Seawater

J a m e s F. J e n k i n s J

BASICS
As IN OTHERNATURALenvironments, corrosion testing in seawater is dependent upon the actual environmental conditions experienced by the exposed materials during the entire duration of exposure. These environmental conditions can vary widely in any specific location. Normal seasonal variations as well as variations from year to year and temporary natural or manmade conditions can dramatically affect the conditions of exposure that control overall corrosion behavior of materials. Seasonal variations include changes in temperature, dissolved oxygen content, and the type and extent of biological fouling. Significant year-to-year variations such as those caused by the aperiodic general ocean surface water warming in the eastern Pacific Ocean, called E1 Nifio, also affect the seawater environment over a wide area. Temporary natural conditions may include natural proliferation of microorganisms such as the "red tide" blooms of algae that can significantly reduce dissolved oxygen availability. Temporary manmade conditions such as spills of oil, chemicals, and sewage can also have a dramatic effect on the local environment that can affect corrosion. A further complication is that these variations may not affect the deterioration of materials in a simple manner. In m a n y cases, metal corrosion is dependent upon surface films that form u p o n exposure to seawater. Variations of initial exposure conditions can affect the protective nature of these films, which can affect the further corrosion behavior of the material. Thus, a sample first exposed u n d e r conditions conducive to the formation of a protective film may perform very differently than the same material exposed for an identical period, but was first exposed to conditions that resulted in the formation of a film that was less protective. In other cases, short-term variations in environment may be sufficient to initiate attack that would not occur during typical conditions and that, once initiated, can continue over extended exposures. The interaction between biological activity and material performance is very significant in seawater. Macrofouling such as barnacles and mussels can be either protective or can result in accelerated corrosion depending on the material exposed and the extent of the accumulation of fouling. Anaerobic conditions are frequently found at the base of extensive fouling accumulation and this can dramatically affect corrosion of m a n y materials. Seasonal variations a n d 1329 Drake Street, Cambria, CA 93428.
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temporary upsets can also result in the death and sloughing off of specific types of fouling organisms, which can cause temporary upsets of conditions at the surface of the material. Because of the highly variable nature of the seawater environment, the results of corrosion testing in seawater are subject to significant variability. Reference 1 describes several test programs that demonstrate this variability. Considerable variability in the corrosion behavior of steel, a l u m i n u m and copper-nickel was also demonstrated in a worldwide seawater corrosivity test program described in Ref 3. To properly interpret the results of such tests, it is important to include control samples in the testing program. These control samples should include materials whose corrosion performance in the environment is well established. One control should be a material such as mild steel, which corrodes significantly in the environment so that corrosion rates for the control can be established. Another control should be a material that has marginal resistance to the environment so that upset conditions that may cause unusual initiation of corrosion can be detected. Additional control materials with compositions and characteristics similar to those being tested should also be included. For example, if performance of a newly developed stainless steel is being evaluated, samples of previously tested stainless steels should be included as controls.

SPECIMEN CONFIGURATION
There are no specific standards for the configuration of samples for seawater testing. A few general guidelines should be considered when determining the appropriate specimen configuration and size. As metallurgical condition is an important variable in the performance of m a n y metals, specimens with metallurgical condition similar to that of the material of interest should be included in the test. For example, if plate material is of primary interest, plate material should be selected for testing. If the metallurgical condition of interest is not defined, or several conditions are of interest, specimens of the material with different metallurgical conditions should be exposed. ASTM G 52 (see section on standards at the end of this chapter) recommends a n o m i n a l sample size of 100 by 300 mm. In general, larger specimens are preferred over smaller specimens. First, larger specimens will expose a greater a m o u n t of surface area which will increase the probability of initiation of localized attack such as pitting.

CHAPTER 1 2 - - S E A W A T E R
Second, where m e a s u r e m e n t of corrosion rate by mass loss is important, mass losses for larger specimens will be greater, thus requiring lower precision in weighing for equivalent precision in mass loss per unit area. Third, for m a n y sheet and plate materials, exposed edges may corrode differently than exposed faces. Corrosion potential differences resulting from these differences m a y accelerate the corrosion of either the edges or faces. This effect is minimized in larger samples because the ratio of face area to edge area is minimized. Increasing the sample size beyond approximately 300 by 300 mm, however, has little further effect in minimizing the influence of the edges on face behavior of most materials. Unlike laboratory tests where the volume of solution must be adjusted for sample size, this is not a factor in natural seawater exposures.

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can be measured on specimens of nearly any configuration. Specimen size, however, may dictate the type of instrumentation that is utilized in these measurements.

Galvanic Corrosion
Galvanic corrosion tendencies can be evaluated by developing a galvanic series for the materials of interest as described in ASTM G 82. Galvanic corrosion rates can be established by exposure of galvanic couples as described in ASTM G 71.

Crevice Corrosion
For many alloys such as stainless steels that rely on passivity for corrosion resistance, crevice corrosion can be a limiting factor in their seawater corrosion resistance. For a specific alloy, resistance to crevice corrosion in seawater is predominantly dependent u p o n the tightness and depth of the crevice formed and on the ratio of exposed surface inside and outside the crevice. Many crevice corrosion tests have been developed that attempt to control these three primary factors in crevice corrosion. ASTM G 78 describes a variety of crevice-forming assemblies and other test considerations. Both flat and cylindrical specimens are described in the latest version of ASTM G 78. It should, however, be remembered that even simple immersion tests include crevice testing because natural crevices form where the specimens are held in the test racks and m a y also be present at such features as sheared edges and drilled holes as well as u n d e r fouling organisms such as barnacles. Therefore, when specimens specifically configured for crevice corrosion evaluation are not included in a test program, special attention should be given to inspection of the specimens at these inherent crevice sites for indications of susceptibility to crevice attack. When artificial crevice formers are used, other crevices can he avoided by using the crevice former fastener to hold the specimen.

Duration of Exposure
Because long-term durability is required for most marine applications, corrosion test exposures for periods of less than six months usually are not sufficient for engineering purposes. Exposures of 0.5, 1, 2, 5, 10, and 20 years are r e c o m m e n d e d in ASTM G 52. For control specimens, information on environmental variability can be obtained by exposing specimens for periods of one-fourth of a year where the specimens are initially exposed one-fourth of a year, a half-year, and theequarters of a year after the start of the test. Year-to-year variability can be evaluated by exposing a series of specimens that are initially exposed at one-year intervals after the start of the test and removed after one year of exposure. Testing for shorter periods may be appropriate when the test sample configuration intentionally provides more severe conditions than anticipated in service. Crevice corrosion tests using severe artificial crevice geometries m a y only require 30-90 days of exposure to establish relative crevice corrosion resistance.

N u m b e r of Test Specimens
The n u m b e r of replicate test specimens depends u p o n the desired reliability of the results of the test. ASTM G 16 gives guidance for establishing the required n u m b e r of replicate specimens. In general, as r e c o m m e n d e d in ASTM G 52, triplicate specimens for each exposure period are sufficient for m a n y seawater corrosion tests.

Stress Corrosion
While m a n y laboratory tests for resistance of metals to stress corrosion cracking have been developed, only a few tests are amenable to actual in-situ testing in seawater. These primarily consist of the exposure of statically stressed type test specimens such as described in ASTM G 30, G 38, G 39, and ISO 7539-2, ISO 7539-3, and ISO 7539-5. In addition, welded specimens such as described in ASTM G 58 are excellent for evaluation of the stress corrosion resistance of weldments in simple immersion tests. Evaluation of corrosion fatigue is usually limited to laboratory testing.

TESTS FOR SPECIFIC TYPES OF C O R R O S I O N

If susceptibility to specific types of corrosion is of interest, specialized sample configurations can be used. If the corrosion performance of the material in seawater is completely unknown, at a m i n i m u m it should be evaluated for general corrosion and pitting, galvanic corrosion, crevice corrosion, and stress corrosion.

SPECIMEN PREPARATION
Because multiple samples will normally be exposed in a seawater test program, specimens should be labeled in a manner whereby the sample can be easily identified during sample preparation and evaluation. ASTM G 52 recommends several methods of such specimen labeling including the use of coded drilled holes, edge notches, corrosion-resistant tags, and stamped numerals. In some cases, the use of stamped

General Corrosion and Pitting

Evaluation of general corrosion and pitting does not require any special specimen configuration. Mass loss and pit depths

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CORROSION TESTS AND STANDARDS MANUAL

specimens should be limited to about 50 kg for manual handling by two persons. Allowance should also be made for the fouling that will accumulate on the test specimens and racks. To identify problems such as frayed suspension ropes and rack entanglement, inspection of the exposure site at weekly intervals as a m i n i m u m with additional inspections during stormy periods is recommended. In most cases, specimens that become detached can be replaced in the test racks without serious effect on the test results if the samples are retrieved and replaced in the racks within a few days.

numerals may introduce significant local residual stress in the sample which may cause cracking in susceptible materials. In addition, location of the specimens on the exposure racks should be recorded as a backup identification method. To develop quantitative and reproducible corrosion performance data in any corrosion test p r o g r a m it is important to properly prepare the specimens for exposure. ASTM G 1, Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens, gives guidelines for specimen preparation for exposure. This standard includes guidelines for cleaning, measuring, and weighing the samples prior to exposure. In m a n y marine corrosion studies, multiple samples will be placed on racks before exposure and a considerable period of time may elapse between specimen cleaning and exposure. In these cases, it may be necessary to store the specimens and racks in a low-humidity environment prior to exposure. In addition, care must be taken in handling the specimens to prevent contamination of the specimens with oils, salts, or other contaminants on people's hands.

Velocity Testing
Testing of materials for resistance to seawater under velocity conditions such as testing for resistance to erosion-corrosion, cavitation, and direct impingement can he performed in the ocean but are more commonly performed in water pumped into tanks and troughs. Velocity can be achieved by moving the specimen through the water, but is more commonly accomplished by moving the seawater past fixed specimens. Flow troughs can be designed to give flow velocities up to 2 m/s. Tests at higher velocities are essentially laboratory tests performed in continuously or intermittently refreshed seawater. There are several testing procedures that have been developed to perform these tests under standardized conditions. ASTM G 32 and G 73 are standard methods for vibratory cavitation erosion and liquid impingement erosion testing, respectively, and can be performed using refreshed seawater. Jet impingement testing usually requires filtration of the incoming seawater to avoid clogging of the jet orifices. Tests using spinning disk samples are described in Ref 3. Other tests at very high velocities have been developed as described in Ref 5. For testing at extreme velocities, such as those encountered by hydrofoils, special test apparatus using spinning circular water troughs have been developed. Other nonstandard velocity tests can be performed using subscale or even full-scale systems. An example of such tests is the evaluation of condenser tubing using p u m p e d seawater. While these tests provide results useful for the development of specific systems, the results m a y not be readily applicable to systems of different design or using different materials. Where water is pumped, such as in testing of condenser tubes and pipes, particular attention must be paid to the effects of turbulence and surface shear stress. The hydrodynamics at the test sample surface m u s t be similar to the hydrodynamics anticipated in service.

S P E C I M E N E X P O S U R E AND RETRIEVAL
An obvious but not trivial consideration in seawater corrosion testing is that the samples must not become lost prior to the end of the exposure period. The test racks and suspension systems must be resistant to corrosion failures during the exposure period. In-surface exposures, storms, mechanical damage by floating debris, vandalism, and m a n y others m a y result in specimen loss. Frequent inspection of the exposure site is necessary to identify potential problems before specimen loss occurs. In deep ocean exposures, storm damage is less of a problem, but methods for locating and handling the racks requires considerable planning and ocean engineering experience in order to expose and retrieve the specimens without loss or damage.

Static Testing in Surface Environments

Several test rack designs are described in Ref 3. For surface exposures where fouling accumulations are likely to he extensive, test racks that boldly expose the specimen surfaces such as shown in Fig. 3-3 and 3-6 of Ref 3 are preferred over basket-type racks such as shown in Fig. 3-7, where the spaces between the faces of the specimens can become completely clogged with fouling organisms and potentially affect the test results. As described in ASTM G 52, test racks should be fabricated from materials that are reasonably corrosion resistant. Wooden racks are usually limited to a one-year life. Aluminum alloy 5086 test racks may be suitable for exposures of up to five years. Welded nickel-copper alloy 400 racks have essentially indefinite life in surface seawater, but are expensive and heavy. Nickelcopper alloy 400 is subject to crevice attack in seawater and this m a y be significant on fasteners. Reinforced plastic structural shapes, fastened with corrosion-resistant fasteners such as titanium, are relatively inexpensive, lightweight, and durable for long exposure periods. In designing test racks and exposure facilities, consideration must be given to handling of the test racks. In many cases, material handling equipment will not be provided and the racks will be handled by hand. The total weight of the rack plus

Deep Ocean Testing

Deep ocean testing is performed to determine the effect of depth-related environmental variables on material performance. To determine the relative effects of variation in environment, tests sites with significant variation in environment should be selected. For example, where oxygen content is the major variable of interest, sites with high, minimum, and intermediate oxygen content should be used. To compare deep ocean test results with results from surface seawater, testing of replicate specimens in the deep ocean and in surface seawater is often performed. The emplacement and retrieval of deep ocean test samples is expensive and involves the coordinated efforts of

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various ocean engineering disciplines such as navigation, ship handling, rigging, oceanography, and marine geotechnology. As in all ocean operations, considerable planning is required for successful emplacement and retrieval of deep ocean corrosion test samples. Sample configuration and preparation for deep ocean testing is similar to that for surface seawater exposures. For deep ocean exposures it is c o m m o n to emplace and retrieve large assemblies of multiple racks containing individual samples. The test samples should be protected from atmospheric and salt spray corrosion during transit to the test site. This can be accomplished by transporting the racks below deck for small racks or by covering larger racks with plastic sheeting. The test rack assembly design is dependent on the deployment and retrieval method selected. One test rack assembly design and the method for emplacement and retrieval of the test rack is described in Ref 6. In deep ocean testing, the accumulation of fouling organisms is much less than in near surface waters and basket-type racks can be used as the spaces between the sample faces will not become clogged with fouling organisms. Contamination of samples by corrosion products from other test samples can be minimized by grouping samples of similar types in separate racks. Particular attention should be given to vertical location of test samples. For example, aluminum samples should be located above copper alloys as copper corrosion products falling onto the aluminum alloys can cause contamination of the aluminum alloys, whereas the aluminum corrosion products have little effect on the copper alloys. Painted carbon steel, 5083 and 5086 aluminum alloys, and reinforced plastic test racks and rack assemblies have all been successfully used for deep ocean testing. To provide different removal times, replicate rack assemblies can be emplaced and retrieved separately. As an alternative to removal of replicate racks, it is possible to design a rack assembly such that individual racks or even individual samples can be removed by remote operated vehicles or m a n n e d submersibles. Although not proven, autonomous systems that release racks or individual specimens at intervals for surface retrieval are within the capability of m o d e r n ocean engineering technology. Once these racks reached the surface they could report their location through satellite systems for location and recovery by a surface vessel.

SPECIMEN EVALUATION
The evaluation of the specimens in any corrosion test must be appropriate for the type of corrosion that actually occurs on the samples. In m a n y cases, the actual sample evaluation requirements will not be known until the samples are retrieved and examined visually. This can complicate the administration of the testing p r o g r a m as the cost of specimen evaluation and the time to perform the evaluation cannot be planned in advance. For example, if general corrosion is the only form of corrosion experienced, the cost of sample evaluation by mass loss m e a s u r e m e n t is relatively inexpensive, whereas a form of corrosion such as stress corrosion cracking may require a high cost evaluation. Upon removal from exposure, the specimens should be examined visually as soon as possible after retrieval. If more than a few hours will elapse between the removal of the specimens

and this initial examination, the samples should be rinsed with fresh water after removal. For deep ocean tests, this will usually be performed at sea and sufficient fresh water for this purpose must be provided. Whenever possible, the samples should be photographed to record their appearance upon retrieval. After initial visual examination, the specimens should be cleaned. ASTM G 52 gives guidelines for evaluation of specimens after exposure to surface seawater. In surface seawater exposures, the accumulation of fouling organisms may be removed using wooden or plastic scrapers and bristle brushes prior to chemical cleaning. In deep ocean and velocity tests, the accumulation of fouling organisms is usually very limited and scraping is usually not required. It may be appropriate to visually re-examine the samples and rephotograph them at this stage of the evaluation. The specimens should be cleaned in accordance with the methods r e c o m m e n d e d in ASTM G 1 or ISO 8407. The samples should then be remeasured to determine geometric changes and reweighed to determine mass loss. Nonuniform attack m u s t be evaluated using methods appropriate for the type of attack experienced. Pitting corrosion should be evaluated using the methods described in ASTM G 46. Pitting evaluation of a l u m i n u m alloys can also be performed using the practices recomm e n d e d in ISO 8993 and 8994. As crevice corrosion often results in pitting attack, crevice attack is frequently evaluated using techniques outlined in ASTM G 46. Due to the effect of material and surface condition on pitting, statistical analysis methods described in ASTM G 16 should be applied to estimating the confidence interval of the pitting. In addition, the statistical analysis methods described in ASTM G 16 can be applied to crevice corrosion data where not only the material and surface condition, but also the inevitable variability in crevice tightness may influence susceptibility. Other forms of attack such as exfoliation of aluminum alloys and dezincification of brasses require specialized evaluation and interpretation. Methods and standards for evaluation of exfoliation of aluminum alloys which are given in ASTM G 34 and G 66 are for materials exposed to artificial environments but may be used for evaluation of materials exposed to natural environments such as seawater. Many forms of attack can be best evaluated by microscopic or mechanical tests. ASTM E 3 gives standard methods for preparation of metallographic specimens, but does not provide specific guidelines for use of metallographic analysis in evaluation of corrosion. There are many standards for mechanical testing, such as ASTM A 370 for mechanical testing of steel products, that can be used in evaluating corrosion damage.

STANDARDS
Standards applicable to field testing in natural seawater are given below:

ASTM
E 3 G 1 Methods of Preparation of Metallographic Specimens Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens

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TESTS AND STANDARDS

MANUAL

G 15 Terminology Relating to Corrosion and Corrosion Testing G 16 Guide for Applying Statistics to Analysis of Corrosion Data G 3 0 Practice for Making and Using U-Bend StressCorrosion Test Specimens G 32 Test Method for Cavitation Erosion Using of Vibratory Apparatus G 34 Test Method for Exfoliation Corrosion Susceptibility in 2XXX and 7XXX Series Aluminum Alloys (EXCO Test) G 3 8 Practices for Making and Using C-Ring StressCorrosion Test Specimens G 39 Practice for Preparation and Use of Bent-Beam Stress-Corrosion Test Specimens G 46 Practice for Examination and Evaluation of Pitting Corrosion G 52 Practice for Exposing and Evaluating Metals and Alloys in Surface Seawater G 58 Practice for the Preparation of Stress-Corrosion Test Specimens for Weldments G 66 Method for Visual Assessment of Exfoliation Corrosion Susceptibility of 5XXX Series Aluminum Alloys (Asset Test) G 71 Guide for Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes G 73 Practice for Liquid Impingement Erosion Testing G 78 Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stainless Alloys in Seawater and Other Chloride-Containing Aqueous Environments G 82 Guide for Development of a Galvanic Series for Predicting Galvanic Corrosion Performance

7539-2

7539-3

7539-5

8407 8993

8994

Corrosion of Metals and Alloys-Stress Corrosion Testing-Part 1: Preparation and Use of BentBeam Specimens Corrosion of Metals and Alloys-Stress Corrosion Testing-Part 3: Preparation and Use of U-Bend Specimens Corrosion of Metals and Alloys-Stress Corrosion Testing-Part 5" Preparation and Use of C-Ring Specimens Metals and Alloys-Procedures for Removal of Corrosion Products from Corrosion Test Specimens Anodized Aluminum and Aluminum Alloys-Rating System for the Evaluation of Pitting CorrosionChart Method Anodized Aluminum and Aluminum Alloys-Rating System for the Evaluation of Pitting CorrosionGrid Method

REFERENCES
[z] Corrosion in Natural Waters, ASTM STP 1086, C. H. Baloun, Ed., ASTM International, West Conshohocken, PA, 1990. [2] Corrosion in Natural Waters--2nd Volume, ASTM STP 1300, R. N Kain & W. T. Young, Eds., ASTM International West Conshohocken, PA, 1997. E32 La Que, F. L., Marine Corrosion Causes and Prevention John Wiley & Sons, New York, 1975, pp. 45-52. E42 La Que, F. L., Marine Corrosion Causes and Prevention John Wiley & Sons, New York, 1975, pp. 56-57. [5] La Que, F. L., Marine Corrosion Causes and Prevention, John Wiley & Sons, New York, 1975, pp. 62-63. E62 Reinhart, F. M., Technical Report R-834: Naval Civil Engineering Laboratory, Corrosion of Metals and Alloys in the Deep Ocean, February 1976.

International Standards Organization (ISO)

7539-1 Corrosion of Metals and Alloys-Stress Corrosion Testing-Part 1: General Guidance on Testing Procedures