‘oez8i2010 oo hans men m0 Article: An analysis of stress corrosion crack growth by 380549 205.227.91.222 oe WM Arlir, Delivery INTO ISSN: 0360-2133 EISSN Bey Delivery Infornation Volume: 12 ‘Method (circle one): Issue. 6 ARIEL Quarer MAIL ‘Season: FAX Number OTHER Month: ‘Note: Library's preferred delivery method is indicated by >> << Day: — Year, 1981 © Patron's Library Information 6 Address: Wayne State University, Purdy/Kresge Library, Interlibrary Loan/Document Delivery, 5285 Pages: 923 - 931 Gass Ave. in 122, Detrt, MI 48202-3059 a Emait wid@wayne edu Fax. 319577-8587 BE Paton ipaation: ‘Staff Note: Patron Number: .p1144087@za014 Patron Type: ARLIR faculty, Paged Locations: >>za014<<, 9wsu0, 9csib, 6wash, Patron Email: ay6786@wayne.edu ‘Susyd, ... (1 of 8 sites paged) Preference: Electronic Location: Sci and Engg Library Periodicals Call Number: Shelved as: Metallurgical transactions A: physical metallurgy and materials science Courtesy of Wayne State Library Services For further assistance, please contact your library. NOTICE: This material may be protected by copyright law (Title 17 U.S. Code),TO An Analysis of Stress Corrosion Crack Growth by Anodic Dissolution P. DOIG AND P. E. J. FLEWITT An analysis of the distribution of electrode potential within a stress corrosion crack which is growing by an anodic dissolution process has been used to define the electrode potential at the tip of the crack. This potential is used to predict the kinetics of crack growth. The influence of the applied stress intensity and the electrochemical properties of the crack tip and surface on the growth rate have been considered for low alloy steels in concentrated hydroxide solution and aluminum alloys in acidic chloride solution. Crack growth rates obtained in high concentration solutions are extrapolated to lower concentration solutions which may be expected in servi agreement with published data. THE widely reported and discussed catastrophic fail- ue of an L. P. turbine disc at Hinkley Point Power Station’ and subsequent examination of other similar plant’ have highlighted the susceptibility of low alloy Ferrite steels to stress corrosion cracking in condensing steam environments. In attempting to predict the growth kinetics and allow reliable extrapolation of experimental cracking data to service conditions, much effort has been directed towards establishing the basic mechansims of cracking, Perhaps the most widely accepted mechanism for the growth of stress corrosion eracks in aqueous cavironments is that of ‘slip-dissolution’ *” The mech- anism has been variously developed from the original repos of Logan and ineludes an enhanced anodic disoliton atthe tip ofa growing crack whichis fected by the mechanical rupture of the protective oxide film. Such enhanced anodic dissolution at a ‘bare surface’ results in a rapid erack advance by a metal loss Drove, These models for stress corrosion crack growth based on calculation of a maximum growth rate ‘hich is faradaically related to the maximum anodic Gaent density atthe crack tip. However, these pre Gited growth rates are often several orders of mag Ride greater than those measured experimentally or {ifienced in service components. Consequently, ishas led to the introduction of a varity of rate ap ling parameters, other than maximum dissolu- MepeteR density, in oder to reduce the maximum oretieal crack growth rate to more realistic values. pace Parameters include diffusional processes, re Passivation rate, micro-creep, solution renewal and "ical charge concepts. ing ftRet: the various electrochemical parameters esi the various growth models have been iment under laboratory conditions using bulk spee- has thee Potential dependence on these parameters they been investigated in an attempt to evaluate mage Otttibution to stress corrosion crack growth rates ted at the same potentials. Implicit in such a > od Coe Officer and P.E.J, FLEWITT is Secon, Ctra Electricity Generating Board, South Easirn Region Mc Services Dept, Gravesend, Kent, U:K- submitted Apri 28, 1980. mer, FALLURGICAL TRANSACTIONS A {ISSN 0360-2133/81/611-0923500.7510 © 1981 AMERICAN SOCIETY FOR METALS AND ‘THE METALLURGICAL SOCIETY OF AIME environments. Predicted crack growth rates are in good correlation is the assumption that the electrode poten- tial which is determined for the bulk stress corrosion specimen is the potential prevailing at the tip of a ‘growing crack. Recently, however, it has been shown'™* that such an assumption is not generally valid and therefore any direct correlation of growth rate with other electrochemical parameters may be ill-founded. Stress corrosion crack growth rates in service envi- ronments are often sufficiently low that the experi- ‘mental determination of relative susceptibility of a range of materials is obtained using accelerated test methods. Experimental stress corrosion growth rates are often measured from tests in concentrated solutions which are chosen to accelerate the assumed controlling electrode kineties. Extrapolation of this data to the more dilute environments usually encountered in serv- ice is then effected on the basis of some arbitrary empiricism. Any improvement in such extrapolation Fequires some analytical evaluation of growth based on ‘a mechanistic interpretation of the cracking process. ‘ina previous paper” the authors presented a theo~ retical analysis of the electrode potential distribution ‘within a stress corrosion crack which was growing as a result of an anodic dissolution process. This analysis allowed the electrode potential at the crack tip to be taleulated from the bulk electrochemical properties of the crack surfaces and crack tip. The purpose of the present paper is to extend that analysis to the predic- tion of stress corrosion rates and investigate the in- fluence of corrosion product formation on the crack surface, applied stress intensity and various elec- trochemical properties as controlled by the environ- nent and material composition and structure local to the crack path. 1. ANALYSIS OF STRESS CORROSION CRACK GROWTH ‘The distribution of electrode potential within a stress corrosion crack which is advancing by an anodic metal Toss at the plastically deforming crack tip has been analyzed previously.” The crack geometry is shown schematically in Fig. . Since the crack width w is very much less than its length, the analysis was simplified by ‘Considering unidirectional ion current flow along the VOLUME 12A, JUNE 1981-923‘crack. Figure 2 shows a schematic polarisation diagram ‘of the electrochemical reactions which occur within the crack. The cathodie reaction I occurs on the crack surfaces with the current density vs electrode potential relationship described by line 1. The “bare surface’ or active anodic dissolution reaction occurs at the crack tip with a current density vs electrode potential behavior described by line 2, and the anodie dissolution reaction on the oxide covered ‘passive’ crack surfaces occurs at a constant current density, line 3. This analysis assumes the rate ofthis last reaction to be independent of electrode potential, iz. the slop of line 3 is infinite, and that the crack tip anodic dissolution reaction, line 2, and the cathodic reaction, line 1, obey Tafel kinetics. For an anodic ion current flow from the crack tip an electrode potential gradient must exist along the crack. This gives rise to an ‘excess’ cathodic current on the crack surfaces near to the tip which complements the anodic dissolution at the erack tip. Equilibrium is established when the electrode potential at the crack tip produces an anodic current which is balanced by the {otal excess cathodic current on the crack surfaces. It is this electrode potential at the crack tip whch controls the anodic dissolution and consequent crack growth rate, The previous analysis" allows this potential £,, to be evaluated from: REACTION REACTION | Fig. 1-Schemati diagram of «stress corrosion crack showing the principal electrode reactions (Fig 2). ELECTRODE POTENTIAL: In CURRENT DENSITY) — Fi. 2 Schemate polation aga fo) Cathode redvtion Teacon on sch Sra (2) Ano hoon fasion he Crack ti. 0) Andi scluen reaction on hepsi corte auch sass 924—VOLUME 124, JUNE 1981 E+ A{ex( where i, is the anodic dissolution current density ofthe crack tip at potential £, and a is the Tafel constant for the reaction, /,and E, are the equilibrium corrosion current density and corrosion potential on the crack surfaces, f is the Tafel constant describing the cathodic reduction reaction kinetics on the crack surfaces, wis the width of the crack (see Fig. 1) and C is the onie conductivity of the solution within the erack (here assumed constant). The crack width, w, may be equated to the crack opening displacement, 6, given by: KR paos { a, } By where K is the applied stress intensity, a, is the material yield strength and E, is the Young's modulus of elasticity. The only tinknown in Eq. [1] is the value £, ‘The other variables are obtained experimentally from conventional polarization measurements. Thus E, may be evaluated from Eq. [1] and used to predict the erack growth rate vfrom:!” E, ¥ irexo( zy) M/ (pFn) pi) where M is the molar mass of the material, pis the density, F is the Faraday and n is the charge number of the anodic electrode reaction. The crack growth rateis therefore related to the electrochemical properties ofthe crack tip and surface, the solution conductivity, the applied stress intensity and the bulk mechanical prop- erties of the sample. As shown in the previous paper,” this analysis, as it stands, predicted a crack growth rate which slowly decreases with increasing applied stress intensity. However, during crack growth, solid corro- sion products are deposited on the crack surfaces by reaction of metal ions from the crack tip with the cathodic reduction products of the solution as well as by continued general corrosion (characterized by i, The presence of this product on the crack surfaces effectively reduces the width of the ion conducting path in the crack such that Eq. I becomes: where ris the limiting corrosion product film thickness. ‘This reduces E, and the associated growth rate by an amount which becomes more significant as the value of wis decreased, i.e. at lower stress intensities. Clearly 21 must be less than w for any realistic solution to this, METALLURGICAL TRANSACTIONS Aequation and the condition when w = 2r provides a pwssible criterion for a threshold stress intensity for continued crack growth, 2, PREDICTIONS OF THE ANALYSIS The above analysis may be applied to any alloy system where the relevant electrochemical and me- chanical parameters may be measured. In the present ‘ork, ithas been applied to stress corrosion cracking of atypical low alloy ferrtic steel in high concentration (8M) hydroxide solution at 373 K and an aluminum alloy in acidic chloride solution at room temperature. Table | lists values for the various electrochemical and mechanical parameters typical of those encountered for ihese alloy/environment systems. However, specific values will vary according to the particular alloy nicrostructures and composition and environment. The reults ofthis section are directed towards investigating the influence of changes in the various parameters on the predicted stress corrosion crack growth rates. 2.1 Influence of Applied Stress Intensity and Corrosion Product Layer Thickness We shall consider the effective crack width to be ‘orstant over large distances relative to the crack opening displacement such that the present analysis for 4 parallel sided crack applies. The crack width is therefore given by the crack opening displacement, Eq. 8} Typical values for tow alloy steels are ~ 1.6 um for K'=20MNm>? with 6, = 600MNm-~ and for ‘gehardened aluminum base alloys are ~ 11 um for K = 20MNmm?? with « = 250MNm-2 Metallographic examination of sections through pro- pagaling cracks confirm that crack surfaces are covered bya protective corrosion product. Generally, corrosion products occupy a greater volume than the metal substrate such that they effectively reduce the crack Table |. Electrochemical and Mechanical Parameters Used in the Present Analysis “Typical Low Alloy Ferritic Steel in Typ ow a) ©: @-imy £:Waa) EeY sce) fe (Am) paren Faq 4 hteger 5 MN) Ne) 2 tem 195105 Mtg 5.6 1025 ‘eee to he tatorted calomel reference decode Sats. 2526 te Ret 33, ‘Wet. 7 ane eaneenee SEE METALLURGICAL TRANSACTIONS A ‘width for ion transport in the solution. This is ac- comodated in the present analysis by inclusion of a film thickness ¢in Eq. 4. Values of crack growth rate for a low alloy steel and an aluminum’ alloy have been evaluated from Eq. [2} [3] and [4] for a range of stress intensities and film thicknesses and the results are shown in Fig. 3. Both systems show similar characteristics. For zero film thickness, the previous analysis!” predicted that crack growth rates decrease by a factor of up to 4 with increasing applied stress intensities and tend towards a constant lower value. For filmed erack surfaces, how= ever, the present analysis shows that a threshold stress intensity for crack growth is established which increases with increasing value of r Furthermore, the crack growth rate is reduced for all values of stress intensity by an amount which increases with increasing film thickness and decreasing siress intensity such that the commonly observed two stage growth kinetics behavior is established with the more usually reported plateau in ‘growth rate kineties. Thus, a region where the growth is initially highly dependent on the stress intensity (stage 1) is followed by a region where the growth rate is virtually independent of the stress intensity (stage 2) E tals j s STRESS INTENSITY: MN«i92 é o E 5 : gz STRESS INTENSITY : N37 Fig, 3—~Calculated plots of stress corrosion crack growth rate +8 applied stress intensity fora range of oxide thickaess t fr {@) Low alloy stel in hydroxide solution. (6) Aluminum alloy in acidic chloride solution. (Electrochemical and mechanical parame- {ers as listed in Table I; film thickness values ate shown in am.) VOLUME 12A, JUNE 19K1—9284 é a) > 2 0 ae log C; si" tw) -¢ 7 > g e) T log ¢ ; amv ) Fig. Calculated plots of the stress corrosion erack growth rate as a function of solution conductivity fo: () Low alloy see! in Ihydroxide solution. (0) Aluminum alloy in acidic chloride solution. (Applied stress intensity = 30 MNa-?” and onide thickness ¢ = 0.5, ‘um, Other parameters as listed in Table 1.) ‘over the range considered here. This latter velocity represents a characteristic crack growth rate for the particular system. The predicted rate of 5 x 10? ms! for the low alloy steel in hydroxide solution, Fig, 3(a), sin good agreement with reported values in the range 10 *to 10°? ms: 12%" Tris noteworthy that the predicted stage 2 growth rates are almost independent ‘of film thickness for the range of values considered. In addition the decrease in growth rate with increasing stress intensity is reduced with increasing film thickness toa value which is less than the accuracy of experi- mental measurement, Further the analysis yields real- istic threshold stress intensity values for observed film thickness."*2! The result for the aluminum alloy is consistent with values typical of such systems." Here. the calculated value of 2 X 10°? ms" lies in the range observed for an Al-7 Mg alloy subjected to a 926—VOLUME 2A, JUNE 1981 constant strain rate test." This calculated valueis many orders of magnitude lower than that predicted by models which assume an anodic dissolution reaction a the crack tip occurring at the normal bulk corrosion potential.”!? Here also, the predicted growth rates almost independent of the oxide film thickness 2.2 The Influence of Solution Conductivity In practice, changes in the operating environment may occur which result in changes in sotution conduc. tivity without affecting the kinetics of the various electrochemical reactions. Typically this may arise from deliberate dosing additions or unplanned contamina tion from otherwise inert substances. In general any effect of changes in the conduetivity will be influenced by the operating electrode kinetics. However, the spe- cific effect of such changes on crack growth rate has been considered for the present systems using those parameters in Table I together with an applied stress intensity of 30MIN m-2, yield stress values of 600MNm-~? for a low alloy steel and 250MNm~?foran aluminum alloy, together with a fixed film thickness of 0.5 pm in both cases. ‘The results in Fig. 4 show that changing the conduc- tivity over four orders of magnitude yields less than ax8 change in the growth rate for the steel (Fig. 4(a)) whereas a similar change in the aluminum alloy- produces a change of x35 (Fig. 4(b)). Clearly, differences in conductivity brought about by otherwise inert solu- tion components are of only secondary importance in controlling crack growth rate, particularly for the ste! system, 2.3 The Influence of Electrode Reaction Kinetics The analysis includes as variables the electrode reaction kinetics shown schematically in the polariza- tion diagram of Fig. 2. Here the active anodic disso- lution kinetics of the crack tip are described by line 2 (Ep, ir and a), the ‘passive’ anodic reaction kinetics on the ‘oxide’ covered crack surfaces by line 3 (i), and the cathodic reduction kinetics on the crack surfaces by line 1 (i,, E.and B. In general all of these electrode processes may be dependent on the solution chemistry and temperature as well as the composition and crystal structure of the material local to the crack path. Inthe present analysis we assume the solution variables to Temain constant within the crack. Each of the electro- chemical parameters required for the analysis is readily obtained using conventional experimental procedures on bulk samples with composition and structure simi lar to those occurring at the crack path.!*2 Since in the present analysis the threshold value of stress intensity for crack growth is not directly influ- ‘enced by the various electrochemical parameters we shall only consider their influence on stage 2 growth rate for fixed values of applied stress intensity on oxide film thickness. The predicted changes in growth rate as a function of the crack tip dissolution kinetics (line 2 Fig2) are shown in Fig. 5. Here, the value of i, refers the anodic dissolution current density at the fixed value METALLURGICAL TRANSACTIONS A£, given in Table I. Other parameters are as given in ‘Table I for an applied stress intensity of 30MNm72, oxide thickness of 0.5 um and yield stress values as above. Crack growth rates are shown for different cathodic reaction kinetics (line | Fig. 2). These cathodic rmaction rates are characterized by the current density atthe potential E, listed in Table I. Thus these curves ilusrate the influence of both the crack tip anodic reaction kinetics and the crack surface cathodic reac- tion kinetics on the calculated growth rate. ‘The calculated results clearly show the relative effects of inreasing the crack tip anodic and crack surface cathodic reaction kinetics. For the low alloy steel sys (Fig, 5(a), increasing the anodic reaction kinet- its by an order of magnitude from 10 to 100 Am? increases the crack growth rate by a factor of x3 (for a fined cathodic current density of 1 Am~*) whereas increasing the cathodic reaction kinetics by an order of, magnitude from I to 10 Am=? (for fixed iy = 10 Am”? increases the crack growth rate by a factor of x8. Cery, therefore, small changes in the cathodic reac- tion kinetics on the crack surfaces are of more impor- tance than corresponding changes in the crack tip dissolution behavior of this system. This relative behav- ine, however, will be dependent on the values of the oiher relevant electrochemical parameters. ‘The results calculated for the aluminum alloy are stown in Fig, 5 (6). Here we observe that changes in both the cathodic reaction kinetics and anodic reaction Kinetics ([,) are equivatent in their effect on the growth ‘ate. An order of magnitude change in either rate results ina growth rate change of ~ x2. Differences in the anodic dissolution behavior of the crack surfaces (line 3 in Fig, 2) are given from changes inthe corrosion current density value, i,. Here, more Protective films will decrease the value of i,. The influence of small changes in this parameter on the ‘aleulated crack growth rate are shown in Fig. 6, In the low alloy stel system, small increases above 0.1 Am™* "sult in a very rapid decrease in measured crack powth rate (Fig. 6(a)). For values less than ~0.1 Am-%, et, the crack growth rate is almost unaffected by anges inthe value of /,. Crack growth rates for the aluminum alloy system, Fig. 6(6), are insensitive to stanges in the corrosion current i. 24 Influence of Solution pH and Extrapolation of Accelerated Test Data As stated above, much stress corrosion crack growth daia is and has been obtained using procedures where Bowth rates are accelerated to give measurable changes ‘merack length in a time scale appropriate 10.8 ‘laboratory test. Acceleration is most frequently effected inreasing the concentration of active species in the ‘orosive environment. The present analysis provides lonly a means of calculating crack growth rates from i electrochemical parameters but in addition allows ‘entitication of those parameters which are of most Spnficance when extrapolating to the usually more ‘diute environments which are encountered in service Conditions, METALLURGICAL TRANSACTIONS A, log ig 5 Ani \ a . oo > & 2 3. 43 fog iy Am? 7) Fig. $—Caleulted pots of crack growah rate vs crack tip anodic dissolution current density fora range of crack surface cathodic current densities for: (a) Low alloy see in hydroxide yolution. {@) Aluminum alloy in acidic chloride solution. (Applied strexs intensity = 30 MN? and oxide thickness ¢= 0.8 4m. Other parameters as listed in Table L.) Much effort has been expended in the investigation of stress corrosion crack growth in low alloy steets in concentrated hydroxide solutions."*2"", Such efforts have met with some success in providing a relative ranking of various steels and heat treatments based on their susceptibility to stress corrosion cracking (as ‘measured by crack growth rate). However. at present such data has been found to be of little value in predicting the kinetics of cracking in plant components ‘operating in service environments encountered for ex- ample in the low pressure stage of steam turbines used, in the electrical power generating industry. The present analysis, however, provides a basis for predicting crack growth rates in these solutions In low alloy steels the crack tip anodic reaction of interest in low pH solutions involves a first order VOLUME IZA, JUNE 19819272 T 0 Jog ig j Am? log Vi: log i; Ami? o Fig, 6~Caleulated plots of eeack growth rates crack surface corrosion current density fr: (2 Low alloy stel in hydroxide Solution. (6) Aluminum alloy in acidic clotide solution. (Applied sires intensity = 30 MNm"22 and oxide thickness ¢= 0.5xm. Other parameters as listed in Table 1). hhydroxyl ion interaction’ as a rate determining step. However, it has been shown recently that such a reaction is modified at high pH by Temkin adsorption® of hydroxide ions such that the overall reaction kinetics are best described by a half order interaction of hydroxide ion together with a Tafel paramter o = TIF (= AEIAIn i) = 0.032 at 373 K. Conse- ‘quently, we can predict the value of i, at pH values other than in 8M sodium hydroxide at 373 K. Assuming the pH of this solution to be = 14 then j, = 100 X 10T(pH ~ 14)/2) and since conductivity is linearly related to the ion content we may put C = 10 x 10p (pH ~ 14), Hurlen** has shown that the principal cathodic reduction reaction in these high pH solutions is the reduction of water in which the Volmer reaction is modified to: HO +e OH +H, 1 Here the hydrogen evolution reaction is independent of 928—VOLUME 12A, JUNE 1981, pH and has a fixed Tafel slope (— f) of “2RT/F(=AE/A Ini) = —0.064V at 373 K. Finally, the anodic dissolution kinetics of the crack surfaces, Reaction [3], Fig. 2, will be affected by the local environment (ie. pH). To the authors’ knowledge there is no definitive data on the pH dependence of corrosion rate but it is reasonable to assume that such a depen- dence may well be similar to that of the crack tip dissolution behavior. Consequently the anodic dissolv- tion behavior of the crack surfaces is given by i, = 10 X 10}(pH-16)/2). Similarly, the value of E, will change with pH by a proportional amount related othe cathodic Tafel parameter B. Using these pH dependent values of i, ip, Zand C the stage 2.crack growth rate for a low alloy steel in hydroxide solutions has been 73 9 a pH ‘a oH oy Fig. 7—Calevlated plots of erack growth rate versus solution pH fo: {(@) Low alloy stel in hydroxide solution. (6) Aluminum alloy nace chloride solution for the range of chloride molaities shown inthe figure. (Applied stress intensity = 30 MN"? and oxide thickness ¢ 0.5 am, Other parameters as listed in Table 1). METALLURGICAL TRANSACTIONS Acluated as a function of pH. The results are shown in Fig. 1. It is clear from the previous section that any underestimate for the value of i, as a function of pH will have ltt effect on the predicted stage 2crack growth rate ‘Other workers?23122 have proposed that the pH dependence of the erack tip anodic reaction may be dkscribed simply in terms of a first order intera vith hydroxyl ions such that ip = 10 x 10f(pH-14) and i= 10 10}(pH-16) with a Tafel parameter « of (= AE/Aln 1) = 0.016V at 373 K. Crack growth rates as a function of pH predicted from this data are ako shown in Fig, 7(a) as a dashed line for comparison. The results show that the predicted crack growth rate ‘sreases with decreasing pH. The slope AlogV/ApH, however, is not constant such that empirical linear catrapolation of measurements made in high concen- tation solutions is not valid. Difference in growth rates predicted from the two crack tip dissolution mecha- nisms are small particularly at lower pH values. The present extrapolation of electrochemical data from high ‘oncentrations is necessary for prediction of growth ‘aes in near neutral solutions because of the difficulties associated with obtaining such values experimentally. ‘The growth rates predicted for low pH solutions in Fig 7a) are in very good agreement with those ob- sened from cracking in low alloy steel L.P. turbine components operating in condensing steam with a pH inthe range 8 to 9.122" Depending on the particular sta, crack growth rates in the range 10-"! to 10-" ms! have been reported, Siress corrosion crack growth in aluminum alloys is usually associated with low pH (<7) solutions often Containing halide anions." Growth rates are ac- celerated by both reducing pH and increasing anion Conient. Ford? has demonstrated that the anodic dssolution kinetics of the straining crack tip are rela- thely unaffected by either the solution pH or anion Content, o by small changes in the crack path alloy composition. The principal cathodic reduction process cecurring on the crack surface in low pH slutions is the "eduction of hydrogen ions. Here the reaction involves a fist order interaction with hydrogen ions such that the "tes linearly related to the hydrogen ion concentra- ton, ie, the cathodic current density at potential ~10QV sce. is given by (2% 10-4) x 101(1 ~pH) An”?. The solution conductivity is given by the sum of {te contributions from the hydrogen ion concentration and that from any other ionic components, usually sodium chloride. For the case of acidic sodium chloride, the toil conductivity is given by" C = 4 x 101(pH) + 10x NaCl. Finally, the anodic dissolution behavior the passive film covered crack surfaces is dependent on the pH. Chatalov has reported the corrosion rate, ‘lo decrease with increasing pH such that i, = 2 X10"? x 10((1-pH) X 0.7) Am-2, As above, £, ages with pH by an amount proportional to the ‘thodic Tafel parameter. It is generally found that ging chloride ion concentration has litle effect on Passive corrosion rate. stress corrosion erack growth rate for the alu- ‘inum alloy has been calculated as a function of pH ‘2d sodium chloride concentration using the above tochemical data and the results are shown in METALLURGICAL TRANSACTIONS A Fig. 76). The stage 2 crack growth rate decreases with increasing pH and decreasing sodium chloride concen- tration. The influence of pH, however. predominates, particularly for lower concentrations of sodium chlo- ride, Ithas been shown by several workers® that the pH within a growing stress corrosion crack in aluminum base alloys in normally neutral solution is decreased to constant value of ~ 3.5 by the localized hydrolysis of the aluminum ions generated by anodic dissolution of the crack tip. This suggests that the pH should always bbe less than or equal to 35 thus predicting a minimum growth rate of ~10-* ms~! (Fig. 7(6)) which is in agreement with measured values quoted by Ford." DISCUSSION The analysis predicting the stress corrision crack ‘growth rate is based on establishing the electrode potential distribution within a stress corrosion crack which is advancing by a process of enhanced anodic dissolution and shows the electrode potential at the tip of the crack to be lower than the experimentally measured bulk corrosion potential. Since itis the local electrode potential which determines anodic dissolution kinetics the crack growth rate predicted by this analysis is lower than that more usually evaluated by assuming the bulk corrosion potential £, to approximate those conditions at the crack tip. This effect is significant. ‘even in high concentration solutions such as those considered in the present work. Crack growth rates are predicted from a knowledge of the equilibrium electro- chemical properties, including EE. ,.ip.C.aand B, all of which can be readily measured on bulk specimens. and a value for w which may be calculated from Eq, [2]. Asa corollary, itis possible to investigate the influence of environment and material composition variables on stress corrosion crack growth rates simply be examining their contribution to each of the measured electro- chemical properties. Since the anodic and cathodic behavior are often strongly dependent upon material composition and microstructure. itis necessary to have a knowledge of the local material composition along the stress corrosion crack path. Stress corrosion cracks, generally follow well defined microstructural features such as grain boundaries or slip bands and conse- quently it is necessary to characterize any solute seg- regation or precipitation processes which may occur. This is particularly true for intergranular stress corro- sion crack growth in steels where itis established that ‘minor alloying or impurity elements, which are known to segregate to prior austenite grain boundaries. sig- nificantly modify susceptibility.” Such local compo- sitions are becoming increasingly realistic to measure with the availability of high spatial resolution analysis techniques such as scanning transmission electron microscopy’energy dispersive analysis and Auger elec- tron spectroscopy. Electrochemical properties measured ‘on bulk samples with compositions typical of these local regions may be used to evaluate the stress corrosion crack growth rate." # However. itis not vet possible to include the effect of structure in the active crack path. As yet. the sensitivity to stress corrosion cracking. ‘sulting from structure has to be established. VOLUME 124, JUNE 1981-929‘The present work illustrates the influence of mag nitude changes in the various electrochemical param- eters on the predicted stress corrosion erack growth rates for two commercially important alloy systems in environments where such cracking is known to occur. The results presented accomodate that range of electro~ chemical parameters which may be expected for these systems. In general, the results demonstrate that the cathodic reaction kinetics on the crack surfaces may be equally or even more important than the crack tip dissolution kinetics in controlling the stage 2 crack ‘growth rate. This point has been demonstrated exper- mentally by the authors for both low alloy steels!" and aluminum alloys? in environments similar to those considered here. The present analysis requires the crack tip dissolution to bea continuous process which is localized to the plastically straining crack tip. Such a constraint may be satisfied by invoking the concept of a rapid passivation of the locally deformed metal at the tip as the crack advances. This maintains a crack aspect ratio which preserves sufficient stress intensity for continued ‘growth. However, in this analysis no attempt is made to define those passivation kinetics required for continued growth, but rather only predicts the crack growth rate assuming such passivation. Clearly, it is the detailed passivation kinetics which can control whether growth will continue but the present analysis indicates that it ‘may not be necessary to include any such consideration to establish the rate of growth. The accelerated anodic dissolution at the crack tip is assumed to occur over the total width of the strained tip. In general, the strain required to accommodate local displacements at the crack tip are very large and must involve the activation of many slip systems on several non-coplanar variants, Thus itis reasonable to assume that this strain must be distributed over a significant portion of the crack tip region defined by the crack ‘opening displacement. Any error in assuming that an area equal to the crack opening displacement is actively dissolving is equivalent to the proportional error in the value of i,. The results of Fig. 5 show that relatively large changes (or errors) in specifying /, have only a small influence on the predicted growth rate, For the present steel/hydroxide and aluminum/acidic chloride systems an order of magnitude error in specifying the active area at the crack tip (or /,) would result in a ‘change of less than x2 in the predicted growth rate. This analysis provides a basis for theoretically con- sidering the relative contributions of the various electro- ‘chemical parameters to the rate of crack growth in any given environment, Thus, in view of the difficulties ‘currently associated with the experimental determina tion ofall of the necessary material and environmental parameters in operating plant components, the analysis Provides a means of identifying the relative importance of each parameter in controlling the growth rate. Critical parameters can be identified and the accuracy to which they need to be measured may be specified. The extrapolation of electrochemical parameters ob- tained in high concentration solution to lower concen- trations has assumed no change in the various rate controlling processes and does not take into account 930—VOLUME 124, JUNE 1981 those environment changes within the crack. Both the anodic and cathodic processes have been considered to be under activation control with their reaction kinetics obeying a Tafel relationship. Under some circumstances this may not be valid and other rate determining processes may intervene and reaction kinetics may become subject at high current densities and viscosities to, for example, diffusion control. This would require a modification to the present assumed Tafel polarisation. ‘The analysis may be adapted to accommodate any polarization behavior since the basic process by which the electrode potential at the crack tip is evaluated remains unchanged. In general, where other rate con- trolling processes occur to increase the polarization, the overall crack growth rates will decrease to values lower than predicted by assuming Tafel kinetics. Thus the present analysis results in a conservative prediction of crack growth rate, CONCLUSIONS Stress corrosion crack growth rates may be predicted using an analysis of the electrode potential distribution within the growthing crack. This analysis uses electro- chemical data obtained from measurements on bulk samples together with a knowledge of simple mechan- ical properties in order to predict the kinetics of erack growth rate vs applied stress intensity. Results are in ood agreement with those which are phenomeno- logically observed in aqueous stress corrosion cracking in high concentration solutions. The overall growth kinetics are determined by the electrochemical prop- erties of the crack surfaces together with the crack tp. AS a consequence the analysis provides a basis for extrapolation of accelerated stress corrosion crack growth data to lower concentration solutions which are frequently encountered in service environments. LIST OF SYMBOLS (V) Tafel parameter describing the anodic disso- ution behavior of the crack tip. (Tafel parameter describing the cathodic reduc- tion behavior on the erack surface. (Q-!m~) solution conductivity (m) the crack opening displacement -. (V) equilibrium corrosion potential of the crack surfaces + (V) a fixed electrode potential for the erack tip anodic dissolution reaction. . (V) the equilibrium mixed electrode potential atthe tip of a growing stress corrosion crack. Ey (MNm-*) Young's modulus of elasticity F (C) the Faraday (Am™2) the corrosion current density at potential E, (Am) the anodic current density at potential E (MNm~> the yield stress (Mm) the applied stress intensity (m) corrosion product film thickness on the crack surface (kem™?) density (kg) molar mass men wR m = mS = METALLURGICAL TRANSACTIONS Aa ae 1 the charge number of the electrode reaction Y’ (ms~') stress corrosion crack velocity vw (m) the crack width ACKNOWLEDGEMENT This paper is published by permission of the Director General, South Eastern Region, Central Electricity Generating Board. REFERENCES 1. D.Kalderon: Pro. Inst, Mech. Eng, 1972, vol 186, p. 341. 2AM. Hodge and IL: Mogford: Proc. Jnst. Mech. Eng, 1979, vol 1.9.53 3,5 W.Parrand F. G, Stub: Univ. Minois Bull, 1928, p. 177 ‘A. MeEsily and A. P. Bond: J Electrochem. Soc, 1969, vol. 1 pil, 5. EN, Pugh: The Theory of Stress Corasion Cracking i Alloys, 1911, NATO, Brussels. 6. 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