J. Mech, Piss. Solas, Vol. 46, No.6, pp. 1128-1137, 199% 11998 Ehevier Science Lid. All Fights reserved Pergamon Printed in Great Britain (0922-5096/98 $19.00-+-0.00 PIL: $0022-8096(97)00054-9 MECHANICS AND THERMODYNAMICS ON THE STRESS AND HYDROGEN INTERACTION IN CRACK TIP STRESS CORROSION: EXPERIMENT AND THEORY SCOTT X. MAO* and M. LI Department of Mechanical Engineering. The Unversity of Calgary, Calgary, AB, Canada T2N 1N4 (Received 11 November 1996; in revived form 23 July 1997) ABSTRACT. The hydrogen distribution around a erack tip subject to stress corrosion for pipeline steels was measured by secondary ion mass spectrometry (SIMS) and modelled by finite element analysis. The results show that hydrogen will be generated and accumulated around the SCC crack tip. From thermodynamics analysis, it has been found that the interaction between the stress and hydrogen at the crack tip will increase the activation energy for anodic dissolution. Hydrogen plays an important role in the process af SCC for pipeline steels by promoting stress corrosion cracking of anodic dissolution type. © 1998 Elsevier Science Led. All rights reserved. Keywords: A. chemo-mechanicul processes. A. fracture, B. crack mechanies, B. elastic-plastic material, C finite elements, 1. INTRODUCTION The stress corrosion cracking (SCC) of metals and alloys in aqueous solution has been widely studied. Mechanisms have been proposed to explain SCC (Latanision and Stachle, 1969 ; Theus and Stachle, 1977; Dean Jr, 1976; Jani er al., 1991 ; Parkins and Singh, 1990). These could be summarized by anodic dissolution cracking (ADC) and hydrogen induced cracking (HIC). The mechanisms controlling the cracking are dependent on the materials system. These two mechanisms were studied separately and both were supported by certain experiments. However, little attention has been paid to the interaction between hydrogen generated during SCC and ADC, Usually, oxidation of a metal is accompanied by a reduction reaction of hydrogen ions in an aqueous solution. The hydrogen produced during SCC could diffuse into the metal and concentrate at the crack tip zone, In most cases, this generated hydrogen may not be enough to cause hydrogen induced cracking because a critical hydrogen content is required to generate HIC, However, the concentrated hydrogen at the crack tip zone will have an interaction with crack tip stress to generate large free energy changes at the crack tip so as to accelerate the anodi dissolution rate at crack tip. The stress corrosion cracking of low alloy steel as well as pipeline steel in bicar- bonate solution has been studied (Parkins and Singh, 1990; Parkins er a/.. 1993: * To whom correspondence should be addressed.1126 S.X. MAO and M. LI Szhlarska-Smialowska et al., 1994: Liu and Mao, 1995; Parkins er al., 1994; Rebak et al., 1996) and it has been found that anodic dissolution dominates the SCC growth of the materials in high pH bicarbonate (Parkins e7 al., 1988) or highly concentrated bicarbonate solution. This is the so-called classical SCC. However, hydrogen is not considered in this process, In low pH bicarbonate solution, which is a common chemistry under coating disbondment of pipeline buried underground (Liu and Mao, 1995), the SCC mechanism of the steel is different from the classical SCC because of the low pH. It has been reported that the cracking morphology in low pH bicarbonate is transgranular SCC (TGSCC), and the growth rate is higher than the prediction by the anodic distribution model (Parkins er a/., 1994). In the low pH solution, more hydrogen is generated and we have to consider the hydrogen role in the stress corrosion cracking of anodic dissolution type. Synergistic action of stress and hydrogen on anodic dissolution should be taken into account in the mechanism because itis difficult to prevent hydrogen evolution during the SCC in aqueous solution, especially for low pH solution. The purpose of this work is to explore the role of hydrogen in the process of anodic dissolution SCC using thermodynamics. The hydrogen distribution around a stress corrosion crack tip is to be investigated by experimental measurement and ite element modelling. 2 HYDROGEN DISTRIBUTION AT CRACK TIP SUBJECT TO STRESS CORROSION Experimental measurement Compact tensile (CT) specimens (see Fig. 1) were machined from pipeline steel X- 80 with yield stress of 600 MPa, The CT specimens were loaded by a wedge with Fig. 1. Compact tensile specimen. Thickness B= 6 mm, W'= 15.2 mm, a= 7.5 mm.Crack tip stress corrosion 127 different levels of J integral value, and then the self-loaded specimens were immersed in NS-4 solution, the typical test solution for coating disbondment in Canadian pipelines (Liu and Mao, 1995). at free potential for 72 h, The composition of NS-4 solution is as follows: (g/l) 483, NaHCO; 0.12, KCI; 0.137, CaCl, and 0.131, MgCl, -H,0. The J integral was evaluated from the following (Clarke and Landes, 1979) 2af (ta’) Bh| (4x?) f where 4, 6 and B are area under the load vs displacement curve, area of unbroken ligament and specimen thickness, respectively. 2 is a dimensionless function and can be expressed by (20Y,,/2a\ J? fa, 7 “(3 a(7)-| -(5+!} where is the crack length During immersion, hydrogen is generated and diffuse into the highly stressed zone. After 72 h of immersion, measurements of hydrogen distribution in CT specimens were carried out using SIMS (secondary ion mass spectroscope). Primary ion beam of Ar’, accelerating voltage of 15 KV, beam current 1x 10-" A and diameter of ion beam spot <50 um were used. Figure 2 shows the measured hydrogen concentration near crack tip for applied J integral values of 32, 102 and 136 MJm~, It is found that the higher the applied J 10 7 me = 136% 108m? te T= 102 « 10° Mn moe F230 x 10° Sm? - Unstressed, pH =8 0 os 1 1s Relative Hydrogen Concentration, C,(H)/C, wa(H) Distance From the Crack Tip, mm. Fig. 2, Effect of J on hydrogen distribution near the crack tip for X-80 carbon steel in free potential128 S.X. MAO and M. LI integral or stress intensity factor K. the higher the hydrogen concentration near the crack tip. 2.2. Finite element modelling and analytical solution for elastic-plastic material A finite element modelling was carried out using the program ABAQUS to calculate the stress distribution around the crack tip based on the loading and specimen geometry in the experimental study. The grid used in this work is shown in Fig. 3 ‘The elastic: plastic stress vs strain relationship of the pipeline stee! can be expressed as AAU) (b) Fig. 3. Finite element mesh. (a) Globiil mesh and (b) local mesh stround erack tp.Crack tip stress corrosion 129 where cp and a are the yield stress and strain, respectively. is the strain hardening component and satisfies n> 1, and 2 is a dimensionless material constant Since the crack growth during SCC is very slow, we can assume the steady state diffusion of hydrogen. This means that the diffusion time is long enough to allow the hydrogen concentration in front of the crack tip to reach equilibrium state. The hydrogen concentration under equilibrium conditions in front of the crack tip can be expressed as (Dean Jr, 1976) Ce Pu a = Cex | On pe h Q where C, is the hydrogen concentration induced by the applied stress field around the crack tip, Cy is.a bulk hydrogen concentration, 4, and V7, are volume hydrostatic stress and partial molar volume of hydrogen in the metal, respectively. R is molar gas constant, and T is the temperature. The stresses near the crack tip are calculated by FEM based on elastic-plastic material with strain hardening under plane stress. In the FEM calculation for X-80 steel the strain hardening coefficient 1 is taken as 6.6 and 2 is taken as 0.01, and the result for the plane stress condition is shown in Fig. 4 ILis found that the FEM result is close (o the theoretical result of HRR (Hutchinson, 1968: Rice and Rosengren, 1968) which can be expressed as J wat aC yam. @) yy LP where /is the integral value, /, isa constant and 4,,(0) is angular function (Hutchinson, 6.0 ress distribution 0.0 2.0 40 6.0 8.0 Normalized distance from crack tip Yates Fig. 4. Stress distribution along crack tip.130 S.X. MAO and M. LI 1968), r and 0 are illustrated in Fig. 1. The hydrogen concentration Cy, along the crack tip is then calculated using (2) From eqns (2) and (3). the theoretical hydrogen distribution at the crack tip for elastic-plastic material under equilibrium condition can be expressed as JoNer. eel (sana) | “ where 6,(0) = {[4) (O+4s() +4 s(O))/oy and 2, = Pyoo/RT (material constant, 0.48 for X-80 steel). When #) = 0 and r = X, (4) becomes Cn 44-4 (5) } \a69t01,) For the plane stress condition, 6,(0) + 0.65 -(x/J/a,) can be considered as the nor malized distance from the crack tip. The normalized hydrogen distribution along the crack tip is shown in Fig. 5. It is found that the hydrogen distribution along the crack tip obtained by both HRR and FEM goes up at the crack tip and lies close to the experimental result obtained by SIMS. Although the peak values from the experiments are not predicted by our FEM analysis based on the one-parameter J-based fracture mechanics shown as (3). they can be explained successfully by the maximum hydro- static stress field ahead of a mode I loaded crack tip due to the presence of plastic zone in front of the crack tip, which was analysed by many researchers (McMeeking and Parks, 1979: Shih, 1985; Shih and German, 1981: Hutchinson, 1983). A recent Testing Result. y-asiws Measured by SIMS Hydrogen concentration Gu 0.0 2.0 40 6.0 8.0 10.9 Non ized distance from crack tip Nae Fig, 5, Hydrogen concentration along erack tip.Crack tip stress corrosion ar important contribution was made by O'Dowd and Shih (1991) to develop a two- parameter approach to analyse the stress triaxility ahead of a crack tip, which could be employed to further our comparison to the experimental results in this paper. ANALYSIS OF THE HYDROGEN AND STRESS. INTERACTION 3. THERMODYNAMI Hydrogen could evolve, enter the specimen and concentrate at the crack tip during the process of SCC. Hydrogen can cause internal energy change and entropy change of the material and can interact with stress. These changes could result in the increases of anodic dissolution rate and SCC susceptibility According to thermodynamic and electrochemical principles, anodic current can be expressed as a function of free energy change, AG, during the corrosion process (West, 1980). Consider a reaction for the corrosion of a metal M in an aqueous solution. M+2H* = M2) +Hyt (6) Hydrogen might be evolved in some SCC systems. such as low alloy steel in Na,COy solution, stainless steel in hot MgC. solution and aluminium alloys in NaCI solution Itis dependent on the pH level of the solutions. When the metal containing hydrogen is stressed. a reaction at the crack tip can be expressed as Mio, H)+2H° = MO) + Ht oO The products of reaction (7) are the same as those of the reaction (6). Therefore, the differences of electrochemical potential and the reaction rate between reaction (6) and (7) are caused only by the free-energy change AG y(a. H) of the stressed and charged metal, The free-energy changes in reactions (6) and (7) are denoted as AG, and AG, respectively. The corresponding electrochemical potentials Z, and E, at equilibrium state can be derived from the fundamental relationships AG, = Gy Gy, ~Gy~ 2Gy = —nFE), (8) AG. = Gy 4G yu — Gyula H)—2G6, = AG, ~AG (0, H) = —nFEs, (9) where Gy. Gyr. Gyula. H). Gy, and Gy. are formation free energies of M. M+, M(o.H), Hs: and H™, respectively. 1 is the number of electrons exchanged in the reaction, F is Faraday’s constant, and the change AG,(o, M) = Gla. H) —Gy is caused by stress and hydrogen in the metal M. The anodic dissolution current i, without stress and hydrogen effects in reaction (6) is AG, FE i, = nesr|- es wes [er 6} (10) where /fis the charge transfer coefficient. The dissolution current i(@, H) at the str crack tip in reaction (7) isua $.X. MAO und M. LI AG, AG, —AGy(o, H) i(o,H) = igo. ten] - me |= ile. te| - ie ‘| (ly RT If hydrogen and stress do not change the exchange current density jy, then (11) yields AGy(o, H) # Het = top| er (12) AG,(a, H) can be given at constant pressure (stress) and constant temperature as AG, (a. H) = AU-TAS+ PAY, (13) where AU is the internal energy change, AS'is the entropy change, P(= ~a) is the pressure and AV is the volume change. The internal energy U and entropy S including configuration entropy and vibration entropy are functions of chemical composition and temperature. The applied stresses do not change them. For the case of zero stress (P = 0) and AGy(a = 0, H) = AU—TAS, (12) becomes AU-TAS Ho =0.H) = iyexp} pee Klas (4) where ky is a hydrogen factor. The work, PAV, is done on the metal when a stress is applied and can be divided into two terms of U, and U>, where U; is the strain energy density and U, is the interaction energy between the lattice strain induced by hydrogen atoms and external stress field. For the case with stress and no hydrogen, AU, AS and U; are zero, and then U, can be given by (is) where His the molar weight, «), a2 and a are the principal stresses, p is the density and £ is the Young's modulus. Substituting AU=0, AS=0, U;=0 and U, = Wo) +e) +0%)/2Ep into eqns (12) and (13), we get the effect of stress on anodic dissolution rate as Wai +03 +03) io, = 0) =i, exp ee b O nr | (16) where k,, (7 = 1.2.3) are stress factors ‘The interaction energy Uy between the lattice strain induced by hydrogen atoms and external stress field is given by (Li er al.. 1966) U; = 4,0 5. (17) where 0, is (a) +.024+0,)/3, a volume stress. In the presence of both stress and hydro- gen, the synergistic effect of hydrogen and stress on anodic dissolution rate isCrack tip stress corrosion 1133 AU—TAS Wa} ito. = isso : pes oe 3) 5 deprT Vn | xexp [*% a ‘| = kykokwis (18) RT ky, ke and ky, are the effect factors caused by hydrogen, stress and their synergistic action, respectively, k, is the effect of hydrogen on the anodic dissolution rate without stress and k, is the effect of stress without hydrogen. ky, k, and ky, are defined by AU—TAS _ Ce 9) (20) 1 where (Ou, by = F/G. A= Go. Zand 24 are materials constants. For pipeline steel, 4 is in the range 1.1 x 10°* 2.5% 107 and Zy is in 0.32-0.48. At the SCC crack tip, local stress a, can reach five to six times the yield strength of the material as shown in Fig. 4. For pipeline steel X-80, 6, = 600 MPa, W = 55 g/mol, E = 210° MPa and p = 7.8 « 10' kg/m*, Substituting W, T= 298 K and R = 8.31 J/mol+K into (16), considering ¢, = 6, = 3000 MPa and o, = 0, we have i(a) = 1.15i,. This means that anodic dissolution would be inereased by crack tip stress, hence 15, When hydrogen is concentrated at a highly stressed zone around a stress corrosion crack tip, the hydrogen will have a synergistic effect with the crack tip stress on the anodic dissolution. For pipeline steel X-80, substituting, P= 2x10 mmol, R= 8.31 Jmol: K. T= 298 K and a, = 4a, into (22). we have ky, = 2. ‘om (18), i(a. H) = 3.4i,(H). The synergistic effect of stress and hydrogen on the anodic dissolution is much higher than their separate effects. The effects of stress and the interaction of hydrogen and stress on the anodic dissolution as a function of normalized stress are shown in Fig. 6(a) and (b) if we take [i as 0.75 (Uhlig and Revie, 1985). According to Faraday’s law (Mao and Li, 1995), the stress corrosion crack growth rate by anodic dissolution mechanism in the presence of hydrogen can be given by da\ Ww v = io. = kyk kucha 24 (a) NID agg = KakeRuce, Ce) where 17 is the valence of the iron and F is Faraday’s constant. Assuming hydrogen itself does not change the anodic current (i.¢. ky, = 1), (24) becomes134 1.24 1.2 ky a 1.08 Stress factor 1.04 S.X. MAO and M. LI B= 0.75 J expl (6,/ 6.) 2B] " : 4 6 8 10 Normalized stress a/0 Fiz, O(a), The stress effect k. relationship with normalized stress 4, The synergistic effect ky, of hydrogen and stress 4 6 8 10 Normalized volume stress 04/0, Fig, 6(b), The synergistic effect &,,, relationship with normalized volume stress a ( da (de s) tnx (i as where da/dr is the growth rate without the effect of hydrogen.Crack tip stress corrosion nas 4. HYDROGEN EFFECTS ON THE SCC SUSCEPTIBILITY After pre-hydrogen charging of 20 h with cathodic current density of 3 mA/em*, the tensile specimen was stressed in air environment and the ductility was found almost (o be the same as that for the specimen without hydrogen charging in air environment. This demonstrates that the hydrogen content during 20 h of charging (about 2-3 ppm, see Gu and Mao, 1997) is not enough to generate conventional hydrogen induced cracking. However. this amount of hydrogen can have an influence on the anodic dissolution type of stress corrosion cracking. Pre-charged hydrogen increased SCC susceptibility of X-80 pipeline steel in NS-4 solution. Tensile specimens with and without pre-hydrogen charging were tested under different slow strain rates in NS-4 solution. Average SCC growth rates as shown in Fig. 7 were measured by a scanning electron microscope. It is found that pre-hydrogen charging increases the stress corrosion crack growth rate. As can be seen in Fig. 7, SCC growth rate with pre-hydrogen charging is about four times larger than without hydrogen charging although the growth rate increases slightly with strain rate. Since the anodic dissolution mechanism at free potential dominates the SCC of the pipeline steel in NS-4 solution (Parkins 7 af. 1994; Rebak ef al.. 1996), the hydrogen introduced into the steel can promote the anodic dissolution. by a factor of 3.5 for X-80 pipeline steel which can be derived from (24) 5. CONCLUSIONS (J) Hydrogen accumulation at the crack tip subject to stress corrosion has been experimentally measured and modelled by finite element analysis. The con- 36 Q x é E os —*— uncharged 2 —*— precharged 2 * = £5 3 S 0 Q 3 8 5 Strain rate, x 107 Fig. 7, Stress corrosion crack growth rate relationships with strain rate for hydrogen chat X-80 steel in NS-4 solution bubbled with 5% CO. gas. and uncharged1136 S.X. MAO and M. Lt centration of hydrogen at the crack tip increases with applied J integral or stress intensity factor (2) The interaction between crack tip stress and hydrogen will generate large free energy changes at the crack tip which will accelerate SCC growth rate of anodic dissolution type. (3) Hydrogen int susceptibility duced into the steel can promote anodie dissolution and SCC ACKNOWL GEMENTS This work was supported by « Strategie Grant from the Natural Science and Engineering Research Council of Canada. We would like to acknowledge that Dr L. Qiao has done the SIMS measurement and has contributed to the part of modeling, Dr J. Luo at University of Alberta has contribution to this project and Dr B. Gu and W. Yu at The University of Calgary carried out the slow strain rate test and SEM observation, REFERENCES Clarke, G. A, and Landes, J. D. (1979) Evaluation of the J integral for the compact specimen. J. Test Kral. 7, 264 269. Dean Jr. S. W. 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