alloys in the CWA are for the metal in the
passive state and since galvanic corrosion is normally occurring in the active state, it does not
seem consistent to base the galvanic corrosion rate on the general corrosion rate. In addition, the
CWA model is empirical and not based on fundamental principles of electrochemistry.
To remove a number of the assumptions within the galvanic corrosion model used in the CWA, a
new, more mechanistic model was developed [1]. This model uses fundamental principles of
electrochemistry to calculate the galvanic corrosion rate. Part of the development involved a
search of the literature to obtain measured galvanic corrosion rates under well-defined conditions
against which the model could be tested. Although there is a substantial amount of information
in the literature associated with galvanic corrosion, much of the reported work simply involves
the measurement of the potential difference between the dissimilar metals. For the cases were
corrosion rates have been measured, many of the experimental parameters (flow rates,
1-1
Introduction
conductivity, oxygen content, pipe geometry, etc.) are not reported, and so it is impossible to
analyze many of these experiments. The objective of this project is to provide this information
from a series of polarization and flowing loop tests. These experiments are being carried out
under well-characterized conditions on metal couples that are relevant to plant cooling water
systems.
Section 2 of this report gives a brief outline of the new model. Section 3 describes the
experimental work. Sections 4 and 5 present the results. Section 6 discusses and interprets the
results, and Section 7 provides a discussion and summary.
1-2
2
DESCRIPTION OF GALVANIC CORROSIVE MODEL
2.1 Physical Basis of the Model
The model treats galvanic corrosion between two dissimilar metals in a flowing fluid with a
given conductivity. The model is in one dimension and nominally can be viewed as flow
through a pipe consisting of two metals welded together at the galvanic junction. If the
difference between the free corrosion potentials of the two metals is large, then galvanic
corrosion can take place. If the cathode surface area is large compared to the anode surface area
and the solution of high enough conductivity, then significant corrosion of the anode material
will take place.
To model galvanic corrosion, the anodic and cathodic processes at the metal surfaces need to be
simulated. In addition, the transport of charge through the solution from the anode to the cathode
also needs to be modeled. This transport needs to take into account ionic migration, diffusion,
and advection due to any fluid flow. The following sections outline the details of how these
processes are modeled.
2.1.1 Transport Along the Pipe
Chemical species dissolved in the aqueous phase are transported along the pipe by flow, by
diffusion in their concentration gradients, and by drift in the electric potential gradient. For each
species, molecular flux J is given by
C zFDC
J = D '+C
x RT Equation 2-1
where
C is the species concentration

D is the diffusion coefficient
z is the charge number
F is the Faraday constant
R is the gas constant
is the potential gradient
is the flow velocity
x is the distance along the pipe
2-1
Description of Galvanic Corrosive Model
To simplify the notation, subscripts will not be appended to J, C, D and z to differentiate the
species.
Within the pipe, each species obeys a conservation equation, given by
C J
x x x

t 0
Cdx =
0
dx dx
t R 0
x
Equation 2-2
The first term on the right-hand side of this equation is the rate of change of C due to any
chemical reaction. For species involved in anodic or cathodic processes, there is also an electric
current source/sink term. This equation leads directly to the following partial differential
equation for C
C C J
=
t t R x Equation 2-3
The potential is strictly governed by Poissons equation,
2
0 = q
x 2 Equation 2-4
where
o is the permittivity of free space,

is the permittivity of water,
q is the charge density.
The charge density in solution is very small. Therefore, instead of solving Poissons equation, it
is easier to solve for by multiplying equation (2.1) by z and summing over all charged species
to give the following generalized Ohms law equation
= jc jD , Equation 2-5
where
jc is the electric current density flowing in the solution,

jD is the so-called diffusion current density,
is the conductivity.
They are given by the following equations, in which the summations are over all charged
species,
jc = F zJ Equation 2-6
2-2
C
j D = F zD
x
Equation 2-7
F2
=
RT
z 2
DC Equation 2-8
The potential is obtained from the integral of its gradient together with the boundary condition
(0) = 1 where 1 is the free corrosion potential of the first metal.
x
= dx
0 Equation 2-9
The equation of continuity of electric charge that is imposed on the system of equations is:
q
j c dS = t dV
S V Equation 2-10
Since the charge density is so small, the right-hand side of equation (2.10) can be approximated
by setting it equal to zero. The integral of the electric current density is then zero over the
surface of the pipe. This is equivalent to saying that the sum of all anodic and cathodic currents
must equal zero, which is the principle of mixed potential theory.
2.1.2 Corrosion at the Metal Surface
Corrosion of metal (1) by anodic dissolution is described by the following reaction,
M = Mz+ + ze- Equation 2-11
The anodic corrosion current density is given by the Tafel equation,
1
jca = io ,1 exp( ( Ec ,1 m ))
RT Equation 2-12
where
io ,1 and 1 are characteristic constants for the metal (1),

E c,1 is the corrosion potential of the anodic polarized metal (1),
m is the potential in solution at the surface of the metal (1).
m will be a function of position along the metal surface, when the metal/solution interface is not
uniform (e.g., in the region of a galvanic couple when the identity of the metal changes), and so
jca is also a function of x.
2-3
At the cathodic metal (2) surface, several cathodic processes are possible:
z+ -
M + ze = M Equation 2-13
O2 + 4H+ + 4e- = 2H2O Equation 2-14
+ -
H + e = H2 Equation 2-15
corresponding to reduction of the metal ions, oxygen and H+ respectively, all of which should be
considered to get the total cathodic current. However, in systems with a large excess of oxygen,
the reduction of this species is likely to be the dominant contributor to the cathodic current. Each
of these processes can be described by a Tafel equation similar to equation (2.12),
2
j cc = io , 2 exp( ( E c , 2 m )) Equation 2-16
RT
Often the io, 2 is a function of the species concentration in solution.
Reference [1] describes the numerical implementation of the above equations along with the
particular set of Tafel parameters used in that initial study. The Tafel parameters used in the
initial work were for a particular grade of steel not encountered in cooling water systems. It was
clear, therefore, that in order to take this development further, Tafel parameters (as described
above) for alloys of relevance to the cooling water system needed to be determined. Such
parameters are usually determined under very well defined and usually relatively clean
conditions, unlike the conditions experienced in a cooling water system. The transport and
deposition of colloidal material in real cooling water systems is likely to change the structure of
the metal surface, and, therefore, perturb the local Tafel constants away from their values under
clean conditions. In order to obtain a practical model, these effects needed to be accounted for,
and, for this reason, two sets of experiments have been undertaken. The two sets of experiments
are:
Polarization studies, aimed at obtaining Tafel parameters under relatively clean conditions
Flowing loop studies to provide actual galvanic corrosion rates that can be used to modify the
Tafel parameters from the polarization work.
The details of the experimental work are described in the next section.
2-4
3
DESCRIPTION OF EXPERIMENTAL WORK
3.1 Outline of Work Program
The required work splits into two sets of tests.
(a) Polarization tests on individual, commonly used metals, to establish their Tafel
parameters,
(b) Flowing loop tests in which galvanic couples are connected under dynamic
conditions and the steady state corrosion current measured.
The metals of interest to this study are as follows:

Carbon steel
Stainless steel 316L
Stainless steel 304L
Admiralty brass
Titanium
Copper
Al6XN molybdenum alloy steel
Cu90/Ni10 copper-nickel bronze
Cu70/Ni30 copper-nickel bronze
Each of these metals has been tested in both saline (sea water) and lake water conditions. (Saline
conditions were included to ensure measurements where corrosion is active. In order to provide
cross-comparison with other published data, the degree of salinity was chosen to be that of sea
water, for which there is a significant body of literature information). The specification for lake
water was that of a relatively low conductivity, set at 1 mS/cm (1 milliSiemens/cm).
The galvanic couple tests also required lake water and saline water conditions. The couples to be
used were selected from the following table. Priorities were provided by EPRI and are shown in
the shaded cells. The numbers in the cells indicate the relative priority.
3-1
Description of Experimental Work
Table 3-1
Selection of Galvanic Couples
Stainless
steel 6%
Common Zinc
Admir- alloys Molyb-
martensitic when
Carbon Cast alty 70:30 90:10 Al such as denum Titan-
Copper steel alloys used as a
steel iron brass Cu/Ni Cu/Ni bronze 304, materials ium
(e. g., 400 sacrificial
alloys 304L, such as
series) anode
316, and AL6XN
316L
Carbon steel - 1 1 1 1 1 2 1 2 1 1 2
Cast iron - 3 3 3 3 3 2 3 3 3 2
Admiralty brass - 3 3 3 3 2 3 3 3 3
Copper - 3 3 3 2 3 2 2 3
70:30 Cu/Ni - 3 3 3 3 2 2 3
90:10 Cu/Ni - 3 3 3 2 2 3
Aluminum bronze - 3 3 3 3 3
Stainless steel alloys 304,
- 3 1 2 3
304L, 316, and 316L
Common martensitic steel
- 3 3 3
alloys (e. g., 400 series)
6% Molybdenum materials,
- 3 3
such as AL6XN
Titanium - 3
Zinc when used as a

-
sacrificial anode
Key:
1= top priority
2=lower priority
3=combination not commonly used
3-2
3.2 Experimental Technique
3.2.1 Polarization Experiments
General Description
These measurements are intended to provide information on the rate of change of current as a
function of voltage, i.e., the slope of the Tafel plot. These tests are performed on each metal,
individually, in a simple cell within a glass vessel. Tests were carried out varying the water
chemistry from low-conductivity lake water (i.e., 1 mS/cm) to high-conductivity sea-water
(about 75 mS/cm). This latter conductivity is slightly higher than for true sea water because the
test solutions used only NaCl (not the full chemistry of sea water) at a chloride ion concentration
approximately the same as sea water, which is 0.56M (rounded to 0.6M for the tests).
Process
Samples of various metals have been obtained as tube specimens. These are typically 25-cm
long, and have an internal diameter of 10 mm and a wall thickness of a few mm. All tube
samples are coated (on the external surface) with a suitable non-conductive enamel to restrict the
area subject to corrosion, to a region of 5-cm length from one end (and enamel is not applied to
one cm at the other end of the sample, to allow electrical connection). Each tube sample in turn
is clamped within a threaded PTFE rod that restricts water access to the outer surface only, then
located in a polarization cell (further details are given below). When located within the cell, the
tube is electrically connected to a wire by a mechanical clip fixed to the 1-cm bare metal surface.
The cell is also equipped with a platinum wire electrode as a loop around the center-line of the
exposed 5-cm length of metal. This arrangement has the advantage of a uniform (radial) ionic
conduction path. The vessel is filled with suitable electrolyte, such as simulant sea water (0.6M
NaCl in deionized water), or simulant lake water (0.0085M NaCl). A Calomel reference
electrode is also present in the cell, having a luggin probe tip, terminating very close to the metal
tube surface. The metal/platinum/reference cell is connected to a computer-controlled
potentiostat which incorporates a zero resistance ammeter. This arrangement is connected to a
PTI-100 interface box and controlled by a dedicated computer. The cell is also equipped with
the means of sparging air through the water, and a stirrer for mixing the solution thoroughly.
The platinum wire electrode is always more noble than the tube metal, so the anodic process is
dissolution of the tube metal, and the cathodic process is the reduction of O2 to produce
hydroxide ions. Due to the relatively short timescale of these tests, the pH of the solution
remains effectively constant.
The nature of the tests is to vary the applied potential and measure the resulting corrosion
current. They start with a low potential, which is gradually increased, and stopped at a high
potential.
The method has evolved through this work. In the early stages, some materials were tested by
performing potentiostatic detailed measurements in simulant sea water, i.e., a selected potential
was applied, and the resulting current was allowed to stabilize before being recorded. A stable
3-3
current was defined as a drift of less than 2.5 A per minute. By its nature, this had to be by
manual control. Each incremental step in voltage (say 0.02 V in the Tafel region, 0.03 V
elsewhere) was allowed to stabilize in this way. Up to 30-minute stabilization was required per
step. A single test may have taken up to 15 hours. However, such potentiostatic tests were
found to be somewhat irreproducible. Simply due to the length of time they required, the surface
partly oxidized and, for some easily corroded metals, the results obtained depended on the degree
of sensitivity of the chosen drift allowance and stabilization time. It was concluded that a
uniform approach should be adopted, with a common procedure starting with a clean fresh
surface, and a potentiodynamic scan rate of either 1 or 2 mV per second. In the earlier tests, this
was 2 mV/s; however, it became clear as the work progressed that numerical smoothing of the
results would be needed, and as this smoothing required more data points, the scan rate was
reduced to 1 mV/s.
3-4
Equipment (see diagram Figure 3-1 and photograph Figure 3-2)
The individual items of equipment are:

Potential measurement cell containing saline solution or deionized water, above drip tray.
Electrodes, i.e., sample tube, platinum ring, Calomel (via luggin). The platinum ring
electrode encircles the bare metal area of the working electrode at its half-height point.
Magnetic stirrer beneath cell, also in drip tray.
Potentiostat.
PCI-100 interface module.
PC for controlling the PCI-100.
Pt ring Ministat
Ele ctrode
Pote ntiostat
Gas Sparge Re fe re nce

In/out Ele ctrode
(luggin tip)
Ce ll
containing PCI - 100
e le ctrolyte
Inte rface module
Me tal Tube ,
uppe r e nd insulate d
Stirre r Drip
Tray CONTROL
P. C.
Figure 3-1
Schematic Diagram of Polarization Test Equipment
3-5
Figure 3-2
Polarization Test Equipment
This shows (top, from the left) the control computer, the potentiostat, on top of which are the conductivity
and pH meters, and to the right of picture the stirrer and the glass polarization cell. The lower picture
shows the polarization cell, fitted with a bare metal working electrode; the red top of the Calomel
electrode in its luggin housing is visible, as is the white lower tip of the gas sparge line (which has a frit
on the end).
3-6
Method
The principle of operation is that the potential applied to the cell is changed through an
appropriate range. As the applied voltage is initially negative, the metal tube is initially
protected against corrosion (cathodically protected). As the potential is increased, the surface
becomes more susceptible to corrosion, and at a certain characteristic potential (for passive
metals) the protective surface oxide fails and corrosion ensues. The apparatus also measures the
resulting corrosion current (normally in the microamp to milliamp range) and gives a plot of
applied potential against the measured (cathodic or anodic) current. The rate of change of
potential (with time) can be set using the control computer and the potentiostat, and is typically
of the order 1.0 or 0.1 mV per second.
The samples, all metal tubes, are prepared by abrasion of the external surface to a 1200-grit
finish using emery paper, then degreased before painting, using acetone in an ultrasonic bath for
10 minutes. The painting process was done only using gloved hands: the external surface was
coated with an insulating enamel paint leaving bands of bare metal of 5-cm length at one end of
the tube and 1-2 cm at the other end of the tube. The painted surfaces were allowed to dry out
and harden for at least seven days before further use. The paint-coated samples were then
abraded again (at the exposed metal areas) to a 1200-grit finish using silicon carbide paper, and
washed clean with water and then wiped with a tissue soaked in methanol, and allowed to dry.
When mounted in the corrosion cell, the internal surfaces are not wetted: a threaded plastic rod
through the center of the tube and plastic end-washers and seals are used to prevent water access
to the center and end faces of the tube. The 5-cm bare metal end is the wetted end, and the 1-cm
bare metal end is used for electrical connection.
The corrosion cell is set up with the wetted end of the sample tube centralized radially and
vertically within the compass of the platinum ring counter electrode. (See Figure 3-2). The
luggin probe tip of the reference electrode, containing the same electrolyte as in the test, is
positioned as close as possible to (but not touching) the exposed surface of the metal tube. For
this work, the distance was set at 2 mm, this being the wall thickness of the glass capillary tubing
used at the tip of the luggin probe. The tube samples have an external diameter in the region of
2
1.5 cm, and, therefore, an exposed (wetted) surface area of the order of 24 cm .
Before starting the measurements, the free corrosion potential (between the test metal and the
Calomel reference electrode) is measured until it reaches a stable value. The control computer
converts all the measured potentials to be relative to the Saturated Hydrogen Electrode.
At the end of the test, the measurement cell is turned off and the pipe section removed from the
holder. The specimens are stored in plastic bottles, immersed in the solution in which they have
been polarized. (Some specimens were required for re-polarization, after a period of surface
oxidation in the relevant solution).
Tests have been repeated for each of the materials listed in Section 3.1, in both lake water and
sea water simulant solutions (conductivities adjusted using NaCl).
3-7
3.2.2 Flowing Loop Tests
General Description
The requirement was to measure the corrosion potential and steady state corrosion current that
would flow between dissimilar metals when connected by an ammeter and via an electrolyte. In
addition, it is necessary to characterize the test conditions using standard techniques such as pH
measurement, conductivity measurement, temperature, and flow rate.
Tests may last up to 1000 hours each. In order to study a number of dissimilar metal couples
within a reasonable time frame, two experimental couples are studied in parallel, so two tests are
in progress at any one time, using parallel channels of a single flow loop.
The tests are carried out with air-saturated water. Two kinds of solutions are studied:
(a) First, a saline solution to a concentration of NaCl equivalent to sea water (0.6M), and
(b) Second, water with a relatively low conductivity, similar to lake water, nominally 1
mS/cm (made as 0.0085M NaCl).
Samples of various metals were provided as tube specimens. These are typically 15-cm long,
and have an internal diameter of typically 10 to 12 mm and a wall thickness of a few mm. Two
such tube samples are clamped together, with a hollow insulator between them, to form a pipe
test section. The clamping device is made mainly of PTFE, some elastomer O-rings, and held on
a steel base-plate. The only wetted metal surfaces are those of the test specimens. The test
section is connected to a reservoir containing test solution (a) or (b) by plastic tubing (mainly
PTFE, 10-mm internal diameter). The test solution is circulated around the loop by a centrifugal
pump (neoprene impeller in the non-metallic pump head). Between the pump and the test
section, upstream of the specimens, there is in-line measurement of pH, conductivity,
temperature, and flow rate. These are measured using probes attached to relevant indicating
instruments. Reference potentials are measured at the interspace between the two metals. A
schematic diagram of a flow loop is shown in Figure 3-3 and the actual equipment in a
photograph in Figure 3-4.
The more anodic of the two metals will slowly corrode, releasing metal ions to the solution as a
function of time. However, this should make no measurable difference to the conductivity or pH
of the solution, which is of sufficient volume as to make any impurity concentrations
unimportant. The test sections are placed in a drip tray large enough to accommodate the entire
volume of saline solution from the loop and reservoir. This safeguard covers the risk of seal
failure in the specimen-clamping device.
Equipment (see diagram Figure 3-3 and photograph Figure 3-4)

Tube-clamping device in drip tray.
Reservoir vessel containing 10 liters of sea water or lake water simulant.
Stirrer unit beneath reservoir.
3-8
Metal frame for reservoir, stirrer, drip tray beneath reservoir.

Centrifugal pump controlled by speed controller.
PTFE tubing and silicone tubing.
pH meter and electrode.
Conductivity meter and electrode.
Temperature sensor and read-out unit.
Reference electrodes (Calomel).
Voltmeters (highimpedance electrometers) with output connections.
Zero-resistance Ammeters, with output connections.
Flowmeters (both electronic and mechanical, the latter as back-up).
Molytek data logger (and data processing PC).
Drip trays to contain any spill of liquid.
SCHEMATIC DIAGRAM OF CORROSION CURRENT FLOW LOOP

Gas sparge line (if req'd) Analysis Instruments
pH / Conductivity / temperature
Electronic
Flow
Meters
Visible
Zero Flow
Reservoir Resistance Meters
(stirred) Centrifugal Ammeter
Pump
Metal A Metal B
Calomel electrode Volt

Meter
Metal C Metal D
Calomel electrode
Volt
All circuit to be made of insulating plastic, Meter
except metal sections A and B.
Zero Data
As much as possible, PTFE tubing to be used. Resistance Recording
Plastic impeller necessary at pump head Ammeter
Glass for reservoir, and flow meter tube.
Connection fittings PTFE or Nylon.
Figure 3-3
Schematic Diagram of Galvanic Corrosion Test Loop
3-9
Figure 3-4
Galvanic Corrosion Test Loop
This picture shows, from the left, the reservoir (which contains the brown-colored solution),
below which (black) is the pump; the instruments are located above the central drip tray, and the
metal test section clamp jigs are in the right hand drip tray. On the right hand bench is the
Molytek data logger (large grey box) on top of which are the ZRAs, and the temperature and
conductivity meters. On the extreme right is the data collection PC. Foreground, on the trolley,
are the electrometers one for each channel and (blue) the calibrated milliVolt source used to
provide test signals.
Note that it is necessary to calibrate the instruments, such as pH and conductivity, to QA

traceable standards, as part of the loop set-up. The Molytek data logger was re-calibrated before
commissioning by an external test house.
Method
The tube specimens of the metals to be studied are clamped together in the tube-clamping device.
Other tubing is connected to form a complete flow loop between it and the reservoir. Plastic
tubing and connectors are used to the extent possible. (The temperature probe unavoidably does
have some metal surfaces). Within the loop are plastic electrode housings for pH, conductivity,
temperature, and reference potential.
Test solutions with one of two chemistry regimes were made up in the 10-liter reservoir. These
were either sea water, (a 0.6M solution of NaCl in deionized water: 351 g NaCl in 10 liters) or a
simulant lake water having a conductivity of 1 mS/cm (a 0.0085M solution of NaCl in deionized
water: 4.97 g of NaCl in 10 liters). The test solution was circulated around the test loop using
3-10
the centrifugal pump. The solution was aerated (the flow rate of the water returning to the
reservoir was more than enough to agitate and aerate the solution in the reservoir). There was
also a magnetic stirrer at the base of the reservoir.
The test pattern was to perform all the tests using saline solution first, and then to change the
electrolyte to simulant lake water. It was necessary to drain the loop and then flush the loop with
several changes of water to remove the simulant sea water from the instrument and pump
housings. The plastic pipe-work was replaced with new lengths to remove traces of deposited
corrosion products.
Prior to the start of the test, the loop pump was energized and a stable flow condition was
achieved. During the stabilization period, the loop parameters (temperature, pH, conductivity)
were measured. Also, the open-circuit potential between the two metals of the galvanic couple
was measured. Further, the free potential of each of the test metals, relative to a Calomel
reference electrode, was measured. When all these parameters had stabilized, the galvanic
corrosion test was started. In this context, a stable free potential was considered to be a drift of
less than 1 mV per hour. The location of the reference electrode was via a capillary adapter to
the center of the tube-clamp jig.
The galvanic corrosion tests were essentially a measurement of the corrosion current, which was
monitored using a Zero Resistance Ammeter (ZRA). The objective of the test was to obtain a
stabilized corrosion current value under the imposed conditions.
The outputs from the ZRA and from the other instruments were logged using a Molytek data
logger. This was connected to a PC using a standard RS232 serial port connection. All relevant
electronic and analytical modules were electrically tested prior to use. The experimental data
was exported, at the end of each test, into a Lotus-123 worksheet format (which could then be
imported to Microsoft Excel).
Upon conclusion of the test, the tube samples were removed from the loop, washed with pure
water, dried and kept in a vacuum dessicator for future reference.
3-11
MATRIX OF TEST MATERIALS AND CONDITIONS
The following metallic couples were studied in the loops. These were studied two sets at a time,
in parallel arms of the test loop (see Fig 3.2).
Loop 1: Test A1 Carbon steel and Admiralty brass in saline solution
Test B1 Carbon steel and titanium in saline solution
Loop 2: Test C1 Carbon steel and 90:10 Cu/Ni bronze in saline solution
Test D1 Carbon steel and stainless steel in saline solution
Loop 3: Test E1 Carbon steel and AL6XN in saline solution
Test F1 AL6XN and stainless steel in saline solution
Loop 4: Test A2 Carbon steel and Admiralty brass in simulated lake water
Test B2 Carbon steel and titanium in simulated lake water
Loop 5: Test C2 Carbon steel and 90:10 Cu/Ni bronze in simulated lake water
Test D2 Carbon steel and stainless steel in simulated lake water
Loop 6: Test E2 Carbon steel and AL6XN in simulated lake water
Test F2 AL6XN and stainless steel in simulated lake water
3-12
4
POLARIZATION EXPERIMENTAL RESULTS
4.1 Preliminary Tests and Method Development
The polarization test equipment was commissioned, using a spare carbon steel sample as the test
material, and saline solution. The carbon steel tube was partly covered by a corrosion-resistant
enamel paint (Japlac lead-free enamel), to leave at one end a defined area of bare metal 5 cm
in length exposed to the test solution, and at the other end a bare area of metal approximately 1-
to 2-cm length, for electrical connection. The polarization curve was measured
potentiodynamically.
Previous literature references to similar measurements (but in deoxygenated solution) [2] had
noted the benefit of performing measurements using a potentiostatic technique, i.e., by adjusting
the potential manually, in increments, to sweep the required range. In practice, this would mean
setting a potential (manually), and with this potential held constant (potentiostatic), then allowing
the current to equilibrate. When equilibrated, the current would be recorded. Then, the potential
would be adjusted to the next incremental step, and so on. This offers the advantage that if the
current is slow to equilibrate, the potential and current are not out of synchronization. This
approach was investigated; however, it was found that results from the same carbon steel sample
were irreproducible. It was clear that during testing, the carbon steel was oxidizing (corrosion
product was clearly visible) and that as the oxide formed, it set up a surface resistance which
influenced the reading at the next potential increment. The whole scan then depended on the rate
of change of potential, with the longer equilibration times meaning more oxide and more
deviation from the potentiodynamic results. The key feature was clearly the production of oxide,
which would not have occurred under the deoxygenated conditions of reference [2].
It was then concluded that the potentiostatic method was not suited for an oxygenated system,
and should not be used.
Therefore, the measurements made in this study used a potentiodynamic technique. The
measurements were performed as a sweep of the voltage range and a measurement of the
resulting current. This is plotted as Figure 4-1, as an example. In the original approach, the
voltage was swept from cathodic to anodic, and a reverse scan was also carried out. The results
were then re-calculated as the logarithm of the current density, and plotted vs. potential (called a
Tafel plot). This is presented in Figure 4-2 showing reasonably good characteristics. From the
Tafel plot may be extracted the slopes of both the anodic and cathodic responses (Ta and Tc), as
they approach the current density minimum, together with the magnitude of the current density at
the minimum point (icor) and the potential at the minimum point (Ecor). These details area shown
in Figure 4-3. The units of Ta and Tc (being linear/logarithm plots) are mV per decade, by
historical convention.
4-1
Polarization Experimental Results
It also became clear that the condition of the surface (in terms of initial oxide) would be an
important factor. For example, in Figure 4-2, the minima of the forward and reverse sweeps are
at slightly different voltages, because the surface condition has been affected by taking the
sample to anodic conditions where it has actively corroded. This was one of the reasons why the
Tafel plot was calculated from the results of the forward sweep, not the reverse sweep.
Therefore, it was also concluded that all test samples should be new, and not pre-oxidized, and
must be cleaned, abraded, degreased, etc. to a consistent standard and must not be touched by
bare hands.
The sample preparation method that was finally adopted was to degrease the metal samples
before painting, using acetone in an ultrasonic bath for 10 minutes. The painting process must be
done only using gloved hands. The paint-coated samples were then abraded (at the exposed
metal areas) to a 1200-grit finish using silicon carbide paper and washed clean with water and
then wiped with a tissue soaked in methanol and allowed to dry.
The polarization measurements were performed using a scan rate of either 1 or 2 mV per second.
This was on the basis that the more easily oxidized specimens needed a faster sweep to minimize
changes to the surface condition as the test was in progress. However, this had to be balanced
against the need to collect sufficient data points to be able to plot a reasonable Tafel plot, and
very fast sweeps (fewer data points) were therefore inappropriate.
Some measurements were affected by noisy traces in the Tafel plots. These were usually the tests
with the more corrosion-resistant materials, where the transition from cathodic to anodic
behavior was complex, reflecting the intermittent breakdown of passivity, and the transition
sometimes stretched across a wide voltage range. This feature is effectively unavoidable as it
reflects the nature of the material when studied by this technique. In order to overcome the
problem of measurement noise, numerical smoothing of the data was performed. This has
allowed the preparation of better Tafel plots where clearer trends can be seen and the slopes
more conveniently assessed.
It was also clear, for those scans beginning well to the cathodic side of Ecor, that there was a
considerable plateau in the voltage sweep where the measured current did not change
considerably over a significant voltage range. Under these conditions, the cathodic reaction was
the reduction of oxygen. This feature meant that the Tafel plot slope had to be evaluated quite
close to the icor minimum; ideally, the slope should be evaluated some 120 mV or so away from
Ecor, and in deoxygenated conditions, this approach would be possible. But in these tests, it was
not reasonable to do so, and this constraint on the result interpretation is recognized.
From this basis, the following series of polarization tests were carried out.
4-2
Carbon Steel in saline aerated conditions
1600
1400
1200
1000
800
Current (mA)
Forward scan
600
Reverse scan
400
200
-200
-1400 -1200 -1000 -800 -600 -400 -200 0
-400
Voltage (mV)
Figure 4-1
Polarization Commissioning Carbon Steel in Sea Water Solution (Measured Results)
4-3
Carbon Steel in Aerated Seawater Chemistry

Plot of Log Current Density vs Potential
-1
-2
Log (Current Density) / A/cm sq
-3
Forward Sweep
-4
Reverse Sweep
-5
-6
-7
-8
-1400 -1200 -1000 -800 -600 -400 -200 0
Potential (mV)
Figure 4-2
Polarization Commissioning Carbon Steel in Sea Water Solution (Calculated Results)
4-4
Carbon Steel in seawater chemistry

Scan Rate - 2.0 mV / sec
-1 Ta approx. 60
mV/decade
-2 Tc approx 110
mV/decade
Log Current Density
-3
-4
-5 Log Io approx -4.8
-6
-7
-8
-1200 -1150 -1100 -1050 -1000 -950 -900 -850 -800 -750 -700 -650 -600 -550 -500 -450 -400 -350 -300
Potential (mV)
Figure 4-3
Polarization Result Carbon Steel in Sea Water Solution (Tafel Plot)
4-5
4.2 Polarization Tests in Simulant Sea Water
The first series of polarization measurements were made using a high-conductivity solution
simulating sea water. This was chosen on the basis that there is an extensive literature on
corrosion testing in sea water conditions, and for a high conductivity test this would be a logical
test condition to allow cross-comparison with other work.
Test solutions were made up by adding 35.1 grams of NaCl to one liter of Analar (Analytical
grade) water (equivalent to 0.6M solution). The solution was sparged with air and stirred, before
use, to ensure it was air-saturated. The test equipment was as shown in Figures 3-1 and 3-2
above.
The metals tested in the initial set of tests were as follows:
Carbon Steel, 316L Stainless Steel, Admiralty Brass, Titanium, Copper, AL6XN Molybdenum
Steel, and 90:10 Cu/Ni Bronze. These had the dimensions shown in Table 4-1.
Table 4-1
Dimensions of Polarization Samples (length 250 mm).
Sample External Diameter Electrode Area

(mm) (cm2)
Carbon Steel 15.0 23.56

Titanium 12.7 19.95
Admiralty Brass 12.7 19.95

316L Stainless Steel 15.0 23.56
90:10 Cu/Ni Bronze 12.6 19.79
AL6XN Molybdenum Steel 12.8 20.11

Copper 12.9 20.26
For each metal, polarization curves similar to Figures 4-1 and 4-2 were obtained, and these were
recalculated to give Tafel plots similar to Figure 4-3. The slopes of the Tafel plots and the
absolute magnitude of the current density minimum were evaluated. These results are now
tabulated in Table 4-2.
4-6
Table 4-2
Tafel Parameters Taken from Polarization Curves in Sea Water Chemistry
Material Ta Tc icor Ecor

(mV/decade) (mV/decade) (A/cm2) (mV)
Carbon Steel 60 110 1.6E-5 -690
316L Stainless Steel 130 260 6.3E-7 +10

Admiralty Brass 30 35 2.5E-6 -245
Copper 50 110 2.0E-5 -220
Titanium 410 680 1.6E-7 +650
AL6XN 280 730 6.3E-7 +210

90:10 Cu/Ni 60 85 1.8E-5 -250
The polarization plots are presented in Appendix A. The plots for titanium and AL6XN were
very difficult to interpret, having a noisy trace with no clear minimum. This was improved
slightly by smoothing the measurement results by an averaging technique for either seven or
thirteen adjacent points, applied through the result set. Even so, the results for these metals
given in Table 4-2 may be subject to large experimental errors. Interpretation of these plots is
generally difficult with several cathodic processes taking place and with the possibility that
reduction of O2 may be mass-transfer controlled. The solution was sparged with air, and the
vessel was well stirred/agitated to try and minimize mass transfer effects, but the efficiency of
this procedure cannot be quantified.
4.3 Polarization Tests in Simulant Lake Water
The second series of polarization measurements were made using a low-conductivity solution
simulating lake water. This was chosen to have a conductivity of 1 mS/cm, (compared with the
sea water simulant with a conductivity of around 75 mS/cm). This value was itself a
compromise figure, as there are some power plants using fresh-water in the tertiary cooling
systems with an even lower conductivity; however, at very low conductivity, it may be difficult
to measure any corrosion behavior. The noise associated with these measurements also required
numerical smoothing of most of the measurement values in the calculation steps.
A further complication of these studies was that the accurate measurement of the potential of the
working electrode was made more difficult by the lower conductivity of the solution. This is
commonly referred to as the IR drop and is a frequent concern for electrochemical
measurements in low conductivity solutions. As a very rough estimate, if measuring a current of
1 mA in a solution with a conductivity of 1 mS/cm (or resistance of 1000 /cm), then the 2-mm
gap between the luggin probe tip and the surface of the working electrode represents a resistance
of 200 and a voltage drop of 0.2 V. In a context where measurements are being made to an
accuracy of a few milliVolts, a 200-mV offset, which depends on the current, makes accurate
measurement much more difficult.
This was approached by considering only measurements where the current was less than 50 A
(10 mV IR drop), and also re-plotting the Tafel plot with the IR drop added or subtracted (as a
4-7
minimum/maximum range limit see Tables 4-3 and 4-6 relating to lake water), and re-
evaluating the slopes of those plots. The Tafel plot obtained from the (usually smoothed)
experimental results has been taken to represent the base-case, or the best value for deriving the
slopes of the anodic and cathodic responses. The effect of the IR-drop is to make uncertain the
voltage to which the measured current corresponds. The uncertainty is zero at Ecor, where the
current (I) is formally zero, and from V = IR, V is also theoretically zero. R is fixed, as a
consequence of the conductivity and the gap between the luggin probe and the working
electrode. The results have been treated by taking the raw values of I and corresponding V (as
measured, after numerical smoothing) and also calculating, for each data point, the delta-V (the
change in V) corresponding to the current and resistance applying to that point. It is assumed that
the delta-V, which is essentially an uncertainty, may be positive or negative about the optimum
(base-case) value. Therefore, for both the cathodic and anodic sides of the plot, alternative values
for V have been derived, by adding or subtracting delta-V. These have been plotted, as shown in
Figure 4-4 (an example based on 70:30 Cu/Ni bronze in lake water), and "Tafel slopes"
evaluated in the same way as for the base-case results. The Tafel slopes derived in this way
represent "minimum" and "maximum" values for an envelope, within which the base-case results
must sit.
IR drop Tafel plot - 70/30 Cu/Ni bronze in lake water
-5.0
-6.0
Log C urrent D ensity (A /cm sq)
Unmodified results
-7.0
Minimum voltage
variation
Ta max = 16 mV/dec
Maximum voltage
Ta min = 5 mV/dec
variation
Tc max = 20 mV/dec
-8.0 Tc min = 8 mV/dec
-9.0
-140 -130 -120 -110 -100 -90 -80
Potential (mV)
Figure 4-4
Estimation of the Effect of the IR Drop 70:30 Cu/Ni Bronze in Lake Water (Tafel Plot)
It should be noted that within the luggin probe, there may also be a further IR drop between the
probe tip and the tip of the Calomel reference electrode. This is a distance of about 10 cm and the
solution inside the Luggin may be low-conductivity electrolyte, of the same composition as the
test solution. However, in this case the internal IR drop of the luggin probe was overcome by
using a platinum wire inside the luggin probe, this being wound round the Calomel tip at one end
4-8
and extending to the tip of the glass capillary at the other end. This precaution ensured there
could be no potential difference between the Calomel electrode and the capillary tip.
Table 4-3 lists the Tafel constants that have been obtained from the polarization studies on the
various fresh materials in oxygenated lake water solution. Again, the polarization plots are
presented in Appendix A.
Table 4-3
Tafel Parameters Taken from Polarization Curves in Lake Water Chemistry

Carbon Steel 0.5 (33 max, 0 min) 0.6 (33 max, 0 min) 1.3E-6 - 458
316L Stainless 35 (41 max, 32 min) 35 (44 max, 29 min) 1.0E-7 + 325
Admiralty Brass 13 (20 max, 0 min) 25 (30 max, 0 min) 6.3E-7 - 116
Copper 25 (43 max, 15 min) 30 (43 max, 19 min) 5.0E-7 - 125
Titanium 400 (500 max, 350 min) 400 (500 max, 300 min) 6.3E-8 +5
AL6XN 35 (38 max, 29 min) 55 (64 max, 32 min) 4.0E-8 + 275

90:10 Cu/Ni 5 (20 max, 0 min) 8 ( 17 max, 0 min) 5.0E-7 - 87
4.4 Polarization Tests of Additional Metals
During the course of the work it became apparent that it would be of benefit to measure the
polarization characteristics of some other widely-used metals. These were: 304L stainless steel,
and 70:30 Cu/Ni bronze. The chemistry conditions would be both sea water, and lake water, as
above. These materials had the dimensions shown in Table 4-4.
Table 4-4
Dimensions of Additional Sample Materials (Length: 250 mm)
Sample External Diameter Electrode Area

(mm) ( cm2)
304L Stainless Steel 15.3 24.03

30:70 Cu/Ni Bronze 12.7 19.95
From each metal, polarization curves similar to Figures 4-1 and 4-2 were obtained, and these
were recalculated to give Tafel plots similar to Figure 4-3. The slopes of the Tafel plots and the
absolute magnitude of the current minimum were evaluated. These results are now tabulated in
Tables 4-5 and 4-6.
4-9
Table 4-5
Further Tafel Parameters Taken from Polarization Curves in Sea Water Chemistry

304L Stainless Steel 65 220 1.6 E-7 + 90
30/70 Cu/Ni Bronze 60 70 1.6 E-5 - 250
Further polarization measurements were made using lake-water simulant chemistry, as described
above in Section 4.3. The results of these measurements are given in Table 4-6.
Table 4-6
Further Tafel Parameters Taken from Polarization Curves in Lake Water Chemistry.

304L Stainless Steel 20 (28 max, 6 min) 15 (20 max, 4 min) 2.5 E-7 +443 mV
30/70 Cu/Ni Bronze 11 (16 max, 5 min) 15 (20 max, 8 min) 1.6 E-7 - 107 mV
The polarization plots for these measurements are presented in Appendix A.
These results are summarized, alongside all other results, in Section 4.9.
4.5 Polarization Tests at Intermediate Conductivity.
The measurements reported in Sections 4.2 and 4.3 span a wide range of conductivity, i.e.,
approximately 1 and 70 mS/cm. It is recognized that some plant operate with water
conductivities lower than 1 mS/cm, but measurements in that regime would be problematic
because of the IR drop, and also that some plants operate with water conductivities slightly
higher, e.g., from brackish lakes. The possibility of extrapolating or interpolating the
measurements reported above was considered, but as it could not be established whether the
relationship was linear or not, it became clear that a third set of measurements, at a practically
convenient conductivity, would be needed.
Therefore, a set of measurements has been performed at a solution conductivity of about 10

mS/cm, equivalent to a brackish lake. The materials studied were as follows:
Carbon Steel, 316L Stainless Steel, 304L Stainless Steel, AL6XN Molybdenum Steel, Copper,
Admiralty Brass, 90:10 Cu/Ni Bronze, 70:30 Cu/Ni Bronze, and Titanium, i.e., all the metals
studied in the preceding investigations.
The sample dimensions were the same as those reported in Sections 4.2 and 4.4. The solutions
for the tests were prepared from Analar water and sodium chloride, adding approximately 5.84 g
of NaCl per liter of water (0.1M NaCl).
4-10
The test procedure was the same as used previously. The metal samples were partly painted with
a protective enamel, leaving an exposed region of 5 cm as the working surface, and with bare
metal at the other end of the sample for electrical connection. Before painting, the metal was
degreased in acetone, rinsed with water, and dried. After painting, the working area of the metal
was abraded to 1200-grit finish, and wiped with a paper tissue soaked in methanol. Once
degreased, the sample was not touched with bare fingers. All samples were allowed at least 7
days for the paint to dry and harden.
The polarization curve of each sample was made in a fresh solution of brackish water. The
solution conductivity was measured and confirmed as being close to 10 mS/cm. Also, the open-
circuit potential between the metal and a saturated Calomel electrode was checked in each case.
The results of the polarization measurements, and the subsequent Tafel plots, are presented
below in Table 4-7.
Table 4-7
Tafel Parameters Taken from Polarization Curves in Brackish Chemistry

Carbon Steel 19 28 1.0 E-5 -628
316L Stainless 35 200 2.5 E-7 150

304L Stainless 40 160 1.3 E-7 160
AL6XN 180 370 2.3 E-7 730

Copper 45 80 3.2 E-6 -190
Admiralty Brass 12 25 2.0 E-6 -182
90:10 Cu/Ni 14 83 3.2 E-6 -145
70:30 Cu/Ni 25 55 1.3 E-6 -155

Titanium 110 160 3.2 E-7 440
These results are generally consistent with those previously measured for sea water or lake water
conditions, and are generally between the values of the results measured in those tests. This
relationship can be seen more clearly in the tables of the following section.
4.6 Polarization Tests of Oxidized Samples
During the preliminary work, commissioning the equipment and developing a method (Section
4.1), it became apparent that the results could be significantly influenced by the condition of the
metal surface, and the presence of an oxide film there. However, it was also clear that in a real
installed plant, the pipework surfaces are almost never pristine, and pre-oxidized surfaces are
normal. Most literature values for polarization tests are made with reference to new, bright metal
surfaces, in de-oxygenated conditions, where oxide film only slowly builds up. In the case of
real operating plant, however, these conditions are not met: the reality is that most pipework is
aged, and has some measure of oxide film, and the water passing through it is not normally
4-11
deoxygenated, although it may become oxygen-depleted due to oxygen reacting with the
pipework surfaces. Therefore, most literature results are not (in principle) measuring the same
conditions as are relevant to the corrosion engineer seeking to establish inspection and
replacement schedules for operating plant. Therefore, to ensure that the findings of this work
could be applied more reliably to existing plant, further tests were performed to investigate the
effect of aging on polarization measurements.
For these repeat measurements, the following materials were selected: carbon steel, Admiralty
brass, and 90:10 Cu/Ni bronze. Their selection was on the basis that these were likely to have
oxidized and some film would be present. These were studied in both sea water and lake water
simulant solutions. The storage conditions had been that the coated tube sections were placed
inside upright plastic containers with a screw-top closure, and the original liquid from the first
polarization test was poured in: this immersed most of the sample, but not the connection end
which had been used to make the electrical connection to the potentiostat. Approximately the
top three centimeters of the sample were not wetted, of which one to two centimeters were bare
metal. The samples were stored in individual bottles, in a drip-tray, at room temperature.
The period of aging was not uniform. (This was an unavoidable feature of the scheduling of the
work). The actual aging periods were as shown in Table 4-8.
Table 4-8
Aging Period of Oxidized Samples
Material Test Solution Aging Period
Carbon Steel Sea Water 226 days

Carbon Steel Lake Water 85 days
Admiralty Brass Sea Water 227 days
Admiralty Brass Lake Water 80 days
90:10 Cu/Ni Bronze Sea Water 144 days

90:10 Cu/Ni Bronze Lake Water 86 days
The repeat polarizations were carried out under the same conditions as the original polarizations,
as far as was practically possible. Before polarization, the conductivity of each test solution was
re-measured, and recorded (Table 4-9). The original sea water simulant solutions had not been
measured, but these were assumed to be about 75 mS/cm, consistent with measured
conductivities from the flowing loop tests at the same solution composition.
4-12
Table 4-9
Conductivity of Repeat Test Solutions
Material Test Solution Original Conductivity Repeat Conductivity
Carbon Steel Sea Water Not measured. Assume 75 62 mS/cm

mS/cm
Carbon Steel Lake Water 1.0 mS/cm 1.0 mS/cm

Admiralty Brass Sea Water Not measured. Assume 75 62 mS/cm
mS/cm
Admiralty Brass Lake Water 1.0 mS/cm 1.0 mS/cm
90:10 Cu/Ni Bronze Sea Water Not measured. Assume 75 60 mS/cm

mS/cm
90:10 Cu/Ni Bronze Lake Water 1.0 mS/cm 1.0 mS/cm
The physical condition of each of the aged samples was recorded. The descriptions are provided
in Table 4-10.
4-13
Table 4-10
Description of Oxidized Samples
Material & Description

Test Solution
Carbon Steel in Sea The stored solution was deep brown and opaque due to extensive corrosion
Water during the storage period. The metal sample had developed significant
corrosion product growth on both ends of the specimen; the corrosion product
on the connection end had to be removed with a file and the surface
brightened with abrasive, to provide a good electrical connection to the
potentiostat. The paint had blistered, particularly above the water line in the
storage container, and no longer served as a good insulator. The insulation
was reinstated by spiral-winding PTFE tape along the affected area of the
painted surface.
Carbon Steel in Lake The solution had a deep orange/brown coloration. There was not much solid
Water material detached from the metal sample. The sample had developed
corrosion on both exposed ends: the connection end had to be filed and
abraded to restore a bright finish for attachment of electrical connections. The
paint had blistered and stained, and had to be covered by a winding of PTFE
tape to provide insulation from the test solution.
Admiralty Brass in The stored solution had turned green, with a small amount of suspended
Sea Water solids. The metal sample was partly covered with a loosely-adherent
corrosion product. Some of the product detached as the test solution was
poured over it. The oxide on the connection end of the sample had to be
removed using a file and abrasive. The paint had blistered, and the insulation
was reinstated by spiral-winding PTFE tape along the whole area of the
painted surface.
Admiralty Brass in The stored solution did not show any color change. There were no
Lake Water suspended solids. The stored sample showed some small amount of
corrosion product (green color to the surface). The paint layer showed very
slight blistering, but was intact and did not need to be repaired. The
connection end was brightened using abrasive paper.
90:10 Cu/Ni Bronze The stored solution had turned green; however, there was no solid material
in Sea Water evident. The stored sample was partly covered (at the test end) with loosely
adherent corrosion product, but this was less than in the case of Admiralty
Brass. The connection end, which had not been immersed, remained bright
and only needed treatment with fine abrasive to ensure a good connection.
The painted area had blistered slightly, where immersed; this was reinstated
by spiral-winding PTFE tape along the whole area of the painted surface.
90:10 Cu/Ni Bronze The solution did not show any observable color change. The specimen had a
in Lake Water dull brown finish to the test end, but the connection end remained bright,
and only needed treatment with fine abrasive to ensure a good connection.
The paint showed very fine blistering, but no metal was exposed.
4-14
The polarization measurements provided the following results. These are compared with the
results of the original measurements.
Table 4-11
Tafel Parameters Taken from Polarization Curves from Repeat Measurements in Sea Water
Chemistry
Material/Solution Ta Tc icor Ecor

(mV/dec) (mV/dec) (A/cm2) (mV)
Carbon Steel/Sea Water (repeat) 15 17 5.6 E-6 -681
Carbon Steel/Sea Water (original) 60 110 1.6 E-5 -690
Admiralty Brass/Sea Water 80 600 5.0 E-6 -273

(repeat)
Admiralty Brass/Sea Water 30 35 2.5 E-6 -245

(original)
90:10 Cu/Ni Bronze/Sea Water 160 360 1.0 E-5 -333

(repeat)
90:10 Cu/Ni Bronze/Sea Water 60 85 1.8E-5 -250

(original)
Table 4-12
Tafel Parameters Taken from Polarization Curves from Repeat Measurements in Lake
Water Chemistry
Material/Solution Ta Tc icor Ecor

Carbon Steel/Lake Water 25 23 3.2 E-6 -622
(repeat) (110 max, 0 min) (120 max, 0 min)
Carbon Steel/Lake Water 0.5 0.6 1.3 E-6 -458

(original) ( 33 max, 0 min) (33 max, 0 min)
Admiralty Brass/Lake Water 30 28 3.2 E-7 +46

(repeat) (45 max, 20 min) (35 max, 15 min)
Admiralty Brass/Lake Water 13 25 6.3 E-7 -116

(original) (20 max, 0 min) ( 30 max, 0 min)
90:10 Cu/Ni Bronze/Lake 15 17 2.0 E-7 -97

Water (repeat) (22 max, 6 min) (26 max, 12 min)
90:10 Cu/Ni Bronze/Lake 5 8 5.0E-7 -87

Water (original) (20 max, 0 min) (17 max, 0 min)
It can be seen that again there are significant error bars associated with the results, as a
consequence of the IR drop. In future discussions, the error is expressed as a () value, taking
the larger error (in whichever direction) as the value.
4-15
4.7 Polarization Tests at Elevated Temperature.
Raw water pipework beyond the heat exchangers operates at slightly elevated temperatures (up
to 150F), and, therefore, the influence of temperature should be checked before applying results
measured at ambient room temperature to pipework, in general.
To provide materials for these tests, the metals were stored after the original polarization. The
storage conditions had been that the coated tube sections were placed inside upright plastic
containers with a screw-top closure, and the original liquid from the first polarization test was
poured in. This immersed most of the sample, but not the connection end which had been
used to make the electrical connection to the potentiostat. Approximately the top three
centimeters of the sample were not wetted, of which two centimeters were bare metal. The
samples were stored in individual bottles, in a drip-tray, at room temperature.
Two metals were selected for these measurements. One was carbon steel, which would certainly
have an oxide film, and the other one was 316L stainless steel, which would have a minimal
degree of oxidation. The period of aging was very similar for the two metals. However, the
carbon steel had been re-polarized as part of Section 4.5, and was re-measured at higher
temperature after a further 70 days of aging. The actual aging periods were as follows:
Table 4-13
Aging Period for Samples Tested at High Temperature
Material Test Solution Total Aging Period
Carbon Steel Sea water 296 days
316L Stainless Steel Sea water 297 days
To achieve higher temperatures, the polarization cell was mounted inside a hot-water bath, with
the water level almost up to the flange of the cell vessel. The bath also had thermal insulation
floating on the water surface to prevent water loss and to maintain a steady temperature in the
bath. The experimental arrangement is shown in the following photograph. The water bath was
run at a steady 50C (122F) for all these tests.
4-16
Figure 4-5
Polarization Equipment with Heated Cell Arrangement
The repeat polarizations were carried out under the same conditions as the original polarizations,
as far as was practically possible (except temperature). Before placing the polarization cell in the
hot water bath, the conductivity of each test solution was re-measured at room temperature, and
recorded. There was an apparent trend (see Table 4-9) that the conductivity was decreasing with
time.
Table 4-14
Conductivity of High Temperature Test Solutions
Material Test Solution Original Conductivity Repeat Conductivity
Carbon Steel Sea Water Not measured. Assume 57 mS/cm

75 mS/cm
316L Stainless Steel Sea Water Not measured. Assume 56 mS/cm

75 mS/cm
The physical condition of each of the aged samples was recorded. The descriptions are presented
in Table 4-15.
4-17
Table 4-15
Description of Samples Before High Temperature Tests
Material & Description

Test Solution
Carbon Steel in Sea The stored solution was deep brown and opaque due to extensive corrosion
Water during the storage period. Since the repeat measurement, the metal sample
had again developed significant corrosion product growth on both ends of the
specimen. The corrosion product in the connection end had to be removed
with a file and the surface brightened with abrasive, to provide a good
electrical connection to the potentiostat. The remaining paint had also
blistered and no longer served as a good insulator. The insulation was
reinstated by spiral-winding PTFE tape along the whole area of the painted
surface.
316L Stainless Steel The stored solution remained clear and colorless, with only a very small
in Sea Water amount of corrosion product. The metal sample remained bright and in good
condition. The paint had not blistered or degraded.
The polarization measurements provided the following results. These are compared with the
results of the original measurements.
Table 4-16
Tafel Parameters Taken from Polarization Curves from Repeat Measurements at Elevated
Temperatures, in Sea Water Chemistry
Material /Solution Ta Tc icor Ecor

Carbon Steel/Sea Water 14 27 3.2 E-6 -731

(50C Measurements)
Carbon Steel/Sea Water (original) 60 110 1.6 E-5 -690
316L Stainless Steel/Sea Water 90 280 1.3 E-7 0

(50C Measurements)
316L Stainless Steel/Sea Water 130 260 6.3 E-7 +10

(original)
4.8 Summary of the Results of Polarization Tests
The results of all the above tests are summarized in Table 4-17, material-by-material. In addition
to the parameters evaluated above, the table includes the symmetry coefficient terms a and c;
these are equivalent to Ta and Tc (the anodic and cathodic Tafel slopes), but divided by 2.303 so
they are expressed as base e, which is the format in which they will be used in the model
calculations in Section 6. Also, Ecor (the voltage at which the Tafel minimum occurs) is more
correctly denoted as the corrosion potential.
4-18
Table 4-17
Summary of Polarization Measurement Results
Material Water Special Ta Tc a c icor Ecor

Chemistry Conditions (mV/decade) (mV/decade) (mV) (mV) (A/cm2) (mV)
Carbon Steel Sea Water None 60 110 26 48 1.6 E-5 -690

Carbon Steel Brackish None 19 28 8 12 1.0 E-5 -628
Water
Carbon Steel Lake Water None 0.5 (32) 0.6 (32) 0.2 0.2 1.3 E-6 -458
Carbon Steel Sea Water Aged 226 15 17 7 7 5.6 E-6 -681

days
Carbon Steel Sea Water Aged 296 14 27 6 12 3.2 E-6 -731
days, 50 C
Carbon Steel Lake Aged 85 days 25 (85) 23 (95) 11 10 3.2 E-6 -622
Water
AL6XN Sea Water None 280 730 122 317 6.3 E-7 +210
Mo-Alloy
AL6XN Brackish None 180 370 78 161 2.3 E-7 +730

Mo-Alloy Water
AL6XN Lake Water None 35 (6) 55 (23) 15 24 4.0 E-8 +275

Mo-Alloy
Titanium Sea Water None 410 680 178 295 1.6E-7 +650
Titanium Brackish None 110 160 48 69 3.2 E-7 +440
Water
Titanium Lake Water None 400 (100) 400 (100) 174 174 6.3 E-8 +5
4-19
Table 4-17 (continued)


316L Sea Water None 130 260 56 113 6.3 E-7 +10
Stainless
Steel
316L Brackish None 35 200 15 50 2.5 E-7 +150

Stainless Water
Steel
316L Lake Water None 35 (9) 35 (6) 15 15 1.0 E-7 +325
Stainless
Steel
316L Sea Water Aged 297 90 280 39 122 1.3 E-7 0

Stainless days, 50 C
Steel
304L Sea Water None 65 220 28 96 1.6 E-7 +90

Stainless
Steel
304L Brackish None 40 160 17 69 1.3 E-7 +160

Stainless Water
Steel
304L Lake Water None 20 ( 14) 15 ( 11) 9 7 2.5 E-7 +443
Stainless
Steel
4-20


Copper Sea Water None 50 110 22 48 2.0 E-5 -220

Copper Brackish None 45 80 20 35 3.2 E-6 -190
Water
Copper Lake Water None 25 ( 18) 30 ( 13) 11 13 5.0 E-7 -125
Admiralty Sea Water None 30 35 13 15 2.5 E-6 -245

Brass
Admiralty Brackish None 12 25 5 11 2.0 E-6 -182

Brass Water
Admiralty Lake Water None 13 ( 13) 25 ( 25) 6 11 6.3 E-7 -116

Brass
Admiralty Sea Water Aged 227 80 600 35 260 5.0 E-6 -273
Brass days
Admiralty Lake Aged 80 days 30 (15) 28 (13) 13 12 3.2 E-7 +46

Brass Water
4-21

Material Water Special Ta TC A C icor Ecor

Chemistry Conditions (mV/decade) (mV/decade) (mV) (mV) (A / cm sq) (mV)
90:10 Cu/Ni Sea Water None 60 85 26 37 1.8 E-5 -250

Bronze
90:10 Cu/Ni Brackish None 14 83 6 36 3.2 E-6 -145

Bronze Water
90:10 Cu/Ni Lake Water None 5 (15) 8 (9) 2 3 5.0 E-7 -87
Bronze
90:10 Cu/Ni Sea Water Aged 144 160 360 69 156 1.0 E-5 -333
Bronze days
90:10 Cu/Ni Lake Aged 86 days 15 (9) 17 (9) 7 7 2.0 E-7 -97
Bronze Water
70:30 Cu/Ni Sea Water None 60 70 26 30 1.6 E-5 -250

Bronze
70:30 Cu/Ni Brackish None 25 55 11 24 1.3 E-6 -155

Bronze Water
70:30 Cu/Ni Lake Water None 11 (6) 15 (7) 5 7 1.6 E-7 -107
Bronze
4-22
4.9 Discussion of Polarization Results
The polarization studies measure the corrosion potential of the metal relative to a standard
electrode under well defined solution conditions. From the results presented here for sea water
(high conductivity) conditions, the corrosion potentials are ranked as follows:
Carbon Steel < 90:10 and 70:30 Cu/Ni < Admiralty Brass < Cu < 316L SS < 304L SS
< AL6XN < Titanium
This galvanic series defines which metals are anodic and which metals are cathodic when present
in a galvanic couple. Thus carbon steel is anodic with respect to all the other metals, and if it is
part of a galvanic couple with any of the other metals, it will corrode preferentially. In brackish
water (intermediate conductivity), the results presented here indicate the following order to the
galvanic series:
Carbon Steel < Cu < Admiralty Brass < 70:30 Cu/Ni < 90:10 Cu/Ni < 316L SS
< 304L SS < Titanium < AL6XN
For lake water (low conductivity) the measured galvanic series from this work is:
Carbon Steel < Cu < Admiralty Brass < 70:30 Cu/Ni < 90:10 Cu/Ni < Titanium
< AL6XN< 316L SS < 304L SS
These galvanic series show that anodic/cathodic behavior of a galvanic couple will depend on the
conditions determining the corrosion potential. For example, under sea water conditions,
titanium is the metal with the highest potential, and is therefore cathodic with respect to all the
other metals studied. However, under brackish water conditions, titanium is anodic with respect
to AL6XN. In addition, the position of a metal in the galvanic series may change as the metals
corrode. Thus, under lake water conditions for fresh specimens, Admiralty brass is anodic with
respect to 90:10 Cu/Ni. However, for aged specimens under lake water conditions, the results
obtained here indicate the reverse is true. Care should be used in interpreting these results
though, because, as already mentioned, measurements at low conductivity may have significant
errors.
The effect of aging on icor and the corrosion potentials of the metal samples was not large. The
growth of the oxide film did not seem to affect these terms significantly. What it did affect
significantly were the symmetry terms a and c (Ta and Tc), which in some cases changed by an
order of magnitude.
The behavior of icor and the corrosion potential with temperature is complicated. This is because
these terms are a function of the exchange current density terms for the individual redox
processes taking place at the metal surface, the equilibrium potentials associated with these redox
processes, and the associated symmetry factors. All of these are functions of temperature. From
the work presented here for carbon steel, both Io and the corrosion potential decreased upon
o o
increasing the temperature from 25 C to 50 C and the symmetry factors changing significantly.
Overall, the effect of increasing temperature for carbon steel is an increase in its anodic corrosion
4-23
rate; for example, at -680 mV, the predicted corrosion current is ~10-5 A/cm2 at 25oC, while at
50oC, it would be three orders of magnitude larger at 1.6x10-2 A/cm2. For 316L, the effect of
temperature on the overall corrosion rate is much smaller; for example, at 15mV, the predicted
corrosion currents would be 8.6x10-8 and 7.6x10-8 A/cm2 at 25 and 50oC, respectively. Such a
small difference is within the bounds of the experimental errors associated with the polarization
parameters for this metal. The effect of temperature and further assessment of the polarization
terms is discussed in Section 6, which analyzes the results from the flow loop studies.
4-24
5
FLOW LOOP EXPERIMENTAL RESULTS
Commissioning of the loop was carried out before any tests were performed. The flow path was
tested for leak tightness, and for correct operation of all instruments attached to the loop. The
data logger was connected to the instruments and digital values recorded for all parameters. Data
sampling was on a 10-second frequency for commissioning, and 10-minute frequency during
measurement runs. The PC was attached to the data logger and exported data was collected in
spreadsheet format, as a way of proving the correct import/export of the data streams. In
addition to the automated output, a manual record of readings was taken on a clip-board each
working day (as far as was reasonably possible).
The tube samples used in these tests had slightly different diameters and wall thicknesses for the
various metals. The dimensions of the samples are summarized in Table 5-1.
Table 5-1
Sample Dimensions
Sample Internal External Length Wall Wetted

Diameter Diameter (mm) Thickness Surface Area
(mm) (mm) (mm) (cm2)
Carbon Steel 10.5 15.0 150 2.25 49.5

Titanium 10.5 12.5 150 1.0 49.5
Admiralty Brass 10.0 13.0 150 1.5 47.1

316L Stainless Steel 12.0 15.0 150 1.5 56.6
90:10 Cu/Ni Bronze 10.5 12.5 150 1.0 49.5

AL6XN Molybdenum 8.8 12.8 150 2.0 41.5
Steel
The wetted surface area relates to the inside surface of each sample.
In each of the tests, the flow rate through the tube samples was measured as a bulk flow rate
(liters per minute); however, for interpretation of the results, this needs to be compared as a
linear velocity, since the different diameters of the tubes affect the linear velocity. These
relationships are detailed in Figure 5-1.
5-1
Flow Loop Experimental Results
Linear Flow Velocity Depending on Bulk Flow Rate and Tube Internal Diameter
1.20
1.00
Linear FLow Velocity (meters / sec)
0.80
ID 8.8 mm
ID 10 mm
0.60
ID 10.5 mm
ID 12 mm
0.40
0.20
0.00
1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8
Bulk Flow Rate (liters / minute)
Figure 5-1
Linear Flow Velocity Depending on Tube Internal Diameter and Bulk Flow Rate
5-2
5.1 Loop Test #1
The two metal couples studied in this test were:
(A) Carbon Steel/Admiralty Brass, and

(B) Carbon Steel/Titanium.
These were connected in the flowing loop as shown in Figure 3-3. After establishing a steady
flow, the open-circuit potential was measured using high impedance electrometers. The steady
state potentials measured were -1.29 V (couple A) and +0.88 V (couple B), at 32C, pH 7, 73
mS/cm, and at a flow rate of about 3 liters/ minute.
With a flow rate of about 3 liters/minute, the linear flow velocity was, therefore, around 0.58
meters per second (carbon steel and titanium) and 0.64 meters per second for Admiralty brass.
The measured results from Loop Test #1 are presented in Figure 5-2. This shows the time-
dependent results of all parameters. The time axis is with reference to the starting point of
current flow: the initial condition corresponded to the time when the open-circuit potential was
first measured, and when it had stabilized, the system was switched to current measurement
(time = 0), and the galvanic currents were monitored.
The two parallel flow channels are designated A and B: this identification was common to all
flow loop experiments, and has no significance apart from identifying each signal fed to the data
logger.
The measured current values stabilized after about a week to give results of 0.55 mA (couple A)
and 0.33 mA (couple B). It was immediately noticeable that a ferruginous corrosion product was
generated. The color of the solution turned into a deep brown. The corrosion product appeared
to be a colloidal dispersion, or its agglomerate. All pipework sections and instrument housings
were coated with a fine deposit of this corrosion product. The automated flow meters (which
rely on a photo-optical detector) failed after a period of several days, during which the detector
windows became obscured with corrosion product. However, the manually observed flow
meters remained operational: the clip-board readings indicated no change or drift to the actual
flow rates.
Other parameters remained unaltered apart from temperature: the room air-conditioning control
was malfunctioning and stabilized at about 16C. It was considered that the actual temperature
was unimportant provided it was accurately known and stable. The temperature profile is shown
in Figure 4-2, showing the various peaks and variations during the settling process (thought to be
mainly linked to the erratic temperature control), followed by a period of relative stability and
steady measurements between 450 and 700 hours. After 700 hours, the recirculation pump
began to experience problems; the flow rate was difficult to control, and a day later, the pump
ceased to function. The test was aborted at that point, since steady-state data had already been
obtained.
The digital values extracted from the test are summarized in Table 5-2, in Section 5.7.
5-3
On completion of the test, the pipework was completely dismantled and cleaned, due to the
adherent fine corrosion product. This also coated all the metal tube samples, such that further
surface examination would have been meaningless without cleaning the surface. (And if carried
out, that process would probably have removed any underlying oxide that would have been the
intended subject of any further surface study). Therefore, all samples were retained without
further examination.
5-4
Loop 1 Measurements
Channel A = Carbon Steel / Admiralty Brass, Channel B = Carbon Steel / Titanium
100 2.5
90 2
80 1.5
pH, temperature, conductivity, flow
70 1
pH
Conductivity (milliS/cm)
Volts, milli-Amps
60 0.5 Temp C
Flow A (l/min)
50 0 Flow B (l/min)
milli-Amps A
40 -0.5 milli-Amps B
Volts A
Volts B
30 -1
20 -1.5
10 -2
0 -2.5
-200 0 200 400 600 800 1000
Elapsed Time (hours)
Figure 5-2
Galvanic Corrosion Loop Test #1 Results
5-5
5.2 Loop Test #2
(A) Carbon Steel/90:10 Cu/Ni Bronze, and

(B) Carbon Steel/316L Stainless Steel.
state potentials measured were 0.65 V (couple A) and 0.96 V (couple B), at 27C, pH 7, 76
mS/cm, and at a flow rate of about 3 liters/minute. The pump that had caused problems with the
first loop was stood down: the approach had been to obtain two pumps, one for duty and one for
standby, intending that maintenance could be carried out, if necessary, when another pump was
in use.
meters per second (carbon steel and Cu/Ni bronze) and 0.44 meters per second for stainless steel.
These relationships are again detailed in Figure 5-1.
However, this experiment encountered difficulties. After about two days, the recirculation pump
started to admit air; it was presumed that the impeller housing had an inward leak of some kind.
The ingress was severe enough to cause all instruments to measure values clearly out of normal
range. The pump was changed (re-using the pump which had been used for the first test). The
pump change took only a few minutes, and the data logging was not interrupted.
The loop ran correctly for one more day; then, the pump failed completely. Water flow stopped,
and measurements of flow rate and chemistry parameters all took step-change values. This
pump failure was accompanied by a loss of liquid from the loop (about 3 liters). The pump was
removed from the loop.
The pump that had previously been admitting air was serviced, and additional O-rings were fitted
to attempt to prevent air ingress or liquid egress. This was done in less than one day, and the
loop was re-started as quickly as possible. The liquid lost was replaced by fresh solution. The
air ingress appeared to have been cured, and the measured values stabilized almost immediately,
to give results of 0.67 mA (couple A) and 0.57 mA (couple B).
Other parameters remained at their steady values of about 76 mS/cm conductivity, pH 7, and
27C temperature. The room air-conditioning ceased to be an issue.
However, after two more days of operations, the water pump failed completely, and left the loop
without recirculating water. At this point, the run was aborted. Altogether, the loop had been in
operation for almost 400 hours. During this time, the ferruginous corrosion product of the type
observed in Loop Test #1 had begun to form again, and all surfaces were affected by a fine
deposit of orangebrown material.
5-6
The failed pumps were returned to the manufacturer, serviced and repaired, and reinstated in the
loop. The experiment was re-started. The measured results from Loop Test #2 are presented in
Figure 5-3. This shows the time-dependent results of all parameters. The time axis is with
reference to the starting point of current flow: the initial condition corresponded to the time when
the open-circuit potential was first measured, and when it had stabilized, the system was
switched to current measurement (time = 0), and the galvanic currents were monitored.
It was found that the measurements equilibrated relatively quickly (within twenty hours). Again,
the automated flow meters proved problematic due to the build up of corrosion product on the
photo-optic cell window. The test was continued for over 100 hours of stable measurements, and
then terminated.
The digital values extracted from the test are summarized in Table 5-2, in Section 5-7. The
voltage measurements presented in Table 5-1 are those obtained at the outset of the test (i.e.,
when the materials were fresh) for consistency with the other loop tests.
On completion of the test, the pipework was completely dismantled and cleaned, due to the
adherent fine corrosion product. This also coated all the metal tube samples, such that further
surface examination would have been meaningless without cleaning the surface. (And if carried
out, that process would probably have removed any underlying oxide that would have been the
intended subject of any further surface study). Therefore, all samples were retained without
further examination.
5-7
Loop 2 - repeat measurements

Channel A = carbon steel / 90:10 Cu:Ni bronze, Channel B = carbon steel / 316L stainless steel
100 2
90
80 1.5
ph, temperature, conductivity, flow
70
pH
milli-Siemens/cm
Volts, milli-Amps
60 1 temp
Flow A
50 Flow B
milli-amps A
40 0.5 milli-Amps B
Volts A
Volts B
30
20 0
10
0 -0.5
-40 -20 0 20 40 60 80 100 120 140 160
Elapsed time (hours)
Figure 5-3
5-8
5.3 Loop Test #3
(A) Carbon Steel/AL6XN Molybdenum Steel, and

(B) 316L Stainless Steel/AL6XN Molybdenum Steel.
These were connected in to the flowing loop as shown in Figure 3-3. After establishing a steady
state potentials measured were 0.42 V (couple A) and 0.014 V (couple B), at 31C, pH 6.4, 77
mS/cm, and at a flow rate of about 3 liters/minute.
meters per second (carbon steel), 0.44 meters per second for stainless steel, and 0.85 meters per
second for AL6XN. These relationships are again detailed in Figure 5-1.
The main parameters remained at their steady values of about 77 mS/cm conductivity, pH 6.4,
and 31C temperature.
(time = 0), and the galvanic currents were monitored. For this loop, the voltage equilibration
measurements were recorded with a finer time resolution, and were not part of the same data set
as presented in Figure 5-4.
It was found that the current measurement for the carbon steel/AL6XN couple equilibrated
within approximately two hundred hours. However, the current flow in the 316L stainless
steel/AL6XN couple was very low in magnitude (to make it discernable, the values are
multiplied by a factor of 50 in Figure 5-4), and took longer to equilibrate (approximately 400
hours). It was also noticeable that the current measurements were tracking the daily variations in
temperature.
Again, the automated flow meters proved problematic due to the build up of corrosion product
on the photo-optic cell window. The automated data were supplemented by manual readings
from the visible flowmeters. The test was continued for over 500 hours, when the centrifugal
pump again developed a fault and gave unstable readings. Since the loop had by that time
provided at least 100 hours of relatively stable measurements, the experiment was terminated.
The digital values extracted from the test are summarized in Table 5-2, in Section 5.7. The
voltage measurements presented in Table 5-2 are those obtained at the outset of the test (i.e.
when the materials were fresh) for consistency with the other loop tests.
On completion of the test, the pipework was completely dismantled. All instrument housings
were cleaned of the adherent fine corrosion product. All straight pipe sections were replaced.
5-9
The corrosion product also coated all the metal tube samples, such that further surface
examination would have been meaningless without cleaning the surface.
Also, the centrifugal pump was replaced with a different design/supply of unit, for use in
subsequent tests.
5-10
Loop 3 Measurements
Channel A = Carbon Steel / AL6XN, Channel B = 316L stainless steel / AL6XN
100 1.0
90 0.9
80 0.8
pH, temperatuer, conductivity, flow
70 0.7
pH
60 0.6 milli-Siemen/cm
milli-Amps
Temp
50 0.5 Flow A
Flow B
40 0.4 milli-Amps A
Current B x50
30 0.3
20 0.2
10 0.1
0 0.0
0 100 200 300 400 500 600
Elapsed time (hours)
Figure 5-4
5-11
5.4 Loop Test #4
(A) Carbon Steel/Admiralty Brass, and

(B) Carbon Steel/Titanium.
flow, the open-circuit potential (using high impedance electrometers) was measured. The steady
mS/cm, and at a flow rate of about 2 liters/minute in each channel. (It should be noted that the
replacement pump design had a lower total flow rate than the previous type).
meters per second (carbon steel and titanium) and 0.5 meters per second for Admiralty brass.
These relationships are again detailed in Figure 5-1.
The main parameters remained at their steady values of about pH 7.8 and 30C. The
conductivity increased slightly during the test, from 1 to 1.7 mS/cm, which may be attributed to
the release of ionic corrosion products.
(time = 0), and the galvanic currents were monitored. For this loop, the voltage equilibration
It was found that the current measurement for both couples equilibrated within approximately
one hundred hours. It was again noticeable that the current measurements were tracking the
daily variations in temperature. The absolute magnitude of the measured current was
significantly lower than in the previous tests at higher conductivity. Nevertheless, there was still
a significant release of ferruginous corrosion product within the loop.
from the visible flowmeters. The test was continued for over 500 hours. Since the loop had by
that time provided at least 400 hours of relatively stable measurements, the experiment was
terminated. The new pump had performed well, with no difficulties or problems.
when the materials were fresh).
5-12
On completion of the test, the pipework was completely dismantled. All instrument housings
were cleaned of the adherent fine corrosion product. All straight pipe sections were cleaned.
The corrosion product also coated all the metal tube samples, such that further surface
examination would have been meaningless without cleaning the surface.
5-13
Loop 4 Measurements - Low Conductivity

Channel A = Carbon Steel / Admiralty Brass, Channel B = Carbon Steel / Titanium
50
45
40
pH, Conductivity, Temp, Flow, Current
35
pH
30 MilliS/cm
T C
25 Flow A l/min
Flow B l/min
20 microAmps A
microAmps B
15
10
0
-100 0 100 200 300 400 500 600 700
Figure 5-5
5-14
5.5 Loop Test #5
(A) Carbon Steel/90:10 Cu/Ni Bronze, and

(B) Carbon Steel/316L Stainless Steel.
mS/cm, and at a flow rate of about 2 liters/minute in each channel.
meters per second (carbon steel and 90:10 Cu/Ni bronze) and 0.3 meters per second for 316L
stainless steel. These relationships are again detailed in Figure 5-1.
The main parameters remained at their steady values of about pH 7.2, and 28C. The
conductivity increased slightly during the test, from 1 to 1.6 mS/cm, which may be attributed to
the release of ionic corrosion products.
current flow: the initial condition corresponded to when the open-circuit potential was first
measured, and when it had stabilized, the system was switched to current measurement (time =
0), and the galvanic currents were monitored. For this loop, the voltage equilibration
It was found that the current measurement for both couples equilibrated within approximately
one hundred hours. It was again noted that the current measurements were (to some extent)
tracking the daily variations in temperature. The absolute magnitude of the measured current
was again significantly lower than in the previous tests at higher conductivity with the same
metals. Nevertheless, there was still a significant release of ferruginous corrosion product within
the loop.
There was a period of spurious noise in the current signal from Couple A, at about 220 hours in
to the test. This occurred overnight (less than a 10-hour period), and had returned to its previous
reading before any operator observation or intervention was possible. It is assumed that this is
due to external effects and not a feature of the test.
from the visible flowmeters. The test was continued for over 350 hours. Since the loop had by
that time provided at least 250 hours of relatively stable measurements, the experiment was
terminated. The new pump had performed well, with no difficulties, or problems.
5-15
when the materials were fresh).
On completion of the test, the pipework was again completely dismantled. All instrument
housings were cleaned of the adherent fine corrosion product. All straight pipe sections were
cleaned. The corrosion product had again coated all the metal tube samples, such that further
surface examination would have been impossible to interpret.
5-16

Channel A = Carbon Steel / 90:10 Cu:Ni bronze, Channel B = Carbon Steel / 316L Stainless Steel
40
35
pH, temp, Conductivity, Flow, micro-Amps
30
25 pH
MilliSm/cm
Temp
20 A litre/min
B litre/min
micro-Amps A
15 micro-Amps B
10
0
-50 0 50 100 150 200 250 300 350 400
Figure 5-6
5-17
5.6 Loop Test #6
(A) Carbon Steel/AL6XN Molybdenum, and

(B) AL6XN Molybdenum/316L Stainless Steel.
mS/cm, and at a flow rate of about 2 liters/minute in each channel.
With a flow rate of about 2 liters per minute, the linear flow velocity was, therefore, around 0.4
meters per second (carbon steel), 0.5 meters per second (AL6XN), and 0.3 meters per second for
316L stainless steel. These relationships are again detailed in Figure 5-1.
The main parameters remained at their steady values of about pH 7.0, and about 28C. The
conductivity increased slightly during the test, from 1 to 1.7 S/cm, which may be attributed to the
release of ionic corrosion products (from the carbon steel).
current flow: the initial condition corresponded to when the open-circuit potential was first
measured, and when it had stabilized, the system was switched to current measurement (time =
0), and the galvanic currents were monitored. For this loop, the voltage equilibration
It was found that the current measurement for the carbons steel/AL6XN couple equilibrated after
approximately 350 hours, and the AL6XN/316L couple after approximately 400 hours. The
absolute magnitude of the measured current was again significantly lower than in the previous
tests at higher conductivity for the same metals (i.e., carbon steel /AL6XN): the reduction was
approximately a factor of 20. Nevertheless, there was still a significant release of ferruginous
corrosion product within the loop.
The magnitude of the stabilized current for the AL6XN/316L was also lower than the previous
test at higher conductivity. Also, the recorded current shown in Figure 5-7 was negative
(whereas in Figure 5-4. it was positive). This is a function of which terminal of the ZRA
(positive or negative) was connected to which metal, and since the meter operates identically
whichever direction the current flows, this is of no significance.
from the visible flowmeters. The test was continued for 600 hours. Since the loop had by that
time provided at least 200 hours of relatively stable measurements, the experiment was
terminated. The new pump had again performed well, with no difficulties or problems.
5-18

Channel A = Carbon Steel / AL6XN, Channel B = AL6XN / 316L Stainless Steel
40 0.01
35 0.00
pH, Temp, Cond, Flow, micro-Amps (A)
30 -0.01
25 -0.02 pH
micro-Amps (B)
milliSm/cm
Temp
20 -0.03 Flow A
Flow B
micro-Amps A
15 -0.04 micro-Amps B
10 -0.05
5 -0.06
0 -0.07
0 100 200 300 400 500 600 700
Figure 5-7
5-19
5.7 Summary of Flow Loop Test Results
The results of the six flow loop tests are summarized in Tables 5-2 to 5-5.
In these tables, the following should be noted:

The potential measured as Open Circuit is between the two metals corroding as a galvanic
couple. This was measured by connecting an electrometer across the two metals, which are
insulated by a PTFE spacer, when flow and chemistry conditions had been established. The
metal tube clamping arrangement is shown in Figure 5-8, and electrical connections to the
tubes were made via mechanical circular clips external to the test sections.
The current density is calculated as the measured current divided by the available surface
area of the metal considered. As the various metal tubes had slightly different diameters, and
thus surface areas, the current density depends on which metal is being considered. In Table
5-2, these are expressed as cathodic or anodic current densities, depending on which metal
surface is presumed to control the magnitude of the current.
5-20
Calomel Electrode
Connection
Couplings
PTFE CONNECTION SLEEVE

Capillary tube Zinc - Movable
free PTFE
Fixed elastomer block
PTFE Metal Metal O ring
block Tube A Tube B
Tube Lever-
Coupling operated
PPE Guide rail Guide rail piston
clamp
Base
Plate
PTFE support pads
Tubing
Metal Tube A Metal Tube B connection
fittings
Fixed Block Lock nuts on guide rails Metal tubes tyupically 150 mm long, 15 to 20 mm OD.
Figure 5-8
Galvanic Test Section Clamp Jig
5-21
Table 5-2
Input Parameters and Results for High Conductivity Loop Experiments
Loop Test #1
Couple Carbon Steel/Admiralty Brass Carbon Steel/Titanium
Variable
Solution 0.6M NaCl 0.6M NaCl
Open circuit potential 1.29 V 0.88 V
Current density (cathodic) 12.0 A/cm 2
6.4 A/cm2
(anodic) 10.9 A/cm2 6.7 A/cm2
Temperature 16C 16C
pH 7.0 7.0
Conductivity 73 mS/cm 73 mS/cm
Flow velocity 0.67 meters/second (anode) 0.67 meters/second (anode)
0.74 meters/second (cathode) 0.67 meters/second (cathode)
Loop Test #2
Couple Carbon Steel/ 90:10 Cu/Ni Carbon Steel/316L Stainless Steel
Variable Bronze
13.1 A/cm2
Temperature 27C 27C
pH 7.0 7.0
Flow velocity 0.58 meters/second (anodic) 0.58 meters/second (anodic)
0.58 meters/second (cathodic) 0.45 meters/second (cathodic)
Loop Test #3
Couple Carbon Steel/AL6XN 316L Stainless/AL6XN
Variable
0.078 A/cm2
(anodic) 2.83 A/cm2 0.106 A/cm2
Temperature 31C 31C
pH 6.42 6.42
5-22
Table 5-3
Input Parameters and Results for Low Conductivity Loop Experiments
Loop Test #4
Variable
0.39 A/cm2
Temperature 30C 30C
pH 7.8 7.8
Conductivity 1.66 mS/cm 1.66 mS/cm
Flow velocity 0.40 meters/second (anode) 0.37 meters/second (anode)
0.49 meters/second (cathode) 0.34 meters/second (cathode)
Loop Test #5
Couple Carbon Steel/90:10 Cu/Ni Bronze Carbon Steel/316L Stainless Steel
Variable
0.20 A/cm2
Temperature 28C 28C
pH 7.2 7.2
Flow velocity 0.39 meters /second (anodic) 0.37 meters/second (anodic)
Loop Test #6
Couple Carbon Steel/AL6XN 316L Stainless/AL6XN
Variable
0.11 nanoA/cm2
(anodic) 0.11 A/cm2 0.15 nanoA/cm2
Temperature 28C 28C
pH 6.95 6.95
5-23
The loop is equipped with Calomel electrodes interposed between each pair of metal sections,
and potentials between the tube sections and Calomel can also be measured. These readings
were in each case taken before the start of the flow loop current measurements. The
measurements are shown in Table 5-4.
Table 5-4
Free Corrosion Potentials for Metals in the Loop
Loop Test #1
Not Measured
Loop Test #2
Couple Carbon Steel/90:10 Cu/Ni Carbon Steel/316L Stainless

Variable Bronze Steel
Potential Cathode metal to -0.240 V -0.135 V

Calomel
Potential C/S (anode) to -0.595 V

Calomel
Loop Test #3
Couple Carbon Steel/AL6XN AL6XN/316L Stainless Steel

Variable
Potential Cathode metal (-) to 0.189 V 0.104 V

Calomel (+)
Loop Test #4

Variable
Potential Cathode metal (-) to -0.101 V 0.116 V

Calomel (+)
Potential C/S (anode) to -0.633 V
Calomel
Loop Test #5
Couple Carbon Steel/90:10 Cu/Ni Carbon Steel/316L Stainless

Variable Bronze Steel
Potential Cathode metal (-) to -0.740 V -0.085 V

Calomel (+)
Loop Test #6
Couple Carbon Steel/AL6XN AL6XN/316L Stainless

Variable
Potential Cathode metal (-) to -1.20 V 0.041 V

Calomel (+)
5-24
Table 5-5 is a summary of the current and potential measurements obtained from loop testing.
Table 5-5
Summary of Results for Loop Tests
Loop Test # Couple Conductivity Current Potential

(mS/cm) Density (V)
(A/cm2)
1 CS/AB 73 11.5 1.29

1 CS/Ti 73 6.5 .88
2 CS/CN90:10 76 12.0 0.66
2 CS/316L 76 14 0.96
3 CS/AL6XN 77 3.0 0.42
3 316L/AL6XN 77 0.09 0.014
4 CS/AB 1.66 0.65 0.53
4 CS/Ti 1.66 0.4 0.52
5 CS/CN90:10 1.64 0.61 0.50
5 CS/316L 1.64 0.21 0.55

6 CS/AL6XN 1.65 0.12 0.36
6 316L/AL6XN 1.65 1.3x10-4 0.001
Carbon Steel CS, Admiralty Brass AB, Titanium Ti, Cu/Ni 90:10 Bronze CN90:10, 316L Stainless Steel
316L.
5-25
6
INTERPRETATION OF RESULTS
The polarization test on carbon steel, as a demonstration run, indicated that the rest potential of
carbon steel in 0.6M NaCl solution at pH 7 was about -850 mV (versus saturated Calomel).
From the Tafel plot, the evaluated Tafel parameters were c -0.14 V/decade, and a +0.095
V/decade. This compares with published work by Turnbull [2] where de-aerated conditions were
used, in a similar saline solution, and where the corresponding parameters were c = -0.12
V/decade, and a = +0.060 V/decade. Turnbull noted that their work was in slightly acidic
conditions, and the values of the parameters would be expected to slightly increase with pH. It
can be concluded, therefore, that the results obtained here are in reasonable agreement with
Reference 2.
One of the reasons why sea water chemistry was chosen as an experimental condition was to
allow some comparison with other data. It should be noted, however, that when comparing these
results with other work, the experimental conditions may play a significant role in controlling the
polarization results. For example, the use of flowing water, or the use of samples where a
corrosion product has had time to build up, may be important. The similarity in experimental
arrangement between this work and reference [2] makes a cross-comparison meaningful in this
case.
It can be shown that for a metal undergoing corrosion, the current density is related to the
potential of the metal by
E E cor E E
i = icor exp( ) exp( cor )
a c Equation 6-1
The derivation of this equation makes a number of assumptions, not least the assumption that
currents are not limited by mass transfer. The first term in the above equation is the anodic
current associated with dissolution of the metal and the second term is the cathodic current,
+
normally associated either with H or O2 reduction on the metal surface. The corrosion current
icor is then simply the current associated with the metal when anodic and cathodic processes are
equal and the potential is equal to the corrosion potential Ecor. The polarization studies that have
been carried out here plot log(i) versus E and tangents drawn on this curve in the region of i = 0
represent Tafel plots for the anodic and cathodic parts of equation 6.1. These lines cross at
log(icor) and Ecor and have slopes determined by a and c. Table 4-17 tabulates all the relevant
parameters, (io, a, c, Ecor) determined from the polarization curves measured in this study.
In the loop studies, the metal with the lowest value of Ecor will act as the anode while the other
metal will provide the surface on which cathodic reduction of H+ or O2 will take place. An
approximate estimate of the potential difference between the couples and the possible current
6-1
Interpretation of Results
that might be expected can be obtained by equating the anodic part of equation 6.1 for the
material undergoing anodic dissolution with the cathodic part of the cathodic metal. This
balance of the anodic and cathodic currents associated with the different metals ignores the
spatial separation of the materials and assumes zero resistance in the solution. It also assumes the
oxidation kinetics of the two metals do not intersect in the range of interfacial potentials of
interest; it assumes the same for the reduction kinetics, and also the areas of the anode and the
cathode are the same.
The approach therefore gives a very approximate value for the corrosion current and potential.
By equating the two terms the following equation can be written for the potential difference
between the two metals, Egal
a1 c2 icor
2
c1 E cor
2
+ a2 E cor
1
E gal = ln +
a1 + c2 icor
1
a1 + c2 Equation 6-2
where the superscripts 1 and 2 refer to the anodic and cathodic metals. An estimate of the
galvanic corrosion current is then given by
E gal E cor
1 2
E cor E gal
i gal = icor
1
exp( ) = icor
2
exp( )
a1 c2 Equation 6-3
Some of the calculated loop potentials and current densities based on the polarization constants
in Table 4-17 are given below in Table 6-1 along with the experimental values.
Table 6-1
Estimate of Galvanic Potentials and Currents for Loop Couples Using Simple Approach
Couple Conductivity Calculated Measured Calculated Measured

(mS/cm) Potential Potential Current Current
(mV) (mV) Density Density
(A/cm2) (/cm2)
CS/AB 70 - 80 425 1290 411,000 11.5
CS/Ti 70 80 691 880 15 6.9
CS/CN90:10 70 80 506 660 18,000 13.5
CS/316L 70 80 627 960 177 14
CS/AL6XN 70 80 699 420 11 2.8
AL6XN/316L 70 80 40 14 1.1 0.11
CS/AB (Both Aged) 70 80 679 960 23 11.5
CS/AB (lake water) 1-2 311 530 32,000,000 0.65
CS/316L (Both Aged) 70-80 669 960 31 14
6-2
Although the calculations leading to Table 6-1 are gross estimates of the currents and potentials
involved, a number of points can be derived from the results:
The predicted currents are order of magnitudes bigger in some cases than measured implying
mass transfer limitations on the measured currents.
The effect of aging, that is the development of a substantial oxide surface on the metal,
reduces the corrosion currents significantly.
Using the polarization constants determined in low conductivity water (lake water) predicts
an increase in corrosion current, contrary to what is observed and contrary to expectations.
The fact that a number of the predicted currents are well above those measured in the loop
probably indicates that the current is mass transfer controlled, the cathodic reduction of O2 being
the limiting factor. To calculate this limiting current the following equations have been used:
Sh = 0.023 Re 0.88 Sch0.44 Equation 6-4

Sch =
DO 2
Equation 6-5
d
Re = Equation 6-6

and
ShDO2
km =
d Equation 6-7
with the limiting current being given by
i L = k m [O2 ]F Equation 6-8
where Re, Sch and Sh are the Reynolds, Schmidt, and Sherwood numbers, is the viscosity of
water, the flow velocity, the water density, d the pipe diameter, DO2 the diffusion constant of
O2 in water, and F is the Faraday constant. The values for these terms given in Table 6.2 give a
mass transfer limiting current of approximately 15 /cm2, which, on examination of the
experimental loop results given in Table 6-1, is close to a number of the measured current
densities.
6-3
Table 6-2
Parameters Used to Estimate the Limiting Cathodic Current
Parameter Value
Density (g/cm3) 1
Viscosity (g/cm*s) 9.3x10-3
Diameter (cm) 1
2
Diffusion constant for O2 (cm /s) 2x10-5
Velocity (cm/s) 67
[O2] (moles/liter) 8.9x10-6
Since it is possible that the corrosion rate could be controlled by the mass-transfer-limited rate of
oxygen to the cathode surface, the FACSIMILE model and Fortran code that are being used to
model galvanic corrosion were modified to account for this. The cathodic current is given by the
Butler-Volmer equation with an upper limit for the cathodic current of iL defined by the
equations described above. Having implemented these equations in the model, calculations were
carried out for the loop conditions using the polarization constants given in Table 4-17. Table
6-3 below shows the calculated loop currents using the revised FACSIMILE model and the
experimentally observed currents for the various couples.
Table 6-3
Predicted and Measured Currents for Galvanic Couples Using Polarization Parameters for
Fresh Specimens
Loop Couple Conductivity Measured Current Calculated Current

Test # (mS/cm) Density Density
(A/cm2) (A/cm2)
1 CS/AB 73 11.5 14.8
1 CS/Ti 73 6.5 14.8
2 CS/CN90:10 76 12.0 14.8
2 CS/316L 76 14 14.8
3 CS/AL6XN 77 3.0 14.8
3 316L/AL6XN 77 0.09 10.8
4 CS/AB 1.66 0.65 3.2
4 CS/Ti 1.66 0.4 4.3
5 CS/CN90:10 1.64 0.61 3.7
5 CS/316L 1.64 0.21 4.9
6 CS/AL6XN 1.65 0.12 5.6
-4
6 316L/AL6XN 1.65 1.3x10 1.8
Carbon Steel CS, Admiralty Brass AB, Titanium Ti, Cu/Ni 90:10 Bronze CN90:10, 316L Stainless Steel
316L.
6-4
Table 6-3 was generated using the constants derived from the polarization experiments on fresh
metal samples. Clearly, at low conductivity, these constants overpredict the corrosion current by
a factor of 10 in some cases, and the agreement with observed data is not good. Calculations
were therefore carried out with the FACSIMILE model using the polarization constants obtained
on aged specimens. The results of these calculations are shown in Table 6-4.
Table 6-4
Aged Specimens
Loop Couple Conductivity Measured Current Calculated Current

Test # (mS/cm) Density Density
(A/cm2) (A/cm2)
1 CS/AB 73 11.5 14.8

2 CS/CN90:10 76 12.0 14.8
2 CS/316L 76 14 14.8
4 CS/AB 1.66 0.65 3.2
5 CS/CN90:10 1.64 0.61 3.4
5 CS/316L 1.64 0.21 4.0

6 316L/AL6XN 1.65 1.3x10-4 0.9
The use of polarization constants based on aged specimens improves the comparison between the
model and the measured loop corrosion currents slightly, but the comparison is still not very
good. Calculations have also been performed using the polarization constants determined in low
conductivity (lake) water. These constants also do not improve the comparison significantly and
there is also a large degree of uncertainty in the polarization constants because of the difficulties
associated with the polarization measurements at such low conductivities.
It is clear that although the polarization studies show which metals are likely to be anodic and
which metals are likely to be cathodic when part of a galvanic couple, they do not indicate
quantitatively the rate of corrosion observed in the loop studies. The agreement between the
calculated and measured loop currents is better at the high (sea water) conductivity, largely due
to the fact that the current is mass-transfer controlled. The agreement between measured and
calculated corrosion currents at low conductivity is poor. The fact that agreement is not good is
not surprising as in carrying out the loop studies, it is clear that significant amounts of corrosion
product are generated and circulated around the loop. Much of this product deposits on the pipe
walls providing a coating, in addition to the normal oxide coating, slowing the corrosion rate.
The results indicate this process seems particularly important at low conductivity. In order to see
by how much anodic and cathodic currents are reduced by the thick crud layer, calculations were
carried out using the polarization constants given in Table 4-17 for the high conductivity
conditions using fresh metal samples with the polarization constants icor reduced by factors of 10,
2 3
10 , and 10 . Both anodic and cathodic constants were reduced for the calculations. The results
of these calculations are shown in Table 6-5.
6-5
Table 6-5
Fresh Specimens in Sea Water, but Reduced by 10, 102 and 103
Loop Couple Conductivity Measured Calculated

Test # (mS/cm) Current Current
Density Density
(A/cm2) (/cm2)
icor reduced by a factor = 10

1 CS/AB 73 11.5 14.8
1 CS/Ti 73 6.5 11.1
2 CS/CN90:10 76 12.0 14.8

2 CS/316L 76 14 14.8
3 CS/AL6XN 77 3.0 14.8
3 316L/AL6XN 77 0.09 0.1
1 CS/AB 73 11.5 14.8
1 CS/Ti 73 6.5 1.5

2 CS/CN90:10 76 12.0 13.7
2 CS/316L 76 14 11
3 CS/AL6XN 77 3.0 3.0
3 316L/AL6XN 77 0.09 0.01
4 CS/AB 1.66 0.65 1
4 CS/Ti 1.66 0.4 0.1
5 CS/CN90:10 1.64 0.61 0.7

5 CS/316L 1.64 0.21 0.5
6 CS/AL6XN 1.65 0.12 0.2
6 316L/AL6XN 1.65 1.3x10-4 1.2x10-3

Carbon Steel CS, Admiralty Brass AB, Titanium Ti, Cu/Ni 90:10 Bronze
CN90:10, 316L Stainless Steel 316L.
In order to get reasonable comparisons between the model and the loop data at low conductivity
(12 mS/cm), the polarization exchange current densities need to be reduced by a factor of 103.
The high conductivity calculations give a reasonable comparison with the measured loop
2
currents by reducing the polarization exchange currents by a factor of 10 . Therefore, in
applying the model to plant conditions, these factors should be used and have been used to
generate the results in Figures 6-1 and 6-2.
6-6
Figure 6-1 shows the calculated galvanic corrosion rate along the pipe for the carbon
steel/Admiralty brass couple under sea water and lake water conditions.
Figure 6-1
Plot of Corrosion Rate Against Distance from Metal-Metal Joint for Carbon Steel (CS) and
Admiralty Brass (AB) Galvanic Couple. The Low Conductivity Corresponds to Lake Water
at 1-2 mS/cm, the Intermediate Conductivity to Brackish Water at 10 mS/cm, and the High
Conductivity Is for Sea Water at 7080 mS/cm
Figure 6-2 presents the equivalent plots for the carbon steel/AL6XN couple.
6-7
Figure 6-2
Plot of Corrosion Rate Against Distance from Metal-Metal Joint for Carbon Steel (CS) and
AL6XN Galvanic Couple. The Low Conductivity Corresponds to Lake Water at 1-2 mS/cm,
the Intermediate Conductivity to Brackish Water at 10 mS/cm, and the High Conductivity Is
for Sea Water at 7080 mS/cm
Figures 6-1 and 6-2 both show that galvanic corrosion rates are large compared to general
corrosion and the corrosion rate is largest near the metal-metal junction and falls off with
increasing distance from this location. The corrosion rate is much higher at the high
conductivity, as expected; in the case of the carbon steel/Admiralty brass couple, the corrosion
rate 15 cm away from the junction at the higher conductivity is as high as the corrosion rate at
the junction at the lower conductivity. The calculations indicate that the Admiralty brass/carbon
steel couple is corroding about a factor of ten faster than the carbon steel/AL6XN couple, which
is simply a reflection of the lower exchange current associated with AL6XN compared to
Admiralty brass. It is also interesting to note that for the carbon steel/AL6XN couple, the
corrosion rate near the metal junction for the low conductivity water is higher than for the
intermediate conductivity. The overall corrosion of the carbon steel pipe in brackish
(intermediate conductivity) water is, however, higher than for lake (low conductivity) water
because the corrosion is spread over a longer section of the pipe.
Figure 6-3 shows the effect of temperature on corrosion for a carbon steel/Admiralty brass
couple. For the calculations carried out at 25C, the polarization parameters for carbon steel
determined at this temperature in this study were used. A 25-degree increase in temperature
leads to a factor of 2 to 3 increase in the carbon steel corrosion rate.
6-8
Equation 6-3
Plot of Corrosion Rate Against Distance from Metal-Metal Joint for a Carbon Steel
(CS)/Admiralty Brass Couple. Calculations Were Carried Out for Sea Water Conditions.
6-9
7
DISCUSSION AND SUMMARY
The development of a galvanic corrosion model requires the measurement of galvanic corrosion
rates on relevant materials against which to benchmark the model. The key input parameters to
the model are the Tafel parameters for the relevant anodic and cathodic processes taking place on
these metal surfaces. In typical cooling water systems, the water is likely to be saturated with
corrosion products and contain a large amount of colloidal material. Deposition on the metal
surface is likely to change the Tafel parameters with time and this is why the rate of galvanic
corrosion often falls with time. The growth of oxide on the surface and deposition of crud may
in fact change the corrosion potential associated with the metal and is one reason why a reversal
with time of the galvanic corrosion current sometimes occurs.
Polarization experiments have been described for obtaining the Tafel parameters on relatively
clean surfaces and the results from these experiments have also been described. Polarization
work on carbon steel has been carried out and the results are reasonably consistent with similar
studies reported in reference [2]. In addition polarization measurements have been carried on the
alloys: Admiralty brass, AL6XN, titanium, 316L SS, 304L SS, copper, 90:10 and 70:30 Cu/Ni
bronzes. Measurements have been made under high conductivity conditions (7080 mS/cm)
corresponding to sea water, low conductivity conditions (1-2 mS/cm) corresponding to lake
water, and intermediate conductivity (~10 mS/cm) corresponding to brackish water.
Measurements have also been carried out on specimens that have been stored in solution (aged
specimens) for significant periods. The results of all these polarization measurements have been
reported here; however, it should be emphasized that the confidence in the results from these
experiments falls as the conductivity in solution falls, because of the increasing importance of
the solution IR drop. It should also be realized that there are several ways of treating the data
from these tests, which may also give differing results for the Tafel constants.
In addition, there are a number of general deficiencies in the approach adopted here, particularly
in understanding the cathodic portion of the polarization curve. A better approach would be to
use a rotating disk electrode to characterize the mass transfer rates in the system and to perform
experiments over a range of oxygen concentrations (zero to air saturated) and pHs. For each
material, this would have involved a large number of experiments, which would have been
impracticable in the present study.
Obtaining definite values of the Tafel constants though was not the aim of the current
experiments, but rather to obtain some approximate starting values to use in analyzing the loop
data and to order the materials in a galvanic series. The constants from any polarization study
would always need to be modified to explain the loop data because the polarization data are
obtained on relatively clean surfaces, in clean water, and over a short time duration. The loop
studies indicate clearly that the current between the galvanic couple changes dramatically from
the start of the experiment (clean conditions) to its completion (dirty conditions), which may
7-1
Discussion and Summary
take several weeks, indicating similar changes in either associated polarization constants or
available metal surface area.
Crud movement and deposition will affect galvanic corrosion rates, and it is important to
appreciate the significance of this to actual cooling water systems. In order to do this, a series of
flowing loop studies was carried out for a number of galvanic couples. These have been
described in detail here. Loop studies were performed on the couples: carbon steel/Admiralty
brass, carbon steel/titanium, carbon steel/90:10 Cu/Ni, carbon steel/316L, carbon steel/Al6XN
and 316L SS/Al6XN. Experiments were carried out in both high and low conductivity water
corresponding to sea and lake water. The corrosion current was measured for these couples for
periods of weeks to months until steady state had been achieved for a significant length of time.
In all these studies, significant amounts of colloidal material was observed floating around in the
system (dirty brown water) and significant deposits were observed on the pipe walls after the test
sections had been removed from the loop. This material floating around in the system caused a
number of problems associated with pump failures and flow meter failures, but these were
overcome.
Modeling the flowing loop data using the FACSIMILE model developed previously [1] and
using the Tafel constants from the polarization studies indicated the following:
At high conductivity (sea water), the corrosion current is close to what would be expected for
the carbon steel couples, if the process was controlled by mass transfer of O2 to the cathodic
surface.
At low conductivity (lake water), the mass transfer corrosion current is approximately an
order of magnitude higher than the measured current.
The Tafel constants derived from the polarization studies are too large to explain the
corrosion currents measured in the loop. At high conductivity, the calculated polarization
2
exchange current density needs to be reduced by a factor 10 , and at low conductivity by a
3
factor 10 to get reasonable agreement with the measured corrosion rates.
With the measured polarization constants and the weighting factors for the exchange current
density terms, it may be possible to use the model as a scoping tool. However, care must be
taken in this regard in that:
1. No loop experiments were carried out at intermediate conductivities.
2. No loop studies have been performed to look at the effect of: flow rate, pipe dimensions,
temperature, and water chemistry.
That is, the model has only been tested over a limited range of possible plant conditions.
Changing the weighting-factor parameters for the polarization constants based on plant
observations could allow the model to be tuned to particular plant conditions. However, the
well characterized experimental data obtained in this study show that more work remains to be
performed before a truly predictive model for galvanic corrosion model becomes available.
Possible future experiments have been mentioned above.
7-2
8
REFERENCES
1. A. V. Chambers, R. Haines, J. Henshaw, Development of a Galvanic Corrosion Model,

EPRI/2081/1, 2001.
2. A. Turnbull and M. K. Gardner, Corrosion Science, Vol. 22, pp. 661-672 (1982).
3. A. Turnbull, D. H. Ferriss Mathematical modeling of the electrochemistry in corrosion
fatigue cracks in steel corroding in marine environments, Corrosion Science, Vol. 27, No.
12, pp. 1323-1350, 1987.
4. A. Turnbull, Brit. Corros. J. 15, 162 (1980).
5. P. Doig and P. E. J. Flewitt. A Finite Difference Numerical Analysis of Galvanic Corrosion
for Semi-Infinite Linear Coplanar Electrodes J. Electrochem Soc, December 1979.
6. F. L. LaQue, Corrosion Testing, in ASTM Proceedings, Vol. 51, American Society for
Testing and Materials, 1951, pp. 495-582.
th
7. Metals Handbook, 9 Edition, Volume 13: Corrosion, pp. 894-900, ASM International, 1990.
8. R. Kircheim et al., The passivity of iron-chromium alloys, Corrosion Science, Vol. 29, No.
7, pp. 899-917, 1989.
9. EPRI Cooling Water Application Models (July 26, 1999).
8-1
A
TAFEL PLOTS FROM THE POLARIZATION STUDIES
A.1 Polarization Studies in Sea Water Chemistry
This section presents the Tafel plots obtained from the polarization studies in sea water
simulation chemistry. These include the original set of measurements, together with the
additional materials, repeat measurements, and elevated temperature measurements.
In all cases, the conditions refer to aerated, stirred, and sparged. The potential scan rate is
indicated on each plot. In all cases, the data capture rate was one point per second.
In general, these plots gave clean profiles where the tangents to the curve could be drawn at a
number of possible positions. The choice of precisely where to draw the tangents has been made
on the basis that the point of intersection should be as low as possible on the y-axis, and above
the minimum in the plot (on the x-axis).
The parameters were easier to obtain from the more easily corrodible metals (e.g., carbon steel,
Admiralty brass) but more difficult for the more inert metals (e.g., titanium) where the plot
minimum was more difficult to establish. The procedure was generally to start with a scan
across a wide potential range, at a rate of 2 mV per second or faster. Then, when the potential of
the minimum was established, the procedure was to perform a slower scan across a more
confined range, on either side of the current minimum. This was generally successful, and the
initial scan was often good enough to be used directly (as in the case of carbon steel, copper,
brass, and the bronzes). However, for the more inert metals (stainless and molybdenum steels,
and titanium), there was sometimes a problem that the initial scan built up enough of a protective
oxide that the minimum potential changed, or was so difficult to infer, that the second scan was
unhelpful. In these cases, one of two options were taken, either (a) to use the data from the first,
fast scan (if the data are good enough, as in the case of titanium), or (b) perform some numerical
smoothing on the results of either scan, provided the potential of the minimum had not changed
significantly from the first scan (as in the case of AL6XN).
The graphs for the Tafel plots in sea water chemistry are now presented.
A-1
Tafel Plots from the Polarization Studies
Carbon Steel in seawater chemistry

Scan Rate - 2.0 mV / sec
-1 Ta approx. 60
mV/decade
-2 Tc approx 110
mV/decade
Log Current Density
-3
-4
Log icor
-5
approx -4.8
-6
-7
-8
-1200 -1150 -1100 -1050 -1000 -950 -900 -850 -800 -750 -700 -650 -600 -550 -500 -450 -400 -350 -300
Potential (mV)
A-2
Copper in seawater chemistry

Scan rate 2.0 mV / sec
-2
-3 Tc approx
110 mV / dec
Log Current Density (A / cm sq)
-4
Ta approx
50 mV / dec
-5
log icor
approx -4.7
-6
-7
-900 -800 -700 -600 -500 -400 -300 -200 -100 0
Potential (mV)
A-3
Admiralty Brass in seawater chemistry

-2
-3
Tc approx
35 mV / dec
-4
-5 Ta approx
30 mV / dec
log icor
approx -5.6
-6
-7
-800 -700 -600 -500 -400 -300 -200 -100 0
Potential (mV)
A-4
90/10 Cu/Ni bronze in seawater chemistry

-2
-3 Tc approx
85 mV / dec
Log Current Density (A/cm sq)
Ta approx
-4 60 mV / dec
Log icor
-5
approx -4.7
-6
-7
-1200 -1000 -800 -600 -400 -200 0
Potential (mV)
A-5
70/30 Cu/Ni bronze in seawater chemistry

-1
Ta approx
60 mV/dec
-2 Tc approx
Log Current Density (A/sq cm)
70 mV/dec
-3
-4
Log icor
-5 approx -4.8
-6
-7
-1200 -1100 -1000 -900 -800 -700 -600 -500 -400 -300 -200 -100 0
Potential (mV)
A-6
316L Stainless Steel in seawater chemistry

Scan Rate = 2.0 mV / sec
-3
-4
-5
Ta approx
Tc approx 130 mV / dec
-6 260 mV / dec
Log icor
-7 approx -6.2
-8
-9
-700 -600 -500 -400 -300 -200 -100 0 100 200 300 400
Potential (mV)
A-7
304L stainless steel in seawater chemistry

-2
-3
Tc approx 220 Ta approx 65

-4 mV / decade mV / decade
Log current density (A / cm sq)
-5
-6
-7 Log icor
approx -6.8
-8
-9
-10
-11
-700 -600 -500 -400 -300 -200 -100 0 100 200 300 400
Potential (mV)
A-8
AL6XN in seawater chemistry

Scan Rate 5 mV / sec (data numerically smoothed)
-3
-4
-5
Tc approx Ta approx
730 mV/dec 280 mV/dec
-6
Log icor
approx -6.2
-7
-8
-1000 -800 -600 -400 -200 0 200 400 600 800 1000
Potential (mV)
A-9
Titanium in seawater chemistry

Scan Rate 10 mV / sec
-3
-4
-5
-6
Ta approx
680 mV / dec
-7
Log icor
approx -6.8
-8
-9
-1000 -500 0 500 1000 1500 2000
Potential (mV)
A-10
Carbon steel in seawater chemistry (repeat after 226 days)

Scan Rate 0.1 mV / sec
-3
-4
-5 Tc approx
Ta approx
17 mV / dec
15 mV / dec
-6 Log icor
approx -5.25
-7
-8
-710 -700 -690 -680 -670 -660 -650
Potential (mV)
A-11
Admiralty Brass in seawaterchemistry (repeat after 227 days)

Scan rate 1 mV / sec
-4
-5
Tc approx Ta approx
600 mV / dec 80 mV / dec
-6 Log icor
approx -5.3
-7
-8
-800 -700 -600 -500 -400 -300 -200 -100 0
Potential (mV)
A-12
90/10 Cu/Ni bronze in seawater chemistry (repeat after 144 days)

Scan rate 1 mV / sec
-3
-4
-5
Tc approx Ta approx
-6
Log icor
approx -5.0
-7
-8
-700 -650 -600 -550 -500 -450 -400 -350 -300 -250 -200 -150 -100
Potential (mV)
A-13
Carbon steel in seawater chemistry at 50 C (repeat after 296 days)

Scan rate 0.1 mV / sec (smoothed data)
-3
-4
-5
Log Abs CD
Tc approx Ta approx
-6
Log icor
approx -5.5
-7
-8
-820 -800 -780 -760 -740 -720 -700 -680
Potential (mV)
A-14
316L stainless steel in seawater chemistry at 50 C (repeat after 297 days)

Scan rate 1 mV / sec (smoothed data)
-4
-5
-6 Tc approx
280 mV / dec Ta approx
90 mV/dec
-7
Log icor
approx -6.9
-8
-9
-10
-700 -600 -500 -400 -300 -200 -100 0 100 200 300
Potential (mV)
A-15
A.2 Polarization Studies in Lake Water Chemistry
This section presents the Tafel plots obtained from the polarization studies in lake water
simulation chemistry (defined as a conductivity of approximately 1 mS/cm). These include the
original set of measurements, together with the additional materials and repeat measurements.
The parameters were generally more difficult to establish than for the sea water chemistry
measurements reported above. The same general procedure was followed, i.e., starting with a
scan across a wide potential range, at a rate of 2 mV per second or faster. Then, when the
potential of the minimum was established, a slower scan across a more confined range was
performed on either side of the current minimum.
However, in many cases, the measurements were difficult to interpret. There were generally two
problems, either that the potential of the current minimum was spread out, across a range, or that
the noise in the current signal was as high as to make the overall shape of the plot indistinct.
The latter problem was necessarily a consequence of the lower conductivity, where (compared
with sea water) lower currents were generally produced for a given applied voltage. An added
complication was the effect of the internal resistance of the gap between the luggin tip and the
metal surface, leading to an uncertainty in the applied voltage as a function of current.
The method used to overcome these problems was to perform some numerical smoothing on the
results of either scan, provided the potential of the minimum has not changed significantly from
the first scan. But because of the IR drop, the helpful measurements were confined to those at
very low currents; therefore (to perform numerical smoothing), it became necessary to generate a
relatively large number of data points within a small voltage range, which in turn meant reducing
the voltage scan rate to as low as 0.1 mV/second.
The graphs for the Tafel plots in lake water chemistry are now presented.
A-16
Carbon steel in lake water chemistry

-4
Tc approx Ta approx
0.6 mV / dec 0.5 mV / dec
L o g C u rren t D en sity (A / cm sq )
-5
Log icor
-6
approx -5.9
-7
-463 -462 -461 -460 -459 -458 -457 -456 -455 -454 -453
Potential (mV)
A-17
Copper in lake water chemistry

-4
-5
Ta approx
Tc approx 25 mV/dec
30 mV/dec
-6
Log icor
approx -6.3
-7
-8
-200 -190 -180 -170 -160 -150 -140 -130 -120 -110 -100 -90 -80 -70 -60 -50
Potential (mV)
A-18
Admiralty Brass in Lake Water chemistry

-4.0
-5.0
L o g C u rren t D en sity (A / c m s q )
Ta approx
-6.0 15 mV / dec
Tc approx
20 mV / dec
-7.0
Log icor
approx -6.2
-8.0
-9.0
-200 -190 -180 -170 -160 -150 -140 -130 -120 -110 -100 -90 -80
Potential (mV)
A-19
90/10 Cu/Ni bronze in lake water

-4
-5
Ta approx
5 mV / dec
Tc approx
-6 8 mV / dec
Log icor
approx -6.3
-7
-8
-140 -130 -120 -110 -100 -90 -80 -70 -60 -50
Potential (mV)
A-20
70/30 Cu/Ni bronze in lake water chemistry

-5.0
-6.0
Tc approx Ta approx
-7.0
15 mV/dec 11 mV/dec
Log icor
-8.0 approx -6.8
-9.0
-150 -140 -130 -120 -110 -100 -90 -80 -70
Potential (mV)
A-21
316L stainless steel in lake water chemistry

-5
-6
-7
Tc approx
35 mV/dec
Ta approx
-8 35 mV/dec
Log icor
approx -7.0
-9
-10
250 260 270 280 290 300 310 320 330 340 350 360 370
Potential (mV)
A-22
304L stainless stel in lake water chemistry

-5
-6
Tc approx Ta approx
15 mV / dec 20 mV/dec
Log icor
-7
approx -6.6
-8
-9
425 430 435 440 445 450 455 460 465
Potential (mV)
A-23
AL6XN in lake water chemistry

-5
Tc approx Ta approx
55 mV / dec 35 mV/dec
-6
-7
-8
Log icor
approx -7.4
-9
-10
0 50 100 150 200 250 300 350 400 450 500
Potential (mV)
A-24
Titanium in lake water chemistry

-6
-7
Log C urrent D ensity (A / cm sq)
Ta approx
-8 400 mV/dec
-9
Tc approx Log icor

-10 400 mV/dec approx -7.2
-11
-500 -400 -300 -200 -100 0 100 200 300 400 500
Potential (mV)
A-25
Carbon steel in lake water chemistry - repeat polarization (aged 85 days)

-3
-4
-5
Ta approx
23 mV / dec
-6
Log icor
approx -5.5
-7
-8
-660 -650 -640 -630 -620 -610 -600 -590 -580
Potential (mV)
A-26
Admiralty Brass in lake water chemistry - repeat polarization (aged 80 days)

-4
-5
Log Current Density (A/ cm sq)
-6
Ta approx
-7 28 mV / dec
Log icor
approx -6.5
-8
-9
-20 -10 0 10 20 30 40 50 60 70 80
Potential (mV)
A-27
90/10 Cu/Ni bronze in lake water chemistry - repeat polarization (aged 86 days)
-5.0
-5.5
-6.0
-6.5
Tc approx Ta approx
-7.0
-7.5
Log icor
-8.0 approx -6.7
-8.5
-9.0
-9.5
-10.0
60 70 80 90 100 110 120
Potential (mV)
A-28
A.3 Polarization Studies in Brackish Water Chemistry
This section presents the Tafel plots obtained from the polarization studies in brackish water
simulation chemistry (defined as a conductivity of approximately 10 mS/cm). These do not
include any repeat measurements, but cover all the materials tested in sea water and lake water
chemistry conditions.
The ease of interpretation of the measurements was intermediate between that of the sea water
and lake water measurements. The main problem was again that the potential of the current
minimum was spread out, across a range; sometimes the noise in the current signal was so high
as to make the overall shape of the plot indistinct. The IR drop problem was less of a concern
with this conductivity. It was comparatively small compared to the measured potentials.
Where necessary, the problems were overcome by performing numerical smoothing on the
results of either scan, provided the potential of the minimum has not changed significantly from
the first scan. Scan rates were adjusted as needed, to provide appropriate raw data.
The graphs for the Tafel plots in brackish water chemistry are now presented.
A-29
Carbon steel in brackish water chemistry

Scan rate 0.1 mV / s
-3
-4
Tc approx Ta approx
28 mV/dec 19 mV/dec
-5
-6
Log icor
approx -5.0
-7
-8
-720 -700 -680 -660 -640 -620 -600 -580
Potential (mV)
A-30
Copper in brackish water chemistry

-3
-4
Ta approx
-5 45 mV / dec
Tc approx
80 mV/dec
-6
Log icor
approx -5.5
-7
-8
-9
-350 -300 -250 -200 -150 -100
Potential (mV)
A-31
Admiralty Brass in brackish water chemistry

-3
Tc approx
-4 26 mV/dec
Ta approx
-5
10 mV/dec
Log icor
-6 approx -5.7
-7
-8
-9
-350 -340 -330 -320 -310 -300 -290 -280 -270 -260 -250 -240 -230 -220 -210 -200 -190 -180 -170 -160 -150 -140 -130 -120 -110 -100
Potential (mV)
A-32
90/10 Cu/Ni bronze in brackish water chemistry

-4
-5
Ta approx
83 mV / dec
-6
Log icor
approx -5.5
-7
-8
-300 -280 -260 -240 -220 -200 -180 -160 -140 -120 -100
Potential (mV)
A-33
70/30 Cu/Ni bronze in brackish water chemistry

-3
-4
Ta approx
-5 25 mV / dec
Tc approx
-6 55 mV / dec
Log icor
approx -5.9
-7
-8
-9
-300 -250 -200 -150 -100 -50
Potential (mV)
A-34
316L stainless steel in brackish water chemistry

Scan rate 0.2 mV / s (smooothed data)
-4
-5
Tc approx
200 mV / dec
-6
Ta approx
35 mV/dec
-7
Log icor
approx -6.6
-8
-9
-250 -200 -150 -100 -50 0 50 100 150 200 250
Potential (mV)
A-35
304L stainless steel in brackish water chemistry

Scan rate1 mV / sec (smoothed data)
-5
-6
Ta approx
40 mV/dec
Tc approx
160 mV/dec
-7
Log icor
approx -6.9
-8
-100 -50 0 50 100 150 200 250 300
Potential (mV)
A-36
AL6XN in brackish water chemistry

Scan rate 0.2 mV / s (smoothed data)
-5
-6
-7 Tc approx Ta approx
370 mV / dec 180 mV /dec
-8
Log icor
-9
approx -6.64
-10
300 350 400 450 500 550 600 650 700 750 800 850 900
Potential (mV)
A-37
Titanium in brackish water chemistry

-5
-6
Tc approx Ta approx
160 mV/dec 110 mV/dec
Log icor
approx -6.5
-7
-8
0 100 200 300 400 500 600
Potential (mV)
A-38
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EPRI Galvanic Corrosion

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EPRI Galvanic Corrosion

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Predictive Model for Galvanic Corrosion

M AT E the Wrapping Material.

Final Report, December 2004

EPRI Project Manager

(A) MAKES ANY WARRANTY OR REPRESENTATION WHATSOEVER, EXPRESS OR IMPLIED, (I)

(B) ASSUMES RESPONSIBILITY FOR ANY DAMAGES OR OTHER LIABILITY WHATSOEVER

ORGANIZATION(S) THAT PREPARED THIS DOCUMENT

This report was prepared by

BNFL Nuclear Sciences & Technology Services

This report describes research sponsored by EPRI.

Significant damage caused by galvanic corrosion is occasionally encountered in nuclear power

2 DESCRIPTION OF GALVANIC CORROSIVE MODEL .........................................................2-1

3 DESCRIPTION OF EXPERIMENTAL WORK ........................................................................3-1

4 POLARIZATION EXPERIMENTAL RESULTS ......................................................................4-1

5 FLOW LOOP EXPERIMENTAL RESULTS ...........................................................................5-1

5.5 Loop Test #5 .................................................................................................................5-15

7 DISCUSSION AND SUMMARY .............................................................................................7-1

A TAFEL PLOTS FROM THE POLARIZATION STUDIES...................................................... A-1

Figure 3-1 Schematic Diagram of Polarization Test Equipment ................................................3-5

Table 3-1 Selection of Galvanic Couples...................................................................................3-2

There are a number of implicit assumptions and simplifications in this approach:

2.1 Physical Basis of the Model

2.1.1 Transport Along the Pipe

C is the species concentration

Description of Galvanic Corrosive Model

Within the pipe, each species obeys a conservation equation, given by

The potential is strictly governed by Poissons equation,

o is the permittivity of free space,

jc is the electric current density flowing in the solution,

Description of Galvanic Corrosive Model

2.1.2 Corrosion at the Metal Surface

Corrosion of metal (1) by anodic dissolution is described by the following reaction,

M = Mz+ + ze- Equation 2-11

The anodic corrosion current density is given by the Tafel equation,

io ,1 and 1 are characteristic constants for the metal (1),

m is the potential in solution at the surface of the metal (1).

Description of Galvanic Corrosive Model

O2 + 4H+ + 4e- = 2H2O Equation 2-14

Often the io, 2 is a function of the species concentration in solution.

3.1 Outline of Work Program

The required work splits into two sets of tests.

The metals of interest to this study are as follows:

Description of Experimental Work

Zinc when used as a

Description of Experimental Work

3.2 Experimental Technique

3.2.1 Polarization Experiments

Description of Experimental Work

Description of Experimental Work

Equipment (see diagram Figure 3-1 and photograph Figure 3-2)

The individual items of equipment are:

Gas Sparge Re fe re nce

Description of Experimental Work

Description of Experimental Work

Description of Experimental Work

3.2.2 Flowing Loop Tests

Equipment (see diagram Figure 3-3 and photograph Figure 3-4)

Description of Experimental Work

Metal frame for reservoir, stirrer, drip tray beneath reservoir.

SCHEMATIC DIAGRAM OF CORROSION CURRENT FLOW LOOP

Calomel electrode Volt

Description of Experimental Work

Note that it is necessary to calibrate the instruments, such as pH and conductivity, to QA

Description of Experimental Work