Laboratory Testing LABORATORY CORROSION TESTS are used to predict corrosion Bchavior sehen service history lacking and time of budget coastraints ‘prohibit simulated service (eld) texting. They an also be wed ay screening tests prior tw Simulated-service testing. Vaboratory tests ave particularly useful for quality contol, materials Selection, materials and environmental compat. fons, and the study of corrosion mechanisms These tests caver a spectrum ranging from simple immersion tests to various kinds of cabinel and aistolave controlled environments sophisticst til electrochemical tests, Most ofthese are accel: fated tests by design: therefore, they must be tesed with caution, Because almost everything tout these tests is based on assumptions. the {esting conditions are arbitrary, and the problems of selecting the most pertinent testing method fad realistic iterprettion are always present ‘Standindized test methods are very usetul for specifications tnd for routine less Used f0 com pre experimental iloys and such products 2s Inhibitors. coatings. and. insulation materials. Many sch tests. are described in the Anqwal Book of ASTM Standards (Vol 08.02, Seta! Conrosion, Brosion, nd Wear) ane in proxhct Specifications, However, iis often necessary for Special ens lobe set up that require creativity on the part ofthe investigator. This stile wil eal swith hase procedures and approaches (labora: tory corrosion testing hut will not attempt to Coverallof the published Itemsture on specialized testing Electrochemical Methods of Corrosion Testing John R. Scully David W. Taylor Noval Ship Research and Development Center ‘Corrosion i an electrochemical process. Elec- trochemicil provesses require anaes and cath- ‘oles in electrical contact and ain oie conduetion pith through an electrolyte, The electrochemical process eludes cleczon low Fetween the anod {and cathodic reas: the rate of this Maw core= sponds tothe eves ofthe cation and reduction reactions thal oer at the surfees. Monitoring this electron flow provides the copabilly of as ‘sesuing the hietics ofthe corrosion process. at Simply. the thermostynamic tendencies for the Process to occur spontaneously nor only the Accumulated meta oss registered alter the tet ‘Measirements of this type have become knowa as electrochemical measurements of corrosion, Several extbooks cover many of Uhe major as pects associated with the application of electro= ‘hernical ethos in corrosion (Ret 18) Electrochemical techniques. are finding. in sreased use in corrosion research and im cnet neering applications. Such methods are pr beeause the eorrosion behavior of matchal-eles- inolyte combinations fe w direct fanetion of the mechanisms ss wells the kinetics ofthe electro ‘ienical reastions responsible. The availabibty fetter electrochemical teshigues and the der ‘onstrated asctracy’ of such methads Tor invest titing corrsion phenomens have been the sub Ject of several retent technical symposia Ref 9 1 “The earliest applications of electrochemical Aechnigues were tractive bocause they offered Uiyect method of ucelerating a corrosion process without ebanging the ceviranment. that adding A strong ovidier or increasing temperature as ‘ther nonelectrochemicsl Inboratory tests, HOw. ever, recent advances have made the technigie nore of « nondestrictive too forthe evaluation of corrosion phenomena and reaction Fates and this offers the posstty of in si (Bela) a wel) fs et tn (laboratory investigations. Ths. elec trochemical techniques cam be used 10 masire ormision rates without romoving the specimen from the environment or altering The sample self. This capability offers distinct advantazes fover weightloss ind visal observation testing acedures ecause the kinetics ofthe coeosion frocess can he quantitatively studied and be- ‘Cause of the added convenicnee. ‘Most. i all, ofthe typical forms of corm sion. including uniform, lealze, galvanic. deal Toya. stress corrosion. and Hydrogen-induted failure, ean be investigated by electrochemical techniques. Topics such as passivation, anodizar tion, ctthodie and anodic protection, and barter find sacrificial coatings of metal substates can falso be investigated by using electrochemical techniques. Also available ate electrochemical techniques that have been optimized fr the study lo hydtdyaarie (muss transport controlled) rosion processes (Ret 15} as well as these tech hiques Uesigned to avoid dominance of the mea Sured quamity by miss transport control, that i ttansient clestecenemical methods (Ret [6) ‘Although they have beea limited to near ambi cnt temperature aqueous cverdsion studies inthe pst, electrochemical techniques afe now being Applied to high-lomperatute. high-pressure aque ‘US applicutions as well go the stody of corto. Sion processes in nonaquedts environments nd ‘hguetus environments of low conductivity. La the remainder of this section, specific examples ‘ull be given on the application of various elec Urockemical metho tothe typical catepories of ormoshon attack mentioned above Fundamentals Corrsion is an electrochemical process that is characterized hy mays trangpert 6s well the slectrical and onic charge transfer associated ‘sith corroding solid oF solids electrialy in contact. The corroding system consists of ance fd ethode sites electrically ip contact and & Stirounding electrolyte (Re 17). According nixed potential theory. any net lectrocherisal Fesction cin be algebraically divided Iate tw ot tore oxidation and reduction reactions, and thee an be no net electrical chayge sceumulation. ha ‘Sorroding systern in the amsence of applied tential, the oxidation of the metal nd the rede- tion of some species in solution aeur smite ‘neously at the metalelectolyte interface (Ret | 3). Under these ctcumstunces, the Wet Resi" 0. however. finite rate of cur ing ut lcd sabe sites on The met Stface, Such current potential relationship is Showa schematically in Fig. 1 ‘When the corrosion potential is Yocated a a potential that is distinctly ferent from the 1e- Nersile electrode pocentals (redox potential. Fr) Of either the corroding metal or te species in solution that are cathuaically reduced, the ‘Oxidation ofthe cathoie species or the reduchion ff any of the sons ofthe corroding metal that are in solution becomes negligible. The coruin Indicates the potential at Waich he fection rate and red externally is 0, the oxi the net current mes fags ~ fog ~ et (eg Because the oxidation current present at the ccorusion potential is the quantity of interes! ie the corroding system, this-pavamstee must be etermined independently ofthe reaction fates of ‘ther adsorbed or dissolved reaetanls. lect ‘chemical polarization methods canbe used 10 ‘determine vorsosion rates, More detailed infor mation onthe findamentulsssociated with agne ‘ous corrdsion un be found in the atiles "The fmodymamies of Aqueous Cerrosion” and NRinetics of Aqueous Corrosion” inthis Ve Conducting an Electrochemic Polarization Experiment ‘The electrochemical polarization of metalic surmples is accomplished with power supe Known ws 2 potentiostat. Ap susifoy electtode supplies the cirent tothe working electrode est Specimen) im order to polarize it. The pave hetween the Working electrode and a ceference slectrode i monitored or seta fixed vale, as in the potentiosatie west Figure fu) illustrates schemotially typical mental arrangement. ‘The system is de ‘only sn exiromely small curreot sin pass hetween the reference electrode and the ‘working electrode: the current needed to polarize0" Enon 20 + 40 SN Total ate of eduction pean sae : | “i i i i | | t Dat om feo Sena sche ptaore lon are coed tm congo cede Fig. 1 Sitfon ond ow anode secrochonclreacion ere conn cure vouge 4 ode, Figue 2) ifostates a typical eleero- aan sate i Ie pteu an sod ie np tation, serped a a Tne of tine arn / (iat aed Poetics) oF Wl at Aecdevt asin the potest cod et eteronce Working azerode Cggh probe Plezaion cell Reference ce PaarenaT Far mpatance sateorige robe | Retarence Seorade 4m S Avan weuteg [ll petaence seatrode sect = sta Instrumentation stip for slacrochen- (al poration experts, Fig. 2(a) the working electrode is supplied from the sux iaty electrode (Ref I). The potentostat actually contains an operational amplifier or similar de vice in order to provide the feedback of the current necessary for maintaining the fixed po- tential Between the Working and reference elec- 18). Conversely the current can be applied in a continuous galvanostatic or stepped. galvano- Staircase manner, and the change i potential monitored. Several American Society for Testing tnd Materials (ASTM) standards discuss methe fds for performing these experiments (Ref 19, 2, Conversion of Electrochemical Current Data to Corrosion Rates ‘Measurement of Jy atthe potential of interest where Jon = Jon Ay O¥€F Known period of time Teads 10 direct determination of the weightloss wale WF a> where W isthe weight loss (grams), 1-7 equals ‘the current multiplied by time or coulombs (C). is the number of clecttons involved in the elec- ‘rochemical reaction, F is Faraday's constant (G6 487 Cigram-equivalead), and is the molec- tlar weight of the electroctive species. This relation is known as Faraday's Law. Rearrange- tment of Ea 2 leads to & straightforward determi= tation of the penetration rate (applicable only ‘hen Zac 8 uniformly distributed over the entire ‘wetted surface area or where the localized active Ty corroding area, 4, is knows), as follows 3.27 10h a BW. oR ay Laboratory Testing / 213 ‘where CR isthe corrosion rate (in millimeters per Year), where E.W. is the equivalent weight in {rams dis the metal or alloy density in grams per ‘eubie Centimeter, anid lei the corrosion current ‘density ia microamps per square centimeter. For alloys, the equivalent weight E.W. should be celoulated using the atomic fractions of each alloying element in an expression such as: Sam Alloy E.W. = a4) where fis the atomic fraction of the ith compo- nent ofthe alloy. M, isthe atomic weight of the ith component element, n, is the electron Toss required to oxidize the fh component element Linder the conditions ofthe corrosion process (n, fs usually equal to the stable valeace of the tlement, or must be determined from either a Pourbaix (potentia-pH) diagram or experimen tally from un analysis of the corroding solution), find m is the aummber of component elements in the alloy. ‘This expression ussumes that all the compo- rent elements oxidize when the alloy corrodes find that they are all oxidizing at essentially a Uniform rate. Tn some situations, these assump- tions are not valid in these cases, the calculated corosion rate will be in error. For example, if an Alloy is composed of two oF more phases and one phase preferentially oxidizes, the calculation mist take this into Consideration. Eloctrochomical Methods For the Study of Uniform Corrosion Polarization Methods. The following rela- tionship observed between applied current and potential provides the basis forthe electrochen- Feal polarization technique (Ref 1, 2. 21: e [2 ME ~ Ba se ~ har B vo BE] €(B) es where lysis the applied current density based on the electfochemical surface 2208; (oy 16 the cor rosion current density; £ 1s ihe applied voltae; Eos is the open-circuit, or freely corroding, potential Cis the interfacial capacitance assoc! ited withthe electrochemical éoublelayer (Ref |, 2); and fare the anodic and cathodic Tafel ‘oeficiens felated tothe siopes ofthe polaria- tion curves inthe anodie and cathodie reximes, respectively; and dB isthe time rate of change in applied potential, or voltage, scan rate. Heal iy, the second term of the expression C dldt proaches Oat, for example, very low potential oan rales. Note that fg, Becomes wpproximately qual to either fo, oF erat large overpotential. At very large anodic of Cathodic overpotenials, Gg Sean be rearranged ina more simplistic form Ref 135.0 n= Bolo (2) 5) Eat) n= -tton (2)214 / Corrosion Testing and Evaluation = Sal-bge Fig. 2(b) Dyclsscrststmets Tafel Extrapolation. By ploiting potential versus log age a linear relationship between ‘eurent densiy und potential can be developed Ref 1, 5. "Extrapolation of the applied ccureni from either the aaadic or the cathodic ‘Tafel region to the open-circuit potential or posi- ‘ion of zero overpotential allows determination of od Invelving Solution Resistance, Polariza: tion techniques can be complicated by several factors, One such factor arises from the resist ity of the solution, depending on the geometry, the location of the reference electrode, and the magnitude of applied current (Ref 2, 6). Place rent ofthe reference clectrode near the working clectrode is facilitated through the use of a Lug- sin-Haber copillary. This arrangement is desired {inorder to minimize the solution resistance error, ‘which can be estimated fram the product of the Applied current, the solution resistivity, and the dtstance from the Luggin probe to the specimen Surface, The error contributes to the measured ‘overpotential in the following manner Map = Mew # Tae eas) Typical elecrocheeal plerization ell stating location for werking ond ari electrode, Where nurs Qual 10 agp Run the resistance of the solution). Thus, The tive overpotental is ‘overestimated at each applied current density, land the Tafel slope becomes inaceurate, The tue Scan rae inthe potentiodynamic technique may also be altered. Several excellent reviews. are available on the subject of the vollage error introduced from solution resistance (Ref 23-29) ‘Complications Involving Concentration Polarization Effects, The Tafel relationship er tablished above is dependent on pure activation contol, oF charge transfer control. An additional ‘consideration involves the concept of concentra- tion polarization. In this ease, the reaction rate is large enough that the clectroactive species is depleted of concentrated at the reacting surface in order to maintain the reaction rate through ‘fusion. The reaction becomes difusion con trolled at the limiting current density, The devi- ation from activation control i described by (Re 5h 2aRr ins a= 2g (1-) 49 ‘where 2 isthe gas constant, and Tis the absolute temperature. Many corroding systems are fre quently under what is termed mixed activation ‘and mass transport contrel (Ref 8). This behvior ‘cam be described matheratially by the algebrac combination of Eq Sand 9. To increase the Feaction rate and thus minimize the contribution of Eq 9 to the overpoential, the diffusional boundary layer thickness Is decreased by soh- lion sting or by the use ofa rotating cylinder ce disk electrode (Ref 15). ‘Other Iseues Concerning Tafel Extropola- tion. Experimentally there ae several problems With the Tafel extrapolation method. Large ap- Dlied current densities may not be representative ‘Of the true cortesion situation occuring st open circuit. This is particularly true in the case of ‘anodic polatization, in which the surface i chang ing because of corrosion and/or passivation of the metal. In the cathodic case, an excess of ad sorbed hydrogen ors build up of hydrox ions ia Solution at the metal surface may result in alter ations of surface chemistry not representative of the freely corroding case. In adtion, concent tiom polarization may eliminate the Tafel region entirely, Polarization Resistance Methods. For sa dic and cathodic polarization within i0 mV of the corresion potential, tis often observed that the applied current density is wpproximately kn ar with potential (Ref 1). This behavior is shown in Fig. 4 forthe type 430 stainless stel in sulfuric acid (1,804). The slope of this plot is determined tata corrosion potential, as shown in Fig. 4 (Ref 26, 27). This slope has units of resistance ares ands known asthe polarization resistance. Stern tnd Geary simplified the fundamental equations Adesepbing charge transfer controlled reaction Ii ‘etigs (Eq 3) forthe ease of small perturbations of the corrosion potential, that is, low polarization or overpotential (Ref 37, 28). This relationship has the form: te (8) (Be) ‘espectively. The value Ris determined from the furtent density, aot the’ current. measurement the surface area of the working electrode must be known. Knowledge of Ry and Tafel slope values permit direct determinatton of the corrosion rae at any instat in time (Ref 27-30). The ASTM Standards G 59 (Ref 20) and D 2776 (Ref 31) Uescribe procedures for conducting polarization Fesistance measurements. These standards do nol auldress smany of the complications that may ‘Complications With Polarization Resis- tance Measurements. Numerous papers have Addressed complieations and possible alternative methods for use of the polarization resistance ‘method (Ref 32-37), Three of the most obvious errors that are possible when using these meth ‘ods involve invalidation of the results through oxidation of some other clectroactive species besides the corroding metal in question, a change in the open-circuit or corrosion potential during the time taken to perform the measurement, urd the application of a large applied potentit result Ing in inadvertent departure from linear current density versus potential behavior, Several tech-Observed portion lt Corcosion caren day g ‘rata slope, 2 3 3 i = once soa i & a 2H 20 Hila) é eet Lasatve Momnet 5 20 ‘cathode branch Fig. 3 txperimertly moose Tol! polrzation pet. Sure: Ref 22 igues actually take advantage of the departure from nonlinearity in order to calculate the anodic and cathodic Tafel slopes ats low overpotential fad thus avoid some of the problems associated ‘With large polarization (Ref 37), ‘Another source of eror involves eases in whieh, both the anedie and cathodic reactions aze not Under charge transfer contro, a required forthe derivation of Eq 10. Possible corrections to Eq 10 {or eases in which pure activation control is ot ‘maintained, such asia the ease of partial diffusion ‘contol or passivation (Ref 38). Other researchers have attempted to calibrate ther results through the use of Weight loss measurements (Ref 39). In fact, in one case, polarization resistance data Tor A quraber of alloy-electrolyte systems were com pared (0 the observed corrosion currents (Ref 4M). A linear correspondence was obtained over ‘ix orders of magnitude in corrosion rates. "Two other frequently encountered complica- tions are the need to correct data for the electro- Iyte (solution) resistance R. and the effects of ‘capacitive hysteresis, C, occurring as & function ofthe voluage scan rate (Ref 2), Hysteresis in the ‘current density-potential plot i observable when the time rate of change, d&/di, of the applied potentials scanned in a cyclic manner under the Conditions in which the sweep rate i large, the Inerfacial capacitance is large, or both. “The effect can be minimized by performing the polar iaation resistance test by taking two or more de current densit}-potential measurements instead ‘of cycling the potential. The solution, oF obmic resistance, on the other hand, sill complicates the measurement because the algebraic Sum of the polarization resistance and the solution resis- tance is measured in a de or pseudo-de measure ment. ‘Many treatments ofthis subject have used the ‘lectical equivalent circuit model, which simi lates. the corroding metalelectroiyie interface (Ret 40, 4). The simplest form of such 2 mod the Randles cir, is shown in Fig. 5. The three parameters discussed above (R,, Rnd C) aze Shown in the relationship to one another that best spproximates a corroding electrochemical inter- face of @ metal. The sum of the polarization resistance and the solution resistance is mea Sued when a de measurement is performed be- ‘cause the capacitive reactance approuches inf ity. Thus, the (ue corrosion rate will be ‘underestimated when , is appreciable. Con- versely, any measurement at a cyclic epplied Dotential that is scanned as a function of time ‘uses the algebraic sum of the ohmic resistance land the resultant parallel impedance ofthe paral lel resistive-capacitive network to be measured. IER, is small compared to, the capacitive eror ‘considered alone will usually result in an overes: Uimation of the true corrosion rate. These com- plications can be overcome, as discussed below. Electrochemical Impedance Methods. Onc approach to determining the corrosion rate of @ ‘etal without the complications discussed above Laboratory Testing / 215 involves the electrochemical impedance (some: Aimes known as ac impedance) method (Ref 40- 43, In this technique, a smallampiude ‘Sinusoidal potential perturbation i applied 10 the Working electrode at a number of discrete fre~ ‘quencies. At each one of these frequencies, the resulting current waveform will exhibit ‘Sinusoidal responte that is out of phase with ibe ppl ‘electrochemical impedance dent proportionality factor that acts as # transfer function by establishing a relationship between the excitalion vollage signal and the current re- sponse ofthe system. AS such, an electrochemi- ‘al impedance is a fundamental characteristic of the electrochemical system it describes. A know ‘edge ofthe frequency dependence of impedance fora corroding system allows a determination of an appropriate equivalent electrical circuit de- Seribing that system. Figure 5 illustrates in the most simple case the equivalent electrical circuit ‘model for sn active corroding metal. The follow ing expression describes the impedance for that system Poa Rt TREO Ja 083 (9 12) where Z isthe impedance magnitude, w = 2af is the frequency of the applied signal in radians per second, € is the interfacial capacitance, and ) — ‘V=I Experimentally. it can be easily seen from Fig. 6 that at very low frequencies: Zanes = Ra + Ry (89 13) while at very large frequencies: Zrwst ~ Re eq) ‘As evident from the above, a calculation of the polarization resistance is possible in media of ‘Quite high resistivity because R, can be mathe- matically separated from R,. In édition, capaci tive hysteresis is eliminated. Other information ‘determined from this techique includes the val- ue of C, the capacitance. In the simple case of sctive corrosion, C may be found to scale linearly With the true electrochemical surface area from the relationship © = cA, where cis a specine capseitance per unit area, and A is the trie tlectrochemieal surface area, Determination of the corrosion rate also requires accurate values for the anodic tnd exthodie Tafel slopes B, and BL, as shown in Eq 10, ‘Methods Based on Mixed-Potential Theo- +. Galvanie corrosion can be described in terms ‘of mixed-potential theory, us schematically ius trated in Fig. 7. However. in the case of bimetal ‘oF multimetal galvanic attack in which {Wo oF ‘more metals are electrically in contact with one ‘nother, there will be at least in theory a. mint ‘mum of two cathodic and two anodic reactions. One of each of these reactions is occurring on each metal. In this ease, the more noble of the two metals is cathodically ‘polarized in theTT | i | i 7 : ee ie be 850 mew if, m'men Cove ‘ SRmkenetoanedt - 1.77 maiem? (Curve 31 5 x a hear f 4g Sheil egal chal oil utes : 7 ( j= 5 celscarcing cnolehcsine ure 3] sevoho Fee 5 oy ; Bo i = g ' ¥ z Tea reac rar a 3 1 z 3 L- a a i 5 a trou Reorads ‘ fade power ogre ph mor Boe et FAR at te agency pede of te scams sen cose —o— Yehaiclimedn fr e a own Fig, 4 Poernvion crs for poerzohn rete mess bse on fe es rom eh need ig. 4 [Seraura for ype 0 ceren seo Wir Care The rua rr, wih end 3 towing #2 sondord dotions, Source Rt 20, clectronegative direction. and its anodic reaction ‘ate wil thus be suppressed. Conversely the less foble, or more sacrificial. anodic mater is Anodically polanzed. andthe anodic reaction rte IS acceleraed. The mbed potential (he galvanic couple potential) ofthe galvanic courle andl the ‘esiting yalvunic curceot can be uniquely deter ‘ined from the sums of all of the anodic and thie currents for each material at cach po- {ental when the Following condition is met Bigs AL= Bes Ay (Ea 13) Where i, Ay isthe sum of the anodic currents {current denstiy multiplied by area), and 31, A, is the sum of the cathodic currents, ‘This relationship ail be uniquely satisied at fone value of the applied potential and can be ‘determined if potential versissnodic and cuthod: fe curtent data ure available for each material in the galvanic couple, Thus, this mixed potential will depend enticely on Kinetic considerations Father than thermodynamic considerations. Ta ‘imple bimetal eases, direct superposition of po- levization data (snnected for wetted surfuce) will yield the same result (Ref 44). This technique is Schematicalyilustrated in Fig. 7. However. be- ause applied currents, not anodic or eathoxc fcurrenis, are actually measured in the polaris. tion experiment, the toohnigue wil introduce the least efror whee the cathodic reaction rate 1 negligible on the anode matertal and the anodic Fescton rate is negligible onthe cathode matenia) at the galvanic couple potential (be mixed poten: lial. Otherwise. 2 correction must be made. Obviously. when the open-circuit potentials of the node and cathode materials are sila, 19S complication 1s more likely to arise. But this axe galvanic corrosion is fess Hike to be signif: icant addition, special care must be takea in the procedures used to develop the polarization ‘tna Ret 44), espacilly i time effects are to be taken into consideration when evaluating galvan- ‘e-corrosion behavior Direct Measurement of Galvonic-Corre- sion Rates. A more straightforward procedure Inwalves immersing the to dissiilar metals it fan electrolyte and electrically connecting the materials together by using a zere-resistance am meter to measure current (Ret 45-47, [0 ths ‘method, the galvanic current can bc directly determined as a function of rime, A reference electrode ca be used i the Usual manner 16 Seermine the galvanic couple potential Electrochemical Methods for the Study of Localized Corrosion iting and erevice corrasin are usally ass iated vith the breakdown of passivity [RET #8) ‘The unoalic electrochemical behavior of pusive alloy in deaerated aeid is ychematically showin in Fig. Sa} Figure 80) llusrates the results foe ype 430 stainiess steel in 11:50. The character istics ofthis diagram will ai in determining the resistance of ally 10 loalized attack Tests for evaluating the suscepuiilyy of & material to plting and revice corrosion include Potentiodynamic tests, galvanostatic test. pote tiosttic tests. seratch poventiostti Cots tabo- ellipsometric methods. piispropagation rate ‘curves snd elecrocTiemical noise measurements (Ref 49). Several excellent review papers Jsctss these methods in more detail (Ket #8, 39,0,Potenal rent rlationdis for he cote of a gohonic couple between wo crrdkvg mel. M, move aor i Fig. 7 sosiemotl,N, tes rable meta. Svic: Rol 3 and 5 Saeete ‘Oxygen (Sette tat TT ees Tag eurrent aerated Alem - 8(a) thon Source Ret 22 Cyclic _Potentiodynamie Polarization. Methods, The ASTM standard G 61 describes & procedure for conducting cyclic potentindynamic polerization measurements to determine el ‘Sisceptbilly to localized corrosion (Ret 5 method is designed for use with iron. oF nickel ‘ase alloys in chloride environments. In this test, 2 eyelic anodic polarization sean is performed at ‘fixed voltage Sean rate Panicular attention is focused on to features on the cyclic anodie polarization behavior dia- tram. These are the potential at which the anodic furrent increutes considerably with applied po- tena or the breakdown potential. In general, the ‘more nable this potential, obtained ats fxed scan ste Un this tes, theless suscepsibie the alloy to Hypeshstical anode ond cathodic polersotion bekevor for © material exhibiting passive arctic the initiation of localized attack. The second feature of grea interests the potential st Which the hysteresis loop is completed upon reverse polanvation scan. Io general, once initiated, 0- alized corrosion can propagate at some potential ‘more electropositive than that at which the hyse teresis loop is completed (when determined at a Fed sean rate). Therefore. the more electroposi- tive the potential at which the hysteresis loop is ‘completed, the les likely that localized corrosion Will occur, This poceetal i known asthe prot ton potential. Figure 9 llsteates evel poliza- mt Behavior foF Hastelloy C276 and type 308 Mainlese ‘tee! in 3.56 sodium chloride (NaCl) Soliton, Based on the sbove criteria for evalua fina, iis evident that Hastelloy C276 relive. ly more resistant 10 localized coro ‘environment Complications With Cyclic Potentio- ‘dynamic Polarization Methods. Althu itis reasonable metho of sereening Vatistions is alloy composition and cavironments, the cyclic poteatiodymamic pelarvation metbod has Been found to have @ numberof shortcomings (Ret 50- 54), Ons major problem conceres the elit ofthe polential scan rate, The vals of Bath the pro {Setion potential und the breakdovsn potential are ts strong function ofthe manner in whch the Fes fre. performed, particularly the potential scan fave employed. This problem is predominately ‘elated fo the induction tine regaled for ping the repassivation estes, und the complications frising from allowing Too ach ping propa tion fo ozeuralong with the accompanyiag ches Fsiry changes Before the reversal im the sean sirection ods for Localized Con of the cyclic potentiodynamic po ‘have become the basis fir several other eke trochemical techniques, Four other methods are schematically ilstaied ip Fi 10. Potentiostt methuuls can be used to overcome the inherent problems involving. scan rate. There are 10 feneral methods. ‘The frst is mainly wssvciated ‘Sih he study of initiation, and the secore! 1s tmuinly associated with the sludy of propazation ang, repessvition. ‘The frst weethod (Fig. 1) simply provides a ncans of determining the breakdown potential by polarizing individisl samples al potentials above fia below an approximate Ey deteretined fom the potentiodysamie method. Eventual initiation isimicated by a curcent increase. In the second method (Fig. 100 and c), initiation of pals Is intentionally induced by applying potential above the breshdown potential and ther quickly Shifting 0. potential below that value. Ifthe fn Applied potential is above the protection poten roypugution of the existing pis wil continue tad the current wil inerease. Hawever. al E lest than the protective potenti, By the ils all ‘eventually repassivate, snd the current will su Seauenily decrease with time. Tho galvanostatic of gulvinestavease technique (Fig. l0d), me sures potential versus time at constant upplied orton. Memurements are often made untl the line rate of change ip potential spproaches 0. The Isehmgie 1s under devewopment In ASTM G 1 a 8 test method fr application wih aluranur alloys ‘The Seratch-Repessivation Method for Lo- ‘alized Corrosion. Une additional technique to be mentioned in the area of localized corros involves the scratch method (Ret 5} In this method, the alloy surface i scratched at t con Sant potential, and the current is measured 3s 3 function uf time. The potential dependencies of the inaction time and the repassivation time are Aetermined by monitoring the current change ‘over a range of different potentials. This isi trated ia Fig. From this information, the trtcal pitting potential. thought to be located Somewhere between the breakdown potential and the protecion potential can he determined. Olly fer methods of studying localized corrosion ate also avilable (Re? $9), Environmental Cracking There are numerous electrochemical tech= igus in the 'aeca of environmental cracking.