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Material

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ACCELERATED CORROSION TESTING

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A MPTIAC

Jeffrey Guthrie, Brigitte Battat and Chris Grethlein AMPTIAC, Rome, NY

“Corrosion is Corrosion” – we have heard that all too often at the AMPTIAC inquiry desk. In our experience, corrosion is one of the most misunderstood and mischaracterized forms of material degradation. Consequently, corrosion analysis and mitigation methods tend to be some of the most misapplied. This MaterialEASE is the third and final installment excerpting a new AMPTIAC State-of-the-Art Review entitled “Accelerated Testing: A Methodology for Determining Life and Degradation of Materials”. It will be published in the near future. This article examines the fundamentals of accelerated corrosion testing, the associated pitfalls therein, and what tools today’s materials engineer will have to battle corrosion. The Problem: As recently as 1995, a major study concluded that the cost impact of corrosion to the U.S. economy totaled nearly $300 billion annually.[1] This represents nearly 4% of the Gross Domestic Product, and is a conservative estimate at best – indirect costs, which are substantial and mostly unreported, would greatly inflate the total estimated cost. Estimates suggest that about two-thirds of present corrosion-related costs are unavoidable. In addition, corrosion affects our Nation’s force effectiveness and readiness levels through the diminished safety and reliability of structures, mechanisms and electronics. In many cases, corrosion is the life-limiting factor of a component. Corrosive failures can occur unexpectedly at the worst possible moment. Corrosion testing can consume enormous blocks of time; particularly in the case of outdoor atmospheric tests. Unfortunately, the timescales involved in such tests preclude the opportunity for proper materials selection. In typical circumstances, new systems may be halfway through their lifecycle before real data on the fielded system would indicate any corrosion problems. Under the right conditions, accelerated testing may yield data beneficial in selecting the most corrosion resistant materials for an application. Accelerated testing isn’t limited to the design stage of a system’s lifecycle, but can be used to provide in-field support, as the emergence of sudden corrosion problems on fielded systems requires quick answers. Managing corrosion in structural components and critical systems, to extend service life and ensure reliability, is paramount. Effective corrosion control requires meaningful test data in a reasonable time frame such that it may be employed to influence materials selection and protection efforts. There are presently hundreds of existing accelerated corrosion test methods and no doubt there will be many more in the future.

Background The most accepted definition for corrosion is the destruction of material due to a chemical reaction of the material with its environment. Generally, this destruction takes place on its surface in the form of material dissolution or redeposition in some other form. Metallic systems are the predominant materials of construction, and as a class, are generally susceptible to corrosion. Consequently, the bulk of corrosion science focuses upon metals and alloys. Corrosion does occur in polymers and ceramics but the mechanisms are quite different from those of metals. As such, this article limits itself to a discussion of metallic corrosion. The Electrochemical Process Corrosion consists of an oxidation reaction and a reduction reaction at the surface of the corroding material. The oxidation reaction generates metal ions and electrons; the electrons are then consumed in the reduction reaction. For environments with water present including moisture in the air, the electrons are consumed by converting oxygen and water to hydroxide ions. In iron and many iron alloys, these hydroxide ions in-turn combine with iron ions to form a hydrated oxide (Fe(OH)2). Subsequent reactions form a mix of magnetite (Fe3O4) and hematite (Fe2O3). This red-brown mixture of iron oxides is rust. The figure below illustrates the basic oxidation/reduction reaction behind corrosion. The higher the ionic conductivity, the quicker this reaction takes place. This is why water containing electrolytes, such as salt, is far more damaging. Another key point to note is that reducing the amount of dissolved oxygen in solution directly can inhibit corrosion. However, many other reduction reactions can consume the electrons.

OH

OH

OH

OH

Fe+2

H 2O e

O2 e

H2O e e

Fe+2

Ir on

Figure 1. Electrochemical Process

The AMPTIAC Quarterly, Volume 6, Number 3

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..... Forms of Corrosion – ASM Classifications[4]........... Static-tensile stress causes stress corrosion cracking (SCC). Crevice .. switch contacts. Differences in the coefficients of thermal expansion (CTE) of the materials in contact increase the risk of SCC.. The diverse environmental factors causing crevice corrosion make it almost impossible to simulate field conditions in the laboratory... leading to the accelerated loss of material.. The rate of corrosion is often presented as a weight loss.. and its rate of attack is hard to quantify. etc.... • Stress-Corrosion Cracking (SCC) • Hydrogen Damage • Liquid Metal Embrittlement • Solid Metal Induced Embrittlement 12 The AMPTIAC Quarterly. Crevice corrosion can occur under washers..... decobaltification... Corrosion caused by an electrochemical reaction between two dissimilar metals when placed in contact or electrically connected with each other in an electrolyte. denickelification...Material E A S E Table 1........ surface deposits.... Predicted life from accelerated tests is also unlikely. One element is preferentially removed from an alloy. Uniform corrosion is very predictable...... It is also called de-alloying or parting... Uniform (General) ... and graphitic corrosion. Pitting .... it is difficult to predict... Galvanic ..... bending... sealing rings. surface scale.. Intergranular . dezincification.. Pitting corrosion is a localized form of corrosion that proceeds with minimal overall metal loss. leaving a residue (often porous) of the elements that are more resistant to the particular environment. and is the basis of most corrosion prediction equations.... Common forms of selective leaching are decarburization..... cold deformation (cold working). Occurs evenly over the entire surface. The stresses initiating SCC damage are in the form of applied mechanical stress or residual stress... Induced by the joint influence of mechanical stress and corrosion processes... usually with slight or negligible attack on the adjacent grains... Corrosion fatigue is often considered to be a form of SCC... This phenomenon occurs preferentially at grain boundaries. Traditional Corrosion Classifications[3].... General Corrosion: Corrosive attack dominated by uniform thinning • Atmospheric Corrosion • Galvanic Corrosion • Stray-Current Corrosion • General Biological Corrosion • Molten Salt Corrosion • Corrosion in Liquid Metals • High-Temperature Corrosion Localized Corrosion: High rates of metal penetration at specific sites • Crevice Corrosion • Filiform Corrosion • Pitting Corrosion • Localized Biological Corrosion Metallurgically Influenced Corrosion: Affected by alloy chemistry & heat treatment • Intergranular Corrosion • Dealloying Corrosion Mechanically Assisted Degradation: Corrosion with a mechanical component • Erosion Corrosion • Fretting Corrosion • Cavitation and Water Drop Impingement • Corrosion Fatigue Environmentally Induced Cracking: Cracking produced by corrosion. Table 2.... as its reaction rate is not quantifiable.. Volume 6... Stress . sleeves.. gaskets. making it difficult to detect.. rivets.. A localized form of corrosion which occurs within the stagnant zones created by the interfaces between two surfaces.... Consequently. debonded coatings.. or electroplating of metallic components can bring about residual stresses.. Number 3 . Selective Leaching .. Erosion . Manufacturing processes such as welding. Cyclic loading brings about corrosion fatigue...... in the presence of stress.. An action involving both corrosion and erosion in the presence of a moving corrosive fluid.... clamps...

The oxide film formed ennobles the metal and reduces electrical current density by as much as six orders of magnitude. Consequently. increases corrosion rate. make sure that the test does not introduce additional corrosion mechanisms.A D VA N C E D M AT E R I A L S AND PROCESSES TECHNOLOGY A MPTIAC Table 3. categorizes various corrosion processes by mechanism of attack. like any other form of accelerated testing. Consequently. This region corresponds to the beginning of corrosion. Transpassive Region . Accelerating tests often represent the worst-case scenario. A thorough study of this environment is suggested before planning any corrosion test. galvanic) ASTM B117. Caution must be exercised to make certain the corrosion mechanism is not altered. becomes increasingly more realistic as the laboratory environment approaches that of the service environment. Inspection of this table indicates that some forms of corrosion affect (relatively) large areas as indicated in the section addressing “General Corrosion” while other mechanisms are very local in nature. In addition to analyzing the characteristics of that environment. For instance. service testing provides the highest fidelity results followed by field testing. stress corrosion. they more appropriately give insight in a qualitative fashion to how materials will behave when subjected to an environment. requiring a very aggressive corroding factor. To account for the variation of corrosion properties with configuration. Corrosion behavior is influenced by the slightest variation in metallurgical structure and surface preparation . The final category identifies corrosion mechanisms that result from the inspection of a “stressed” material in the presence of a corrosive agent. Naturally.Increasing the oxidation potential past the active region reduces the corrosion rate. In either classification system. There are three major types of corrosion tests: Laboratory. However. such as uniform attack. Field. pitting. like those found near sheared surfaces or stamped edges. These tests are typically qualitative. Accelerated testing can be a useful tool in this process as long as the investigator realizes the intent of the test. inadvertently using a bolt and test specimen which create a galvanic couple will lead to spurious results. There are many ASTM and ISO publications describing standard test methods for different types of corrosion testing in various atmospheres. Table 3 shows several common tests addressing a variety of environments.. Given the many reactions that can occur and the corrosion regions possible. c.thus care must be taken while preparing the surface of the testing specimens. Accelerated tests can seldom be used to accurately predict the life of a structure. Selection of Corrosive Media: The corrosion process largely depends on the corrosive environment. The onset of corrosion may seriously accelerate damage in an entirely unpredictable manner. and crevice corrosion. Active Region -Increases in the oxidation potential lead to increasing corrosion rates. the results may not show as aggressive an attack as desired since the amount of dissolved oxygen in a liquid environment greatly impacts the corrosion rate. If the oxidizing potential is raised to high enough levels the oxide film breaks down and the material begins to actively corrode again. accelerated testing for corrosion is difficult to implement. Fog Test (Oldest and Most Widely used Cabinet Test) ASTM G31 (Immersion Corrosion Testing). The AMPTIAC Quarterly. however. Materials like aluminum exhibit three corrosion regions: a. Classes of Corrosion ASM offers a complementary classification of corrosion that can be useful for designers.Increasing the oxidation potential past the passive region. If the corrosion experiment has an extremely stagnant electrolyte for a crevice corrosion test. aluminum forms an oxide scale. Volume 6. Corrosion Testing Typically. all conventional corrosion testing requires long testing times and is expensive. This classification. the corrosion specimen must be prepared in a fashion indicative of the service material. several other standardized tests are performed for particular corrosion types. Before testing Before implementing any corrosion test. the classification of corrosion into groups may be gradually losing its significance as understanding of basic corrosion mechanisms continues to grow. b. and most types of corrosion do not lend themselves to prediction of performance through accelerated tests. as described in Table 1. which influence the initiation and propagation of corrosion. Some of these mechanisms can be easily dealt with or mitigated through proper design and materials selection decisions. most accelerated tests should not be used to predict life or corrosion rates. and Service Testing.g. Similar to iron. the oxide scale formed (alumina) is cohesive. shown in Table 2. care must be taken when selecting the corrosive media and preparing the test specimen. ASTM G50 (Atmospheric Corrosion Testing) The corrosion of iron illustrates that many reactions can occur. accelerating the corrosion process is difficult without altering the corrosion mechanism. the service and field tests have limited prospects for accelerated testing. atmospheric. Avoid excessive heating of the surface from grinding operations to remove scale and remove excessive cold worked surfaces from sample machining. ASTM Standard Test Methods for Various Environments Environment causing corrosion Types of Tests Fresh Water 39 ASTM Standards Seawater Environments General Environments (e. the corrosion categories overlap and often influence each other. Categorizing corrosion forms into specific groups is not straightforward. Salt Spray. and the information obtained from them is best used to down-select the most appropriate materials for use in specific applications. Other corrosion mechanisms are facilitated by metallurgical factors while still others rely upon the movement of two structures relative to each other or a structure or component subjected to moving fluids or slurries. However. adherent and inhibits further corrosion. Passive Region . because such groups have overlapping characteristics. Number 3 13 . Test Specimen Preparation: In addition to carefully selecting the corrosive environment. Traditional Corrosion Classifications. Accelerated corrosion testing. Rather. corrosion is often categorized by how it manifests itself. Because of its intricacy.

There are many other factors affecting corrosion rates.5% to 20%. careful attention to. the results of accelerated testing should correlate to results from more reliable sources. measuring weight loss is unsuitable for localized corrosion effects such as pitting. They are the easiest measurement to make. crevice and intergranular attack since total weight loss can be minimal while local damage can be severe. fabrication history.[4] Other methods.) • Pressure for stress corrosion cracking tests • Acidity in immersion tests • The amount of NO2 and SO2 for atmospheric tests • Relative humidity for atmospheric tests • Impingement velocity in erosion corrosion tests • Current in electronic parts prone to corrosion Additionally for aqueous corrosion. 0. D-2776 Electrochemical impedance G-106 Cyclic potentiodynamic polarization G-61 Galvanostatic polarization D-6208 Scratch-repassivation D-6208 Immersion Tests Total Immersion G-31 Partial immersion G-31 Intermittent immersion G-44 Salt Spray (Fog) Testing Neutral B-117 Acetic Acid G-85 Annex A1 Cyclic Acidified G-85 Annex A2 Cyclic Seawater Acidified G-85 Annex A3 Cyclic SO2 G-85 Annex A4 Dilute Electrolyte Cyclic Fog Dry G-85 Annex A5 Copper-Accelerated Acetic Acid B-368 0. electrochemical polarization methods for measuring corrosion rate are amenable to aqueous corrosion.6 Average Penetration. each test includes a range of test conditions. their procedure is necessary to obtain useful results. e. Example of How Short-Term Corrosion Test Results Can Be Misleading. such as directly measuring a “depth-of-penetration. Several common methods for acceleration include increasing: • Aeration for immersion tests • Temperature (The most common and greatest accelerating factor for many corrosion mechanisms. However. Unfortunately. shape and size of the specimen all affect the corrosion rate. Volume 6.1 0 1 2 4 8 Exposure Time.. the corrosion rate of wrought versus cast alloy will likely be different. Moreover.Material E A S E Table 4. mm 0. years 16 Figure 2. There are fifteen ASTM standards on controlled humidity tests alone. The method of accelerating corrosion testing will depend upon the material being examined.[7] 14 The AMPTIAC Quarterly. The goal is to accelerate the test as much as possible while keeping the test corrosion mechanism the same as the service corrosion mechanism. and meticulous execution of.” can be difficult. corrosion tests can be inherently slow. which lead to countless test methods. For example. Additionally. Standard testing procedures have been set up for the various laboratory tests. gross variations of all these factors can alter the kinetics of several intermediate corrosion reactions leading to spurious results. Since most laboratory corrosion tests are accelerated tests. Summary of Specific Laboratory Corrosion Tests and Their Corresponding Standards Electrochemical Methods ASTM Standard Electrochemical polarization resistance G-59.2 Actual Corrosion Curve 0. These are described in some detail in Reference 5. Interpreting the results In order to correctly interpret the results of any corrosion test. Besides altering the main corrosion mechanisms. Number 3 .4 2-Point Estimate of Linear Rate 0. testers must exercise control of these variables. a complete pedigree of material information and testing parameters should accompany the test results. hence. service experience and field testing.3 0. Classifying materials in broad categories such as “Stainless Steel” or “Aluminum” is a mistake.7 0. the corroding electrolyte and the ionic conductivity help determine the rate of corrosion attack. and an outline of some of the specific tests and their corresponding ASTM standards is given in Table 4. Variations in the material’s chemical composition.g. ASTM B 117 allows the concentration of NaCl solution to range from 3. The changes in specimen weight versus time are most often used to calculate corrosion rates. the environment and the type of corrosion mechanism.5 Acceleration Testing does not have to correlate exactly to the service environment as long as the corrosion mechanism remains the same. Even when accelerated.8 Extrapolation of Initical Corrosion Rate 0.

Many of the corrosion rate formulas are frequently misused. Be extremely cautious when devising any accelerated test technique or using a corrosion rate as gospel for predicting lifetimes. While some debate in this area still exists.A State of the Art Report (AMPT-15). “Electrochemical Methods of Corrosion Testing. 13.” Metals Handbook. it is difficult to design an accelerated test that can predict field reliability. For example. not the reduced area. pp 39-152. Curves α and β were calculated from short-term test data (6-months and 2-year rate respectively). The result was fewer test failures as compared to field conditions.) Even with general corrosion.. where the “pitfalls” are numerous. in the case of accelerated testing of a circuit-pack. thus lowering humidity and inhibiting corrosion. sample shape. to calculate rates. 212-228 [5] Metals Handbook Ninth Edition. 3rd Edition. Adherent scales may exhibit a weight growth even though the material is severely damaged. AMPTIAC. 13. the test increased temperature. a different failure mode (that is usually the first to appear in the field) is masked. 13. and is instead limited to qualitative assessments.G. Number 3 15 . SCC). (Use the original area. The example mentioned earlier describing scale creating sites for pitting or crevice corrosion is a common case of multiple mechanisms at work. one thing is clear: uniform corrosion models cannot and should not be applied to localized phenomena. 1986. Certain factors render components much more susceptible to corrosion. as well as the extra attention paid when building them. On the other hand. small sample size.A MPTIAC A D VA N C E D M AT E R I A L S AND PROCESSES TECHNOLOGY For general corrosion. For example. while substantial. many materials produce a scale. Multiple Failure Modes complicate the design of accelerated testing. ASM International. to validate the data. Test specimens which fail by an alternate mechanism not experienced in the field must be considered invalid. 1987. Editor.W. experience has shown that “smearing” environmental effects in accelerated tests does not provide good prediction of field reliability. care must be taken while testing to correlate a weight loss to a corrosion rate. Climate. 1987. Most common among these is the application of predictive equations (often derived from uniform corrosion phenomena) to characterize and predict the behavior of localized phenomena. 1987. thus rendering test variables highly unpredictable. However. the sample should be carefully examined before cleaning to gain insight into the corrosion mechanism. small numbers of failures. Curve γ is the actual corrosion rate. A classic “snake in the grass” is the case of immersing a steel specimen in water near the boiling point. If this scale is adherent but does not protect the base metal. Because of this. 1995. Life Prediction and Performance Assurance of Structural Materials in Corrosive Environments . The AMPTIAC Quarterly. 79-189 [4] Scully. References [1] Kuruvilla. pp. which resembles a long-term corrosion rate at short exposure times. The following describes some of the more prominent ones. low-carbon steel immersed in a similar environment initially forms a protective film after which the corrosion rate becomes almost linear with time. M. Note. Manufacturing conditions should be closely simulated in the accelerated test. The ASM Handbook on Corrosion[5.K. and (c) help determine corrosion control strategies of fielded items.6] recommends that at least three replicate sets of specimens should be tested through exposure at increased duration.. it may invalidate the contributors of non-accelerated factors. pp. Corrosion Engineering. Model Uncertainty is tremendously amplified via extrapolation of results from the accelerated test.. McGraw-Hill Book Company. such as geometry (crevice corrosion. Vol. greatly affects the environmental conditions.. it must be removed before weighing. “Corrosion Tests and Standards: Application and Interpretation. Consequently. Unquantifiable Corrosion factors are major contributors to the uncertainty of models and their frequent misapplication. Prototype Articles for Laboratory Testing May Vary from Production Units. ASM. Some have attempted to “average” out environmental conditions for accelerated life tests in the hope of reproducing the variable effects of climate. For example. Such effects. Multiple Factors Change Degradation when Multiple Time Scale is Involved. To compound the damage assessment. A. While accelerating one failure mode. ASM International. This is particularly true with accelerated corrosion testing. Acceleration of Specific Variables May Actually Decelerate Failure. 1999. Most failures are the result of several factors. This change in corrosion rate can even undergo cyclical acceleration and deceleration if a scale thickens and sloughs off. [3] Metals Handbook Ninth Edition. Robert. exposure time and density of the specimen. These pitfalls illustrate that. Pitfalls of Accelerated Testing With any accelerated testing. D. Vol. Misapplied Models are responsible for many of the errors of corrosion rate and life prediction. Accelerated corrosion testing is a necessary and powerful tool when used to: (a) help with materials selection as a relative indicator of corrosion resistance. If only one of these factors is accelerated.” ASTM. pitting) or welds (selective leaching.R. [2] Fontana. adherent deposits or encrustations may cause pitting or crevice corrosion. Test units should be taken from the field. and should use raw materials from actual production. 191-317 [6] Baboian. are not readily quantifiable. Materials and parts used to build prototypes may vary from the ones used in production. (uniform thinning) the corrosion rate is proportional to the weight loss and inversely proportional to the area. among other difficulties. partly due to different levels of cleanliness. the field environment is not as carefully controlled as the laboratory. the corrosion rate often changes with time due to film formation on the material’s surface. and large degrees of extrapolation from available data all combine to create great uncertainty. Volume 6. J. New failure modes may appear that can cause the component or the material to degrade or fail. Conclusion Corrosion is a complex electrochemical process dependent upon a myriad of factors. For example. data from accelerated testing cannot provide reliable life predictions in such cases. Taylor. such as pitting or crevice corrosion. Vol. which is supremely stochastic and essentially random. pp. For example. caution must be exercised to gain meaningful results. (b) help examine potential environments for new materials. As the temperature approaches the boiling point the corrosion rate decreases since the free oxygen in the solution is driven off. copper immersed in tropical seawater corrodes at a rate that is proportional to the square root of exposure time and not linear to it (Figure 2).