.

Immersion Testing
R i c h a r d A. C o r b e t t 1

MOST CHEMICALPLANT processes are complex. Materials of construction for process equipment and piping must be selected with care to assure corrosion-free operation of those plants. In a well designed plant, materials selection is based on a n u m b e r of factors: prior service history, field inplant corrosion tests, pilot plant corrosion tests and laboratory corrosion tests, in that relative order of usefulness. ~Often, actual service history regarding materials performance is not available because plants kept poor records, plant personnel were not trained to evaluate corrosion failures, or, in the case of new processes, because there is no service history. The same can be said for field in-plant corrosion tests. Pilot plant testing is usually the best alternative in such cases, but such facilities are typically operated only for short runs and are not well suited for gathering long-term corrosion performance data. For all of these reasons, laboratory corrosion tests are frequently the best available source of data for materials selection. If these tests are well planned, they can provide the information necessary for intelligent plant design and proper selection of materials of construction. Laboratory tests also offer unique advantages over in-plant tests: acceleration of results through variation of parameters or use of electrochemical methods, ability to vary process conditions at will to develop safe "windows" of operation for selected materials, plus the ability to look at a limitless n u m b e r of candidate materials quickly and at relatively low cost. If poorly designed or improperly r u n and interpreted, all corrosion tests can give misleading information likely to lead to costly materials selection errors.

when concentrated inside a pit or crevice. Such factors must be considered when designing a laboratory corrosion test. Laboratory corrosion test parameters are usually separated into two groups: chemical and physical. Chemical parameters include not only the concentration of various compounds, but also such factors as dissociation, pH, phase equilibrium (especially vapor phase chemistry), dissolved gases, conductivity, and degradation reactions caused by the construction materials themselves. Relevant physical parameters include temperature (including temperature gradients and heat transfer), pressure, flow velocity, surface area effects (such as ratio of volume-to-surface area), and time (test duration). Also important are cyclical changes in these parameters. It is often impractical to study effects of all these variables, so educated decisions must be made as to which variables might be important in a particular process and how m a n y variations of each shall be included in the corrosion test program. Depending u p o n the expected mechanism of corrosion (i.e., general or localized pitting, crevice, cracking or galvanic attack), different tests can be designed to detect the susceptibility to attack. Table 1 summarizes some of the more comm o n forms of corrosion and the appropriate laboratory tests used to evaluate the susceptibility of a material to a specific mode of attack [1]. Many of these tests are accelerated rather than simulated service (e.g., an accelerated test used to detect susceptibility to a form of corrosion), and are routinely performed to provide information for use in: * fundamental corrosion evaluation * failure analysis corrosion prevention or control acceptance of quality assurance environmental issues involving corrosion new alloy/nonmetallic or product process development Custom and unique test set-ups to evaluate heat transfer, thermal shock, velocity, fatigue, or abrasion/wear effects are also used to determine the susceptibility of a material to a specific environment or process.

BASIC PRINCIPLES
For any given chemical process it is not always possible to predict which forms of corrosion will occur, or even which chemical or parameter will dominate the corrosion scenario. Process flowcharts define certain chemicals and "normal" operating conditions, but frequently overlook trace elements (impurities), transient conditions, or chemical intermediates. Such factors can have a major effect on corrosion in that process. Subtle changes in pH, for example, can shift electrochemical potentials from, say, a passive range into a pitting range. Certain ionic species, while having little effect in the bulk environment, can act as accelerating charge carriers 1Corrosion and Materials Research Institute, 60 Blue Hen Drive, Suite 1000, Newark, DE 19713-3406

Test Conditions
The selection of the conditions for a laboratory corrosion test should be determined by the expected results and the purpose of the test. If the test is to be a guide for the selection of a material for a particular application, then the limits of the controlling factors u n d e r service conditions must

139

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CORROSION TESTS AND STANDARDS MANUAL

TABLE 1--Common forms of corrosion and laboratory evaluation tests.

Mode of Attack General Corrosion

Stress Corrosion Cracking

Pitting Corrosion

Crevice Corrosion Intergranular

Erosion Corrosion De-alloying

Galvanic

Occurrence in Industry (Typical) EvaluationTests 28 % Total Immersion Tests (Atmospheric & Autoclave) Multiphase (liquid, vapor, condensate, interface) Tests Hot Wall Electrochemical Polarization Electrochemical Impedance 24 % Boiling Chloride U-Bend Tests Wick Test Polythionic Acid Cracking Test Caustic Solution Cracking Tests Custom Process Solution Testing 15 % Ferric Chloride Immersion Test Cyclic Potentiodynamic Polarization (Hysteresis) Critical Pitting/Crevice Temperature Determination Seawater/Marine Exposure Testing Surgical Implant Test Green Death Test Critical Pitting Potential Test (Potentiostatic) 2% Critical Pitting/Crevice Temperature Determination Multi-Crevice Washer/Process Solutions 15 % Electrolytic Oxalic Acid Screening Test Ferric Sulfate-Sulfuric Acid (Streicher Test) Nitric Acid (Huey Test) Copper Sulfate-Sulfuric Acid Test EPR Test (Electrochemical Potentiokinetic Reactivation) 7% Miller Test Rotating Disk Test 2% Total Immersion Testing for De-alloying Galvanic Couple Test Electrochemical Tests Exfoliation of Aluminum Tests 1% Dissimilar Metal Couple Immersion Test Galvanic Couple Test Zero Resistance Ammeter Electrochemical Tests

ASTM Std. (Typical) G 31 G 31 G5 G 106 G 36 C 692 G 35 G 48 G 61 G 48 G 78 F 2129 G5 G 61 G 48 A 262[A] A 262[B] A 262[C] A 262[D] G 108 G 75 G 31 G 71 G5 G 34 G 31 G 71 G3

be determined. Normally these factors include, but are not limited to, service temperature ranges, process fluid flow rates, atmosphere (i.e., air, nitrogen, argon, etc.), aqueous/organic phases, and other characteristics of the bulk solution (e.g., impurities or contaminants). There should be an effort to ensure duplication of the service conditions in the laboratory corrosion test, with conditions adequately controlled during the entire test duration to ensure reproducible results. Experience shows that at least duplicate test specimens should be exposed in each test. Under laboratory tests, corrosion rates of duplicate specimens are usually within 10 % of each other, when the attack is uniform. Occasional exceptions, in which a large difference is observed, can occur under conditions of borderline passivity of alloys that depend on a passive film for their resistance to corrosion. If the rate difference exceeds 10 %, re-testing should be considered, unless it is observed that localized attack is predominant. Corrosion rates are calculated assuming a uniform loss of metal, and therefore when specimens are attacked nonuniformly, the calculated corrosion rates indicate only the relative severity of attack and should not be used to predict the performance of an alloy to the test solution. In such cases, weight loss per unit of surface area may be used to avoid implying a u n i f o r m penetration rate. Ideally, laboratory tests should use actual solutions from plant processes, which is often impractical. Therefore, test

solutions are prepared from reagent chemicals and water. No matter what the source of the test solution, its composition should be controlled accurately and should be described in the test report as completely as possible. Minor constituents should not be overlooked because they often affect the corrosion rate. Chemical content should be reported as percentage by weight, molarity, or normality. If percentage is given, the solution density should also be provided so that molarity can be calculated. The composition of the test solution should be checked before and after testing by analysis to determine the extent of change in composition. Evaporation losses should be controlled by a constant level device, or by frequent additions of the evaporating solution, to m a i n t a i n the original volume within _+1%. In some situations, the composition of the test solution may change as a result of the build-up of corrosion products in the solution, catalytic decomposition, or by reaction with the test specimens. If possible, these changes should be determined, and where required, the consumed constituents should be replenished or a fresh solution provided periodically. Experience has shown that wherever possible, only one type of alloy or family of nonmetallics should be exposed in a given test apparatus. If several alloys or nonmetallics are exposed in the same apparatus the corrosion products from one material may affect the corrosion rate on another material. For example, copper corrosion products can inhibit corrosion of stainless steel but accelerate corrosion of aluminum.

CHAPTER 9--IMMERSION TESTING 141

If different alloys are coupled in a particular process, these couples must be reproduced in the laboratory test. F o r example, in ASTM Standards D 1384, D 2570, or D 2758, copper, brass and solder, found in the radiator and heaters in automobiles, are electrically connected and tested in the same laboratory apparatus. each other physically and electrically, and to insulate the specimens from any metallic container or supporting device used with the apparatus. The shape and form of the specimen support should assure free contact of the specimen with the test solution, the liquid/vapor interface or the vapor phase, whichever is applicable. Common supports include glass or ceramic rods or hooks, glass cradles, fluorocarbon plastic thread or string, and various insulated or coated metallic supports.

Physical Parameters Temperature

The t e m p e r a t u r e of the test solution should be controlled within --IC and should be stated as such in the report of test results. If no specific temperature, such as boiling, is required or if a temperature range is selected, this should also be reported. F o r processes that are c o n d u c t e d u n d e r a m b i e n t conditions, the l a b o r a t o r y tests should be conducted at the highest t e m p e r a t u r e anticipated for stagnant storage during the s u m m e r months. This t e m p e r a t u r e m a y be as high as 55C. L a b o r a t o r y tests c o n d u c t e d at the temp e r a t u r e of a process solution m a y provide misleading results if heat transfer occurs as the metal heats the process stream.

Test Duration
The duration of any laboratory test should be determined by the nature and purpose of the experiment. The a m o u n t of corrosion attack under any given test condition will be directly dependent on the duration of the test. Often it is assumed that corrosion is a linear function of time, and often this is incorrect. Yet this assumption is implied when a corrosion rate is stated. Since corrosion m a y not be linear, it is i m p o r t a n t that tests be m a d e with specimens exposed for an increasing i n c r e m e n t of time, with some durations as long as possible to enable reliable extrapolation of performance. Under such test parameters, it is r e c o m m e n d e d to expose several identical specimens in the c o r r o d a n t and remove t h e m individually at different times over an extended duration. This technique is called the "Planned Interval Test" [2], and the p r o c e d u r e a n d evaluation of the results are presented in Table 2. Materials that experience severe corrosion usually do not require long duration exposure to obtain accurate corrosion rates, and c o m m o n testing periods are 24-240 h. Although this assumption is valid in m a n y cases, there are situations where it is not valid. For example, a l u m i n u m exposed to solutions of sodium hydroxide corrodes at an extremely high rate, often in excess of an inch per year, while it is building a protective corrosion product film; then the rate decreases dramatically so that further corrosion is almost negligible, provided the film is not damaged. Likewise, stainless steels that form passive films m a y have that film broken down under prolonged exposure and subsequently experience r a p i d attack. Experience suggests that laboratory tests of long periods are considerably more realistic than those conducted for short duration. However, this m u s t be qualified because corrosion should not proceed to where the original specimen size or the exposed area is drastically reduced or where the material is perforated or dissolved.

Aeration/Deaeration
Unless specified, the test solution should not be aerated or deaerated. Most laboratory tests used to replicate process equipment should be controlled with the natural atmosphere inherent under process conditions, such as the vapors of the boiling solution. If aeration or deaeration is used, the test specimens should not be located in the direct stream of the gas sparge tube. Undesirable effects can be encountered if the gas stream impinges on the test specimens.

Solution Velocity
The effect of process solution velocity is not usually det e r m i n e d in n o r m a l l a b o r a t o r y tests, although specific tests have been designed for this purpose. Tests u n d e r boiling conditions should be c o n d u c t e d with m i n i m a l heat input, a n d inert m a t e r i a l boiling chips should be used to avoid excessive turbulence a n d bubble impingement. For tests conducted below the boiling point, thermal convection generally is the only source of liquid velocity in the l a b o r a t o r y test. For test solutions with high viscosities or multiple phases, supplemental controlled stirring m a y be recommended.

Test Solution Volume

The volume of the test solution should be large enough to avoid any appreciable change in its corrosiveness either through depletion of the corrodant or accumulations of corrosion products that m a y affect further corrosion. The preferred minimum solution volume-to-specimen surface area ratio is 20 mL/cm 2.

T Y P E S OF T E S T S
The type of laboratory i m m e r s i o n test to be used will be determined mostly by the environmental conditions that are to be simulated. F o r example, if the equipment is i m m e r s e d in service, then the test specimens should be i m m e r s e d in the laboratory test; if the exposure is alternating immersion and atmospheric exposure, then a cyclic exposure test to wet/dry conditions should be used. Another determining factor is the duration of exposure for arriving at the desired results, which is associated with the degree of acceleration that will be required of the test method.

Methods of Supporting Test Specimens

It is important that the supporting device and the test apparatus should not be affected by or cause contamination of the test solution. The method of supporting test specimens will vary with the apparatus used for conducting the test, but should be designed to insulate the specimen from

142

CORROSION TESTS AND STANDARDS MANUAL

T A B L E 2--Planned interval test.

~ Time Specimen #
1

0
I ~

1
I

t
I

t+l
I

2 3
4

-~ -~
4(

Calculated Specimen #3 - #2

The test specimens are placed in the same test vessel which contains the corrosive solution. The test conditions are kept constant during the duration of the test program. The parameter being measured is the penetrationa, as defined below. Criteria Interpretation --Unchanged if 1= 4 Liquid Corrosiveness --Decreases if 1>4 ---Increases if 1<4 --Unchanged if 4=5 Metal Corrodibility --Decreases if 4>5 --Increases if 4<5 Other Combinations of Interpretation: Liquid Corrosiveness Metal Corrodibility Criteria 1. unchanged unchanged 1 -- 4 = 5 2. unchanged decreases 1=4 > 5 3. unchanged increases 1=4 < 5 4. decreases unchanged 1>4 = 5 5. decreases decreases 1>4 > 5 6. decreases increases 1>4<5 7. increases unchanged 1<4=5 8. increases decreases 1<4>5 9. increases increases 1<4 < 5 Example of Planned Interval Corrosion Test Program Exposure: Test specimens were of AISI Type 316L. (UNS $31603) stainless steel (density 7.98 g/cm3), with dimensions of 25 x 50 3 cm (1 x 2 x ]/8 in.), immersed in 500 mL of 15 % methylsulfonic acid + 5 % sulfuric acid, balance water, at atmospheric pressure and 45C. Specimen Number
1

Duration Days 0-1 04 0-5 4-5 calc. 3-2

Mass Loss, mg 1495 2240 2280 95 40

Penetrationa mm mils 0.064 0.095 0.097 0.004 0.002 2.4 3.6 3.7 0.15 0.06

Apparent Corrosion Rateb mrn/y mpy 23 8.7 7.1 1.5 0.7 880 330 270 55 22

2 3 4 5 a

. (mass loss in mg)(C-factor) Penetratmn = (area in mm 2 or in.2)(density in g/cm3)

where C = 1 for ram: or C = 0.061 for mils bApparent Corrosion Rate (Penetration in mm or mils)365 time in days From penetration information: Specimen 1 > 4 > 5 Based on the interpretation criteria, the liquid has decreased its corrosiveness during the test, and suggests the formation of a protective film owing to a decrease in metal corrodibility. The p r i n c i p a l r e a s o n for a c c e l e r a t e d t e s t i n g is t h e n e e d to o b t a i n results s o o n e r t h a n c a n b e o b t a i n e d u n d e r field conditions. A c c e l e r a t i o n is a c h i e v e d b y l e n g t h e n i n g t h e e x p o s u r e to t h e critical c o n d i t i o n s , o r b y i n t e n s i f y i n g t h e c o n d i t i o n s so t h a t t h e c o r r o s i o n r a t e is i n c r e a s e d . The f o r m e r m a y b e achieved by exposing a test s p e c i m e n to a process condition a n o r d e r o f m a g n i t u d e l o n g e r t h a n actual p r a c t i c e . F o r exa m p l e , if a vessel is to b e b a t c h p r o c e s s e d w i t h a c h e m i c a l for 24 h, t h e n a l a b o r a t o r y c o r r o s i o n e x p o s u r e o f 240 h should be considered. Intensifying the test conditions may b e a c h i e v e d b y i n c r e a s i n g t h e s o l u t i o n acidity, salt c o n c e n t r a t i o n , t e m p e r a t u r e , o r o t h e r p a r a m e t e r s . I n s o m e cases, the physical p a r a m e t e r s m a y b e c h a n g e d , s u c h as t h e a m o u n t o f s t r e s s o r t h e d e g r e e o f fatigue. O n c e t h e service c o n d i t i o n s o f t h e t e s t h a v e b e e n d e t e r m i n e d , a n d e v a l u a t i o n t e s t s for all f o r m s o f c o r r o s i o n t h a t m i g h t o c c u r h a v e b e e n d e s i g n e d , t h e n t h e y s h o u l d b e rep e a t e d a s u f f i c i e n t n u m b e r o f t i m e s to d e t e r m i n e w h e t h e r it m e e t s t h e d e s i r e d reliability s t a n d a r d for r e p r o d u c i b i l i t y . C h a n g e s in t h e t e s t p r o c e d u r e m a y b e r e q u i r e d if t h e reliability is n o t satisfactory. If the test p r o c e d u r e is to b e u s e d b y o t h e r laboratories, e i t h e r to qualify o n t h e basis o f a specification o r simply to c o m p a r e results a m o n g laboratories, t h e n it is i m p o r t a n t t h a t r e p r o d u c i b i l i t y of results be d e t e r m i n e d . This is a c c o m p l i s h e d t h r o u g h r o u n d - r o b i n tests t h a t are c o n d u c t e d a m o n g i n t e r e s t e d laboratories to develop s t a n d a r d test p r o c e d u r e s , s u c h as t h o s e t h a t are d e v e l o p e d b y ASTM International, Comit6 E u r o p e a n N o r m a l i z a t i o n (CEN), I n t e r n a t i o n a l Org a n i z a t i o n for S t a n d a r d i z a t i o n (ISO), J a p a n e s e S t a n d a r d s Association (JSA), Materials T e c h n o l o g y Institute (MTI) o f t h e C h e m i c a l P r o c e s s Industries, a n d NACE International.

CHAPTER 9 - - I M M E R S I O N T E S T I N G
TABLE 3--Standard corrosion test procedures.

143

NACE S T A N D A R D
No. TM0169 TM0171 TM0174 TM0274 TM0374 TM0177 TM0284 TM0185 TM0286 Title Laboratory Corrosion Testing of Metals at Atmospheric Pressure Autoclave Testing of Metals in High Temperature Water Laboratory Methods for the Evaluation of Protective Coatings Used as Lining Materials for Immersion Service Dynamic Corrosion Testing of Metals in High Temperature Water Laboratory Screening Tests to Determine the Ability of Scale Inhibitors to Prevent the Precipitation of Calcium Sulfate and Calcium Carbonate from Solution Testing of Metals for Resistance to Sulfide Stress Cracking at Ambient Temperatures Test Method for Evaluation of Pipeline Steels for Resistance to Stepwise Cracking Evaluation of Internal Plastic Coatings for Corrosion Control of Tubular Goods by Autoclave Testing Cooling Water Test Units Incorporating Heat Transfer Surfaces

ASTM S T A N D A R D S
No. A 262 A 763 C 692 D 1384 D 2570 D 2758 F 2129 G1 G3 G4 G5 G 28 G31 G 34 G35 G 36 G 44 G 46 G 48 G 49 Title Practices for Detecting Susceptibility to Intergranular Attack in Austenitic Stainless Steels Practices for Detecting Susceptibility to Intergranular Attack in Ferritic Stainless Steels Method for Evaluation of Insulation (used to measure susceptibility to stress corrosion cracking) Test Method for Corrosion Test for Engine Coolants in Glassware Test Method for Simulated Service Corrosion Testing of Engine Coolants Method of Testing Engine Coolants by Engine Dynamometer Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements to Determine the Corrosion Susceptibility of Small Implant Devices Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens Practice for Conventions Applicable to Electrochemical Measurements in Corrosion Testing Method for Conducting Corrosion Coupon Tests in Plant Equipment Recommended Practice for Standard Reference Method for Making Potentiostatic and Potentiodynamic Measurements Test Methods of Detecting Susceptibility to Intergranular Attack in Wrought Nickel-Rich, Chromium-Bearing Alloys Practice for Laboratory Immersion Corrosion Testing of Metals Test Method for Exfoliation Corrosion Susceptibility in 2XXX and 7XXX Series Aluminum Alloys Practice for Determining the Susceptibility of Stainless Steels and Related Nickel-Chromium-Iron Alloys to Stress-Corrosion Cracking in Polythionic Acids Practice for Performing Stress-Corrosion Cracking Tests in a Boiling Magnesium Chloride Solution Recommended Practice for Alternate Immersion Stress Corrosion Testing in 3.5% Sodium Chloride Solution Practice for Examination and Evaluation of Pitting Corrosion Test Method for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by the Use of Ferric Chloride Solution Recommended Practice for Preparation and Use of Direct Tension Stress Corrosion Test Specimens Practice for Conducting Atmospheric Corrosion Tests on Metals Test Method for Conducting Cyclic Humidity Tests Practice for Conducting Cyclic Potentiodynamic Polarization Measurements for Localized Corrosion Guide for Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes Test Method for Determination of Slurry Ahrasivity (Miller Number) and Slurry Abrasion Response of Materials (SAR Number) Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stainless Alloys in Seawater and Other Chloride-Containing Aqueous Environments Practice for Verification of Algorithm and Equipment for Electrochemical Impedance Measurements Test Method for Electrochemical Reactivation (EPR) for Detecting Sensitization of AISI Type 304 and 304L Stainless Steels

G 50
G 60 G61 G71 G 75 G78 G 106 G 108

MTI METHODS
No. MTI 1 MTI 2 MTI 3 MTI 4 MTI 5 Title Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Standard Ferric Chloride Solution Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Cracking in a Boiling Magnesium Chloride Solution Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative in Sodium Chloride Solutions Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Cracking in a Sodium Chloride Drop Evaporation System Resistance to Corrosion in Selected Media Resistance to Crevice Corrosion in a Resistance to Stress Corrosion Resistance to Crevice Corrosion Resistance to Stress Corrosion

It is n o t u n u s u a l to u s e a l a b o r a t o r y test p r o c e d u r e for w h i c h t h e r e is n o direct c o r r e l a t i o n w i t h service o r field results. S o m e t i m e s c o r r e l a t i o n c a n n o t b e o b t a i n e d i m m e d i ately b e c a u s e service results are e i t h e r n o t available o r are n o t p r a c t i c a l to o b t a i n i n a r e a s o n a b l e time. F o r example,

s u p p o s e a c o m p a n y w i s h e s to offer a lifetime w a r r a n t y of a c o a t i n g e x p o s e d to a n i n d u s t r i a l e n v i r o n m e n t b u t n e e d s d a t a to b a c k u p t h e i r claim. H u m i d i t y c h a m b e r tests plus ultraviolet l i g h t e x p o s u r e c a n give "best guess" results in a m a t t e r of weeks r a t h e r t h a n years of actual e x p o s u r e to t h e elements.

144

C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

2,5 x
3,2

Because the laboratory test is designed a r o u n d a synthesized or contrived environment, it is important that the results provide reliable information that can be used to make decisions on candidate materials of construction.

cm Reducer

2,5 x ~ 2.5 c~
'

3.2

41~

~s
Heater I

cm Reducer QRIFS FOR LPR & CORROSION PECIHENS

Simple Immersion Tests

There are m a n y variations in a laboratory immersion test. ASTM G 31 and NACE International Standard Test Method TM-01-69 are general guides on how these tests may be performed (see Table 3 for these and other standard corrosion test procedures). Basically, small pieces (i.e., 2.5-cm by 5-cm by 0.3-cm thickness) of the candidate material are exposed to the test medium, and the loss of weight of the material is measured for a given period of time. I m m e r s i o n testing remains the best m e t h o d for screening and eliminating from further consideration those materials that obviously should not be considered as useable materials. This technique is frequently the quickest and most economical means for providing a preliminary selection of the best candidate materials. Probably the most serious disadvantage of this method of corrosion study is the assumed average-time weight loss. The corrosion rate could be high initially and then decrease with time. In other cases, the rate of corrosion might increase very gradually with time, it could cycle, or it could be some combination of these things. Remember, "corrosion is not an exact science," and no written information can take the place of a corrosion consultant. Besides the full immersion test, there are several variations that could be used to accentuate certain types of exposure conditions. For example, the test specimen can be partially i m m e r s e d in an electrolyte (liquid or solid) to create an oxygen concentration cell at the vapor-liquid/solid interface (as opposed to an occluded cell).

BRINE LOOP SPECIMEN

575 L

FIG. 1--Scaled-down model, circulating brine cooling/heating heat exchanger system.

Alternate Immersion Testing

Another variation of the immersion test is the cyclic test procedure where a test specimen is i m m e r s e d for a period of time in the test environment, then removed and dried (either air dry or use of heat lamps), then re-immersed to continue the cycle. Normally hundreds of these cycles are completed during the course of the test program. In ASTM G 60, test specimens are dipped in a test solution before being exposed to atmospheres varying in relative humidity. The intent of the test is to develop a layered corrosion product similar to that found on sheltered outdoor exposure test specimens. These tests can be either manually performed or conducted in apparatus equipped for automatic cycling.

of brine corrosion, and use of inhibitors, in the piping system is simulated by the use of full-sized pipe spool pieces of different alloy composition. The test model further incorporates the use of small test specimens and electrochemical monitoring probes. Acceptance tests attempt to use actual service conditions and environments to control the quality of the material being supplied as material of construction. A classic example is the use of acceptance testing for susceptibility of alloys to intergranular corrosion under boiling nitric acid service using the ASTM A 262, Method C test procedure. Another example is to simulate down-hole sour gas or sour oil piping environments by use of the NACE International TM-01-77 procedure for hydrogen induced cracking susceptibility exposure to aqueous hydrogen sulfide.

T E S T S P E C I M E N PREPARATION, CLEANING, AND EVALUATION Preparation

One of the most important parts of corrosion testing is the preparation of the specimen or part to be tested. Although it is desirable to use the same surface conditions for the tests as those found in service, this is not always possible because of the variability of the material's surface in service, but it should always be a desirable objective. Test specimens should have many of the characteristics of the material that will be used for the service application, which typically includes composition (elemental chemistry), mechanical properties (strength, hardness, etc.), form (sheet, plate, bar, etc.), size and shape (surface area-to-corrodant volume ratio, flat-stock, end-grain exposure, etc.), metallurgical treatment (heat treatment, welding, hot or cold working, etc.), surface finish (dye-cut, sheared, saw-cut, mill scale, ground and polished, electropolished, etc.), identification procedures (stamped, engraved, etc.), and cleaning procedures (passivated, degreased, water washed, etc.).

Simulation and Acceptance Testing

The laboratory test should try to simulate actual service conditions. Occasionally, this may be accomplished simply by building a scaled-down model of a particular operation. If the service operation is not too large, actual parts of the system can be modified to a laboratory bench-top to permit a better simulation of the actual process. There are many examples where this approach has been applied. An excellent example is depicted in Fig. 1 of a circulating brine cooling/heating heat exchanger system. The effect

CHAPTER 9 - - I M M E R S I O N TESTING
Although the size and shape of the specimen will depend on the purpose of the test, rectangular specimens of the dimensions 2.5 cm by 5 cm by 0.3 cm thick are common. A typical variation is found when a corrosion test requires the specimen to be mechanically stressed as part of the evaluation procedure. It would be normal in this case to use a standard tensile test specimen for the corrosion test. Other examples are the use of disk-shaped specimens for rotational erosion tests, or special configurations for stress corrosion, exfoliation, or crevice tests. A reproducible surface finish is desirable for repetitive testing. A c o m m o n final surface finish for test specimens is No. 120 grit abrasive p a p e r or cloth, or their equivalent. Whenever possible or known, the same metallurgical treatInent should be used for the test specimen as used for the service part, because heat treatment or cold work can change the surface composition, grain size and structure, and residual stresses. Mechanical operations can affect the materials surface. Cutting, shearing, grinding, and polishing operations should be performed to avoid excessive workhardening or stresses. There are m a n y ways to identify test specimens, such as marking with ink or paint, incise marking, or stamping numbers or letters with a tool that leaves an impression in the surface. Precautions should be observed with the use of any system to avoid excessive stresses, the creation of sites for pit initiation, or the use of materials that will be reactive with the metal. It is important that the identification endures the duration of the test, so some of these problems m a y have to be tolerated.

145

Therefore before cleaning the exposed specimens should be observed and their appearance recorded. Although this method is qualitative it is helpful in assessing the nature and extent of corrosion. Corrosion rates are based on weight loss (consumption of the base material) during the duration of exposure. Therefore cleaning the specimens of their corrosion products is a vital step in the corrosion test protocol. Generally, the cleaning procedure should remove all corrosion products from the specimen with a m i n i m u m removal of sound material. Set procedures for specimen cleaning vary depending on the type of the material being cleaned, and on the degree of adherence of corrosion products. Cleaning methods are divided into three general categories: mechanical, chemical, and electrolytic. Detailed procedures are described in ASTM G 1. After cleaning, the specimens are re-weighed. The weight loss during the test duration is used as the principal measure of corrosion: the corrosion rate.

Evaluation of Results
Even though each step of the corrosion test procedure is important, if not properly evaluated the results can be misused or can lead to erroneous conclusions. It is important to r e m e m b e r that the corrosion rate is based on the extrapolation of results from short-term tests. For example, corrosion rates m a y be reported in the terms of millimeters per year (mmpy) on the basis of results obtained from exposure of one month, one week, or one day. The degree of extrapolation ranges from a multiple of 12 to 365. Since corrosion is rarely linear, with initial rates being extremely high, it is important that the extent of extrapolation be considered in the evaluation phase of the test program. After the specimens have been re-weighed, they should be carefully examined visually and under low-power magnification for the presence of localized attack. If there are pits or creviced areas, the extent of the depth of attack can be measured with a pit gauge or a calibrated microscope which is first focused on the bottom of the pit and then the specimen surface edge (see ASTM G 46 for details). If the test material is suspected of being subject to dealloying (such as dezincification) o r intergranular corrosion, a cross section of the specimen should be microscopically examined. If embrittlement is suspect, simply bending the specimen m a y determine this susceptibility.

Cleaning Specimens Before Testing

After the test specimen has been prepared for testing, it must be cleaned to remove oil, soil, and fingerprints. Either chemical or electrochemical means can be used for the final cleaning, but the effects of cleaning on surface topography must be considered. A r e c o m m e n d e d procedure involves scrubbing with a toothbrush and a bleach-free scouring powder, followed by thorough rinsing in water and a suitable solvent (such as acetone or methanol) and warm air-drying. For relatively soft metals (such as aluminum, magnesium and copper) scrubbing with abrasive powder is not always desirable as it can m a r the surface of the specimen. Ultrasonic techniques may be used, as necessary. If coatings are to be evaluated, it is important that the metal surface be cleaned and the coating applied in a similar m a n n e r to that used in the service application. This step may involve using regular production facilities. After cleaning, the test specimens are weighed on an analytical balance to an accuracy of -+0.5 mg, and dimensional measurements are made to _+0.001 cm to permit accurate calculation of the exposed surface area.

PRECAUTIONS AND VALIDITY OF R E S U L T S

Most metals and alloys are thermodynamically unstable and will therefore attempt to revert back to their native stable state (e.g., red rust or ferric oxide). The rate at which this reversion (corrosion) occurs varies with the particular alloy and the environment to which it is exposed. The purpose of the laboratory corrosion test is to best simulate these conditions, determine corrosion rates, and predict the various modes of attack. Although each data point is important, the results can be misinterpreted and lead to the wrong conclusion if they are not properly evaluated. Therefore, a laboratory corrosion test can be most useful only if the test results can be compared with actual plant or process service experience.

Cleaning Specimens After Testing

The effect that corrosion and the resulting corrosion products have on the test specimen should be determined in order to evaluate the severity of the attack. Locations of deposits or corrosion products are important in evaluating localized attack such as pitting, crevice attack or cracking.

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The precautions mentioned throughout this section focus on the planning and execution of the laboratory test and particularly in the interpretation of results. These cautions are not intended to provide a false impression that corrosion tests are unreliable. Rather, they are intended to emphasize that when corrosion test procedures are executed carefully and interpreted intelligently our knowledge of corrosion may be enhanced. That this is true is evident by the few n u m b e r of cases of unexpected failures by corrosion or gross misapplication of corrosion resistant materials. ASTM International and NACE International. Other organizations, which also issue standards for the m a n y types of corrosion tests, are CEN, ISO, JSA, and MTI. These professional organizations have produced industry accepted recommended practices and test procedures (see Table 3), which allow comparison with others through direct interaction or published data.

REFERENCES
[1] Corbett, R. A., "Using Corrosion Tests Effectively," Chemical Processing, Vol. 50, No. 12, Oct. 1987, pp. 28-32. [2] Wachter, A. and Treseder, R. S., "Corrosion Testing Evaluation of Metals for Process Equipment," Chemical Engineering Progress, Vol. 43, June 1947, pp. 315-326.

STANDARDS
Reference is made throughout this section to standards and test methods issued regularly by technical societies such as