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CHAPTER 3 Experimental Preparation Proper preparation is critical to successful elec- trochemical testing. This chapter examines specific preparation procedures that will lead to a high de- gree of reproducibility in electrochemical tests. Chap- ter 3 is divided into three sections: Specimen Preparation, Solution Preparation, and General Wir- ing/Connections. Specimen Preparation Proper preparation and careful handling of the working electrode specimen is critical in obtaining reproducible results during electrochemical testing Typically, electrochemical testing utilizes relatively small test specimens, and test matrices do not pro- vide for a large number of replicates. For these rea- sons, specimen preparation is even more important for electrochemical testing than it is for other types of corrosion tests. Surface Finish The first thing to consider is the selection of a surface finish. Two primary objectives of a surface preparation procedure are: (1) The surface will respond in electrochemical tests in a manner similar to the response of the commercially produced material in the service of interest, and (2) The procedure is convenient and practical. 29 The former consideration requires minimal dit- ferences between the surface composition and struc- ture of the test specimens and the material that will be put into service. The latter consideration elimi nates procedures difficult to reproduce and time-con- suming procedures unless they are determined to be absolutely necessary. In general, the surface finish should be smooth enough to obtain a uniform surface finish and not so smooth that reproducibility is difficult to maintain. An extremely smooth surface, as achieved by electro- lytic polishing or even by mechanical polishing with a diamond or alumina abrasive paste, typically is not desirable. Such surfaces are not only more difficult to reproduce because of the time and effort required, but they often respond differently in the environment than a commercial surface, e.g., as-rolled. An electropolished surface may have a significantly dif- ferent surtace composition than would be present on commercially produced sheets, tubing, etc. A surface roughness that corresponds to a 400 to 600-grit silica carbide grinding paper finish com- monly is used in corrosion tests. Other consider- ations, such as the desire to test as-received, finished parts or welded specimens could be the controlling factor. The most important aspect is that, within a group of tests to be compared, the surface finish of the specimens be similar. CAUTION: If grinding paper is used for speci- ‘men preparation, it is necessary to use fresh pa- per for each alloy. 30 DC Electrochemical Test Methods For example, grinding aluminum on the same paper as steel will result in steel contamination of the aluminum specimen surfaces. This may result in the acceleration of the corrosion of the aluminum. Grinding and polishing always affects the surface layers of the metal by introducing cold work. The thick- ness affected is a function of “severity” of grinding/ polishing and the grit size, etc. For this reason, it is recommended that grinding operations be minimized Only grind enough to remove prior machine marks and use a ‘light touch”. Significant pressure is not necessary for effective grinding, An additional concern during surface finishing is heat generation during grinding. Whenever possible, wet grinding is used to maintain temperatures at an acceptable level. If dry grinding is performed on a belt or wheel, care must be taken to periodically cool circumstances when intentional crevices are placed ‘on samples. Degreasing Once the surface finish is complete, the speci- men should be washed well to remove any grit and loose particles from the surface. Next, the specimen should be degreased. ASTM Standard G5 suggests degreasing by boiling for five minutes in benzene followed by a distilled water rinse (deionized water is acceptable as well). However, benzene is highly toxic and must be used in a fume hood with extreme care and is not generally recommended. A satisfactory alternative is to degrease by immersion in acetone for one to three minutes, preferably using an ultra- sonic cleaner, followed by rinsing with distilled (deion- ized) water. It is important not to handle specimens with bare hands following degreasing. If the speci- mens have been prepared previously and stored for more than 48 hours prior to immersion into the test cell, it is preterable to butt the surface briefly with the final finishing paper (400-600 grit) and lightly rinse with acetone followed by distilled (deionized) water. Sometimes, the reproducibility of the measurements is affected by the time between final finishing and testing, Mounting Mounting of the specimen also is critical in ob- taining high quality, reproducible results. The primary concern is that the mounting procedure not alter the electrochemical measurements. For meaningful re- sults, the test specimen must behave as the alloy would in service. Two important considerations in selecting a mounting procedure are (1) a crevice is not created during mounting of the specimen, and (2) the mounting material used is inert in the envi- ronment being tested. Because of these considerations, a convenient and commonly used specimen in electrochemical studies is cylindrical with a hole drilled and tapped in one end. The electrode holders use PTFE washers or gaskets for the mating surface to the specimen (Figure 2.12). Upon screwing the specimen onto the threaded rod, the PTFE is compressed forming a tight seal between the specimen, the gasket, and the holder, which minimizes any crevice and provides a suitable mounting arrangement for testing in most aqueous environments, At ambient temperature, hand tightening usually is adequate with PTFE holders. In fact, over-tighten- ing can produce an unwanted crevice due to defor- mation of the PTFE (Figure 3.1). A further consideration is high temperature (75-100°C) ambi- ent pressure tests in which the PTFE can creep (slowly deform) under mechanical load and loosen the seal. Under these conditions, more pressure is required to tighten the specimen than normal, or al- ternative mounting procedures are required. In many electrochemical tests, it is not possible to use cylindrical or disc specimens. A number of cre- ative mounting arrangements have been used. These include: + rod or odd-shaped specimens masked-off with a non-conducting, chemically resistant coating to some distance below the solution/ atmosphere interface; + mounting specimens in various mounting resins followed by grinding and polishing the test surface of interest; Corrosion Testing Made Easy 31 Only Slight Bulging NN Edges Remain Relatively Even a. Proper Tightening Working Electrode lt Severe Bulging \___vertap PTFE Spacer b, Over -Tightening FIGURE 3.1 - Proper tightening of the PTFE gasket. + clamping a cell down onto a specimen using an o-ring or washer so the specimen becomes the bottom of the electrochemical cell; and + using a non-conducting, chemically resistant, adhesive tape to mask off areas of a specimen. Coatings and mounting resins must be inert in the test environment, and the coating must be resis- tant to significant water permeation during the test period. The use of o-rings, gaskets, and washers (other than PTFE) typically will cause more of a crev- ice than the preferred compression PTFE washer. Tapes often have problems with disbonding although 3M Company makes an adhesive PTFE tape (3M Scotch Brand tape #5480) that has been used with some success. The gasket or coating must be suf ciently inert so undesirable species are not leached from the mounting material and affect the specimen behavior. For example, some gaskets, o-rings, and coatings may leach chloride and sulfur species into the test solution and affect the specimen corrosion behavior. Therefore, it is important to check out any new arrangement or mounting material in preliminary tests to ensure crevices are not created and the mounting material is inert. Crevices are easily identi- fied in preliminary tests by removing the working elec- trode and examining it for crevice attack at the specimen-gasket (or coating) interface or beneath the gasket (or coating). Leaching of chemical species from the gasket or coating is much more difficult to discern, and this is why PTFE is the material of choice whenever practical. Obvious changes in hardness or color of the gasket or coating are clear signs the gas- ket or coating has undergone degradation.