Atlas of Polarization Data

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Carderock Division
Naval Surface Warfare Center
Bethesda, Md. 20084-5000
CARDIVNSWC-TR-6194/44
April 1995
Survivability, Structures, and Materials Directorate

Technical Report
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Atlas of Polarization Diagrams for Naval Materials in

Seawater
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Harvey P. Hack
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Carderock Division
April 1995
Survivability, Structures, and Materials Directorate

Technical Report
Atlas of Polarization Diagrams for Naval Materials in

Seawater
by
Harvey P. Hack
DTIC QUALITY IM3PECTED 21
ABSTRACT
Polarization curves were developed in seawater at low (quiescent) flow and at 2.4
m/s flow for nine structural alloys. Potentiostatically generated curves for up to 120 days
are compared with potentiodynamically generated curves at four scan rates with freely
corroding pre-exposures of I or 120 days. Smoothed curves successfully used in computer model predictions ofcathodic protection current and potential distributions are also
presented. These curves are compared with previously published data available for 800
days exposure and with cathodic protection current density design guidelines. Corrosion
rate data as a function ofpotential after up to 120 days exposure are also presented.
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CONTENTS
Page
Abstract
iii
Administrative Information
vi
Acknowledgments
vi
Abbreviations
vi
Introduction
Materials
Apparatus and Procedure
Quiescent Flow, Potentiostatic Tests
Quiescent Flow, Potentiodynamic Tests
Flowing Tests
Data Analysis Techniques
Results and Discussion
Conclusions
10
References
11
Appendix A.
Polarization Curves From This Study for HY-80 Steel
13
Appendix B.
Polarization Curves From This Study for 90-10

Copper-Nickel
25
Polarization Curves From This Study for 70-30

Copper-Nickel
37
Polarization Curves From This Study for Navy Type M

Bronze
47
Polarization Curves From This Study for Nickel-Aluminum

Bronze
59
Appendix F.
Polarization Curves From This Study for Monel
71
Appendix G.
Polarization Curves From This Study for Alloy 625
83
Appendix H.
Polarization Curves From This Study for Titanium 50
95
Appendix C.
Appendix D.
Appendix E.
Appendix I.
Polarization Curves From This Study for Anode Grade Zinc ...
105
Appendix J.
Corrosion Rates From Potentiostatic Tests in This Study
115
Appendix K.
Smoothed Polarization Curves Used in Boundary Element

Study
131
Foster and Moores' 800-Day Polarization Data
135
Appendix L.
Appendix M.
Cathodic Protection Design Data for Steel
149
Initial Distribution
153
Standard Form 298
155
FIGURES
1.
Exposure vessels for quiescent tests
2.
Specimen mounting for quiescent tests
3.
Flowing test cell design
4.
One flowing cell test loop
5.
Four flowing cell test loops
8
TABLE
Nominal composition of alloys tested
ADMINISTRATIVE INFORMATION
This project was funded under the Surface Ship Materials Technology Program
sponsored by the Office of Naval Research (ONR) and managed by Mr. Ivan Caplan. The
work was performed under program element 62761N, task area SF61541-591, work units
1-2803-162 and 1-2803-164. Work was conducted in the Marine Corrosion Branch under the direction of Mr. Robert J. Ferrara.
ACKNOWLEDGMENTS
I wish to particularly acknowledge the contributions of Dr. John R. Scully, who performed many of the experiments described herein. Also acknowledged is the staff at the
LaQue Center for Corrosion Technology for help in the design and conduct of these experiments.
ABBREVIATIONS
ASTM
American Society for Testing and Materials
CARDEROCKDIV, NSWC Carderock Division, Naval Surface Warfare Center
Vi
EG&G PAR
EG&G Princeton Applied Research
IR
Current x Resistance
rms
root mean square
INTRODUCTION
Predicting the amount of galvanic corrosion and the current demand for cathodic
protection in seawater requires accurate polarization data for the materials involved.
Computer models that predict the distribution of galvanic corrosion, stray current corrosion, and cathodic protection also require accurate polarization data.
Rates of galvanic corrosion are commonly predicted using tables of galvanic compatibility,1 differences in corrosion potential between members of the galvanic couple
where the corrosion potentials are obtained from a list or chart,2 or by conducting relatively short-term exposures or electrochemical tests and extrapolating the results to apply
to the item in service.3-4 The first two methods are qualitative, providing only an indication of the tendency for corrosion damage in the galvanic couple. Unfortunately,
polarization curves for most structural materials in seawater are exposure-time dependent
and scan-rate dependent, making quantitative prediction from short-term exposures inaccurate.
Current densities for cathodic protection are frequently predicted from values found
in standards.5'6 These values, although based on long-term exposures, are not complete
polarization curves and are, therefore, not adequate for use in computer modeling.
The need for a single source of polarization curves for commonly used materials in
seawater and for a quantification of exposure time and scan rate effects led to this investigation. Although portions of these data have been presented elsewhere,7-12 this
document presents all of the data collected over the course of the investigation.
MATERIALS
Materials in this study were selected to be representative of the major classes of
structural materials used by the Navy for seawater systems on ships. The following materials were studied:
HY-80 steel (MIL-S-16216H*)
90-10 copper-nickel (C70600)
70-30 copper-nickel (C71500)
Monel 400 (C92200)
Nickel-aluminum bronze (C95800)
Bronze composition M (C92200)
Titanium grade 50 (R50400)
Alloy 625 (N06625)
Anode grade zinc (MIL-A-18001J**).
Nominal compositions of the alloys tested appear in the following table. Corrosion samples were prepared by rough cutting blanks from the supplied bars or plates, milling to
*"Steel Plate, Alloy, Structural, High Yield Strength (HY-80 and HY-100)."
**"Anodes, Sacrificial Zinc Alloy."
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APPARATUS AND PROCEDURE
QUIESCENT FLOW, POTENTIOSTATIC TESTS
For the short-term exposures (5 min and 1 day), specimens were 12.7 mm square by
6.2 mm thick. Exposures were performed sequentially in beakers of fully oxygenated natural seawater heated to a constant 30 C. For the long-term exposures, specimens were
25.4 mm square by 6.2 mm thick. Three specimens of identical material were exposed at
the same potential for different lengths of time connected to the same potentiostat. In this
way, all 30-, 60-, and 120-day exposures were conducted simultaneously. A series of individual exposure vessels was used to avoid ground loops or stray current effects (see
Figure 1). One hundred eight 4-L vessels were fitted into two wooden boxes lined with
thermal insulation. Heated, filtered natural seawater was drip-fed into each container to
maintain oxygen levels in the bulk solution at saturation and temperatures at 30 C.
Quiescent flow was maintained via the low refreshment rate. Corrosion coupons were
suspended in the exposure vessels by means of a threaded rod screwed into a hole tapped
into the specimen edge. This rod was also used for electrical contact to the specimen (see
Figure 2). Water was excluded from the electrical contact/mounting rod by means of a
glass tube and Teflon gasket. Platinum-coated counter electrodes were placed adjacent to
the specimen faces. Ag/AgCl reference electrodes were placed in the plane of the corrosion coupons, directly below the specimens. Some vessels contained three identical,
freely corroding specimens of each material for sequential removal at 30, 60, and 120
days. These vessels also contained reference electrodes, but no counter electrodes.
A bank of 70 potentiostats constructed for this experiment was located in an adjacent temperature-controlled room and was connected to the test cells through insulated
electrical leads. Potential and current readings were taken by a computerized data acquisition system. For the potentiostats employed, a plus or minus 5-mV variation in set
potential was maintained. A thermal instability coefficient of about 1 mV/C air temperature and IR (Current X Resistance) drop through the cabling was identified as the source
of these variations. Electrical leads from the specimen groups of three were connected in
series to 1-ohm resistors for current measurement as potential drop.
Fifteen to seventeen potentials were chosen for each material in potentiostatic polarization experiments. Exposures were conducted in several runs, each run consisting of
simultaneous testing of all materials over the 120-day period. Currents, potentials, and
temperatures were recorded once a minute for the first day of exposure, every 10 minutes
for the first week, and three times daily thereafter.
ASTM-recommended procedures for cleaning , drying, and massing were followed
for mass loss determinations.13 Special care was taken to ensure that the threaded hole
was dry prior to massing. Massing was performed to the nearest 0.1 mg.
QUIESCENT FLOW, POTENTIODYNAMIC TESTS
Exposure vessels and coupon mounting were the same as the potentiostatic exposures. Specimens were 12.7 mm square by 6.2 mm thick. Platinum-coated counter
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electrodes and a saturated calomel reference electrode with Luggin probe were used.
Instrumentation consisted of an EG&G PAR (Princeton Applied Research) model 173
potentiostat with a log current converter and a model 175 programmer. An Apple computer was used for analog-to-digital conversions and for data storage and retrieval.
Specimens were studied under two conditions: 1-hr or 120-day pre-exposure at open
circuit potential in natural seawater. In general, test procedures followed ASTM Standard
G5.14 Separate specimens were independently polarized anodically and cathodically
starting at the corrosion potential. Duplicate specimens were tested at most scan rates.
The following four scan rates were used:
1. 0.5 V/hr (0.14 mV/s)
2. 5V/hr(1.4mV/s)
3. 50V/hr(14mV/s)
4. 100 V/hr (28 mV/s).
FLOWING TESTS
The test cell design for flowing seawater exposures is shown in Figures 3 to 5. The
direction of flow was parallel to the specimen length through a rectangular channel 2.54
cm high by 0.635 cm wide. Eight 1-cm square working electrodes and eight platinum
counter electrodes were mounted flush against the interior wall of the rectangular cross
section facing each other across opposite walls (see Figure 3). An insulated electrical lead
was attached to the dry back face of both counter and working electrodes. The same arrangement was used for potentiostatic and potentiodynamic testing. Reference electrode
ports were drilled through the top interior wall of all parallel plate cell positions (see Figure 3). Hydrostatic pressure forced seawater through a vinyl tube containing
microelectrodes. A 0.42-cm diameter Ag/AgCl microreference electrode was positioned
above the reference electrode port. A valve was positioned between the port and the reference electrode to allow air bubble removal.
Figure 4 shows a single flow-through cell test loop. Heated natural seawater was
pumped from a 70-L (17-gal) holding tank through the test cell and back to the tank. Filtered (8 |xm) natural seawater for refreshment was fed from a common 200-L (50-gal)
preheated makeup tank at a rate of 5 L/min to each holding tank in each loop, where it
was heated to 30 C plus or minus 3 C, and the excess allowed to overflow. The flow
velocity in the test cells was 2.4 m/s. Four flow-through cells were used (see Figure 5).
Concern for electrodeposition on a specimen "downstream" of metal lost from a specimen "upstream" led to careful consideration of specimen placement within each cell and
between the four test loops. Aluminum gutters were also placed in each holding tank.
Flow in this test setup was determined to be turbulent by Reynolds number analysis. Wall
shear stress was calculated to be 17.4 to 18.7 N/m2.
Six to nine potentials were chosen for each material in the potentiostatic tests. Only
single 120-day potentiostatic specimens were exposed. Anodically and cathodically polarized potentiodynamic specimens, pre-exposed for 120 days, were exposed in separate
cells. One-hour, pre-exposed potentiodynamic specimens were exposed in individual
flow-through cells. Potentiodynamic scans were conducted at two scan rates: 0.5 and 5
V/hr (0.14 and 1.4 mV/s, respectively).
REFERENCE ELECTRODE PORT

V.- SPACING BETWEEN SPECIMENS
EPOXY MOUNT FOR ORTHOGONAL
SPECIMEN MOUNTED PARALLEL TO
FLOW 11" DIAMETER MOUNT. 1 cm2
SURFACE AREA SPECIMEN)
OUTLET
FLOW
INLET FLOW
' INSULATED
ELECTRICAL CONNECTION
Figure 3.
Flowing test cell design.
DATA ANALYSIS TECHNIQUES

Potential variability was plus or minus 10 mV. Where the actual potential deviated
significantly from the set potential, the actual potential value was used at the time period
being analyzed. Current resolution was better than 1 percent of the reported values for
5-min exposures, better than 1 \iA/cm2 for 1-day exposures, and better than 0.1 to 0.6
[iA/cm2 for longer exposures, depending on the number of specimens in test. In some
cases, data averaging or curve fitting was used to reduce the quantity of data handled. To
obtain current densities, the current vs. time plots were hand-fitted with smooth curves
and values picked off at the appropriate exposure times, normalizing for the number of
specimens remaining in test at that time. Where duplicate specimen data were available, a
composite curve was constructed. In some cases, due to rapid fluctuations, current was
numerically integrated over the exposure period of interest to get an average value. Depth
of attack measurements made on some specimens after the test duration were linearly ex-
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trapolated to estimate attack depths after 1 yr. Corrosion rates reported are based on metal
loss and surface area and, therefore, do not reflect localization of corrosion.
RESULTS AND DISCUSSION
The results of this investigation are contained in the polarization curves in Appendixes A through I. Detailed descriptions of the behavior of each material, flow, type of
polarization, exposure duration, scan rate, etc., would be too lengthy to state here. Some
general results are that scan rate and pre-exposure time have a significant effect on potentiodynamic polarization behavior. Exposure time has a large effect on potentiostatic
polarization behavior. The polarization current usually levels out after 30 days under
quiescent conditions, except at the most negative potentials where the assumed buildup of
calcareous deposits allows for continued current decay, even up to 120 days. Under
quiescent conditions, the cathodic behavior of all materials is roughly the same, with a
constant current density of about 10 uA/cm2 at potentials well below the corrosion potential and above approximately -900 mV. Flowing potentiostatic data have too much scatter
to make many conclusions other than that current densities are typically significantly
higher than under quiescent conditions. None of the potentiodynamic curves, even those
after a 120-day pre-exposure, resemble the long-term potentiostatic curves sufficiently to
be used for accurate prediction of galvanic or cathodic protection behavior.
Appendix J contains curves showing corrosion rate from mass loss, normalized to 1
yr, of each material except Ti-50 and Alloy 625, which had no measurable mass loss under quiescent flow conditions as a function of exposure time and potential.
Appendix K contains the smoothed 120-day potentiostatic polarization curves used
as boundary conditions for a boundary element model of a 16-m-long, cathodically protected barge in seawater.15 In that paper, the potential and current distributions predicted
by the boundary element model accurately matched those measured on a real barge. This
means that the curves used in the model were representative of the long-term performance of the materials on the barge.
Another study was performed on many of the same materials as this study by Foster
and Moores at the Defence Research Establishment Pacific in Canada.16 Their study was
conducted in water at 9 C for time periods up to 2,000 days exposure, although only data
up to 800 days were reported. Potentials used were as low as -1,100 mV vs. Ag/AgCl.
Only average current densities over the entire test were reported. These are replotted in a
format consistent with the data generated in this study in Appendix L. Foster and
Moores' data are very similar to the long-term potentiostatic data generated here, but
their-1,100-mV specimens usually had significantly higher current densities than the
-1,100-mV specimens from the current study reported in Appendixes A through I.
Comparison of HY-80 steel data from these studies to actual cathodic protection
design current density and potential ranges for steel is instructive. Design data from
NACE International,5 technical guidance from the Naval Sea Systems Command,6 and
several Norwegian and United Kingdom design guidelines, as reported by Wyatt,17 are
shown in Appendix M. While all design guidelines recommend protection to -800 mV
vs. Ag/AgCl, the design current densities used range over more than an order of magnitude, centered roughly around the 10-uA/cm2 value from the steel data in Appendix A.
The data in Appendix A are, therefore, consistent with design practice.
CONCLUSIONS
None of the potentiodynamic curves resembles the long-term potentiostatic curves
sufficiently to be used for accurate prediction of galvanic or cathodic protection behavior.
Adequate prediction requires the use of long-term, potentiostatically derived polarization
curves. Data are presented that have been successfully used to predict cathodic protection
current and potential distribution on a large structure. Data from this study are in agreement with data from other investigators and with cathodic protection current density
design guidelines from several countries.
10
REFERENCES
1.
NACE Corrosion Engineer's Reference Book, R.S. Treseder, Ed., NACE International, Houston, Tex., p. 62 (1980).
2.
LaQue, F.L., Marine CorrosionCauses and Prevention, John Wiley and Sons,
Inc., New York, N.Y., p. 179 (1975).
3.
Aylor, D.M., and H.P. Hack, "Comparative Galvanic Corrosion Effects of Noble
Metals on Bronze in Seawater," CORROSION/82, Paper No. 61, NACE International, Houston, Tex. (1982).
4.
Hack, H.P., and W.L. Adamson, "Analysis of Galvanic Corrosion Between a Titanium Condenser and Copper-Nickel Piping System," CARDEROCKDIV,
NSWC Report 4553 (Jan 1976).
5.
"Standard Recommended PracticeCorrosion Control of Steel, Fixed Offshore

Platforms Associated With Petroleum Production," Standard RP0176, NACE
International, Houston, Tex. (1983).
6.
Naval Ships' Technical Manual, Chapter 633, "Cathodic Protection,"

S9086-VF-STM-O10/CH-633, Naval Sea Systems Command, Crystal City, Va.
(Dec 1991).
7.
Hack, H.P, "Galvanic Corrosion Prediction Using Long-Term Potentiostatic Polarization Curves," CORROSION/83, Paper No. 73, NACE International,
Houston, Tex. (1983).
8.
Hack, H.P, "Exposure Time Effects on Current Densities of Polarized Marine

Materials," CORROSION/83, Paper No. 210, NACE International, Houston,
Tex. (1983).
9.
Scully, J.R., and H.P Hack, "Galvanic Corrosion Prediction Using Long and
Short Term Polarization Curves," CORROSION/84, Paper No. 34, NACE International, Houston, Tex. (1984).
10.
Scully, J.R., and H.P. Hack, "Effect of Exposure Time on the Polarization Behavior of Marine Alloys Under Flowing and Quiescent Conditions,"
CORROSION/85, Paper No. 214, NACE International, Houston, Tex. (1985).
11.
Hack, H.P, and J.R. Scully, "Galvanic Corrosion Prediction Using Long- and
Short-Term Polarization Curves," Corrosion, Vol. 42, No. 2, pp. 79-90 (Feb
1986).
12.
Scully, J.R., H.P. Hack, and D.G. Tipton, "Effect of Exposure Time on the Polarization Behavior of Marine Alloys Under Flowing and Quiescent Conditions,"
Corrosion, Vol 42, No. 8, pp. 462-469 (Aug 1986).
13.
"Standard Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens," Standard Gl, ASTM Book of Standards, Vol 03.02, Philadelphia, Pa
(1986).
11
12
14.
"Reference Test Method for Making Potentiostatic and Potentiodynamic Anodic

Polarization Measurements," Standard G5, ASTM Book of Standards, Vol 03.02,
Philadelphia, Pa (1986).
15.
Hack, H.P., and R.M. Janeczko, "Verification of the Boundary Element Modelling Technique for Cathodic Protection of Large Ship Structures,"
CARDEROCKDIV, NSWC Report CARDIVNSWC-TR-6193/02 (Dec
1993).
16.
Foster, T, and J.G. Moores, "Cathodic Protection Current Demand of Various

Alloys in Sea Water," CORROSION/86, Paper No. 295, NACE International,
Houston, Tex. (1986).
17.
Wyatt, B.S., "Cathodic Protection Monitoring and Survey Requirements for Offshore Platforms and Pipelines: Part 1," Anti-Corrosion (Jun 1985).
APPENDIX A
POLARIZATION CURVES FROM THIS STUDY FOR HY-80 STEEL
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SMOOTHED POLARIZATION CURVES USED IN BOUNDARY ELEMENT STUDY
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APPENDIX M
CATHODIC PROTECTION DESIGN DATA FOR STEEL
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REPORT DOCUMENTATION PAGE
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1. AGENCY USE ONLY (Leave blank)
3. REPORT TYPE AND DATES COVERED
2. REPORT DATE
April 1995
Final
5. FUNDING NUMBERS
4. TITLE AND SUBTITLE
Atlas of Polarization Diagrams for Naval Materials in Seawater

6. AUTHOR(S)
Harvey P. Hack
Program Element 6276 IN

Task Area SF61541-591
Work Units 1-2803-162;
1-2803-164
8. PERFORMING ORGANIZATION
REPORT NUMBER
7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)
Carderock Division
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11. SUPPLEMENTARY NOTES
12b. DISTRIBUTION CODE
12a. DISTRIBUTION/AVAILABILITY STATEMENT
13. ABSTRACT (Maximum 200 words)
Polarization curves were developed in seawater at low (quiescent) flow and at 2.4 m/s
flow for nine structural alloys. Potentiostatically generated curves for up to 120 days are
compared with potentiodynamically generated curves at four scan rates with freely corroding
pre-exposures of 1 or 120 days. Smoothed curves successfully used in computer model predictions of cathodic protection current and potential distributions are also presented. These
curves are compared with previously published data available for 800 days exposure and
with cathodic protection current density design guidelines. Corrosion rate data as a function
of potential after up to 120 days exposure are also presented.
15. NUMBER OF PAGES
14. SUBJECT TERMS
Polarization curves, Seawater, Cathodic protection, Galvanic corrosion, Corrosion rate, Corrosion, Computer modeling, Stray current corrosion, Steel,
Copper-nickel, Bronze, Titanium, Alloy 625, Zinc
17. SECURITY CLASSIFICATION

OF REPORT
Unclassified
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Same as Report
Standard Form 298 (Rev. 2-89)
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Apparatus and Procedure

Quiescent Flow, Potentiostatic Tests

Quiescent Flow, Potentiodynamic Tests

Data Analysis Techniques

Results and Discussion

Polarization Curves From This Study for HY-80 Steel

Polarization Curves From This Study for 90-10

Polarization Curves From This Study for 70-30

Polarization Curves From This Study for Navy Type M

Polarization Curves From This Study for Nickel-Aluminum

Polarization Curves From This Study for Monel

Polarization Curves From This Study for Alloy 625

Polarization Curves From This Study for Titanium 50

Corrosion Rates From Potentiostatic Tests in This Study

Smoothed Polarization Curves Used in Boundary Element

Foster and Moores' 800-Day Polarization Data

Cathodic Protection Design Data for Steel

Standard Form 298

Exposure vessels for quiescent tests

Specimen mounting for quiescent tests

Flowing test cell design

One flowing cell test loop

Four flowing cell test loops

Nominal composition of alloys tested

American Society for Testing and Materials

CARDEROCKDIV, NSWC Carderock Division, Naval Surface Warfare Center

EG&G Princeton Applied Research

root mean square

p.z coco fpco th h "6 6 . En

Specimen mounting for quiescent tests.

REFERENCE ELECTRODE PORT

Flowing test cell design.

DATA ANALYSIS TECHNIQUES

THERMOCOUPLE CONTROL 30C

TO POTENTIOSTATS AND DAS

One flowing cell test loop.

Four flowing cell test loops.

"Standard Recommended PracticeCorrosion Control of Steel, Fixed Offshore

Naval Ships' Technical Manual, Chapter 633, "Cathodic Protection,"

Hack, H.P, "Exposure Time Effects on Current Densities of Polarized Marine

"Reference Test Method for Making Potentiostatic and Potentiodynamic Anodic

Foster, T, and J.G. Moores, "Cathodic Protection Current Demand of Various

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