onesin ence 139 (2018) 276-287 Contents lists available at ScienceDisect Corrosion Science Journal homepage: www.clsevier.com/locate/corsel Corrosion behavior of X65 pipeline steel: Comparison of wet-Dry cycle and ® full immersion Jianxing Yu", Huakun Wang", Yang Yu’, Zhen Luo, Weidong Liu’, Caimei Wang” Sua Ke abr of Uc ger Siti end Sy, jn Unversiy, Tai 200072, Cina "cara moan Gene for Avene Spy and Dp xr, Stag, 200240, china Scholars cence ad Engine, Tat Unversiy, Ta. 300072, China ARTICLE INFO ABSTRACT Keyword Stal dbuton hein eorosion behavior of X6 pipeline steel subjected to wel-dry yelic exposure and fal mersion were Investigate to determine the corenon behavior of N85 pipeline sel In marine splish zone and below the waterine. The scanning electron microscope (SEN) text rests ndeated that pitting corosion ocurred nder ‘weedy eee condition whereas general corosion occurred under fll immersion, The statistical results ofthe ‘measured pit depth and groove depth using SD measuring laser microscope indicted tha both of then follow a legnorral distribution rather than normal distribution. Moreover, the statistical dsibuion of diameter 1 in cates that the nist layer is not protective, whereas m <1 indicates thatthe corrosion process isa deceleration process caused by the pro tective rust layer [23]. Double rust layers were observed in the splash zone [19,23]. The inner layer is dense and adherent to steel, and the ‘outer layer is porous. The rust is composed of mainly ferric oxyhyde ‘oxides (FeOOH), The mass ratio (a/y*) of erystalline «-FeOOH to the total mass of y-FeOOH, -HeOOH, and Fe,Q, in the rust layer i ceferred {os the protective ability index ofthe rust formed on weathering ste. ‘When a/y* > 1, the eorrsion rate fs more than 0.01 mm/year [25] “To date, most ofthe published works on the carosion behavior of itferent steels under wet-dry condition mainly focus on the effect of temperature [271, corrosive medium [21], and mechanical factors [23] from the qualitative perspective. The cortesion damage was deseribed the form of mass loss [3,23-25], and the composition of corrosion product was used to explain the varying corrosion rate (26,29) It has bbeen noted that pitting corrosion occurs under wet-dry condition [23]. In this case, mass loss cannot destrbe the corresion damage well, re sulting in an underestimation. ‘To the best of the authors’ knowledge, there is no study on the ‘characteristics of corrosion damage of X65 pipeline stecl under wet~dry ‘yclic and full immersion conditions in a quantitative manner. This study aims atthe quantitative description of corrosion damage of X65, steel using 3D measuring laser microscope. The measured pit/graove depth was statistically analyzed, and subsequently, the mean pit/ ‘groove depth propagation law was derived. The extreme statistic ana Iysis was also used to derive the corrosion propagation model of max: imum pit depth, which provides the basis for the reliability assessment ‘of marine structures. Moreover, the characteristic of rust layer was ‘quantitatively analyzed using X-ray diffraction (XRD) and scanning ‘electron microscopy (SEM) to determine the discrepancy between ‘wet-dry cycling and full immersion 2, Experimental 2.1, Chemical composiion ‘The tubular structure is most widely used in marine engineering (as the truss structures used between the upper deck and leg of a platform, jacket and riser), and is exposed to wetdry cyclic or fl immersion environment. The manufacturing process of tubular struc tures alfects the distribution of residual stress and thus affects the ‘corrosion process. The pipeline steel (API X65) was used for better re- presentation ofthe earrosion behavior of sch a structure. Specimens of dimensions 25 x 25mm? were machined from a steel pipe of diameter 825mm and thickness 10mm using wice electrical discharge. ma- cchining. Fig. 1 shows the corresponding sampling process and the ‘chemical compositions (w96) are presented in Table 1 22. Testing conditions and procedure ‘The test solutions were prepared by adding deionized water to proper amounts of anlytiealgrade reagents NaCl to obtain the desired oration Soe 13 2018) 275-287 Li ig 1. Sonat fs poceing ‘bie {hemiclcompostion ofthe teste set APLSL NGS composition (3.5% wt, with pH of approximately 7.1, and they were tased to simulate neutral seawater. The solution temperature was maintained at 25°C for wet-dry cylie corrosion, and the average room temperature was 16.6°C. Two experimental paradigms were used to investigate the corrosion behavior of API X65 steel. Group A was ex posed to wel-dry eyelie condition; each wet/dry cycle (24) consisted ofa wet period (12h at 25°C) and a dry period (12h at 16.6°C, 37.55% RH), whereas group B was fully immersed inthe test solutions. The wet- todry ratio (WDR) of the surface of the structure inthe splash zone is closely related to the relative distance between the surface and water ine and the sea state. Generally, WDR decreases as the relative distance increases, For full immersion conditions, WDR = =, sthereas for the region not affected by waves, WDR = 0, It was observed thatthe WDR has a significant impact on the corrosion velocity (30,31), and the ‘maximum corrosion velocity was reached when WDR = 15:9 for X80 Pipeline steel. For WDR = 7, the corrosion rate was almost identical for both cases. Moreover, the cerosion velocity of samples under wet-dry condition was les then full immersion when the immersion time wat less than 9h [30]. Nevertheless, the value of WDR differs significantly Jn the literature {19-21,28,30-33], which represemts the corrosion characteristics of different areas of the splash zane. For convenience, the value of WDR was chosen to be 1 in this study, which was also widely adopted by other researchers [32,33]. Moreover, based on the research by Ren [30], a value of WDR = 1 is applicable forthe quan: ‘ative evaluation of the relationship between wer-dryeyeli corrosion tnd full immersion corraion ‘The surfaces of the specimens were mechanically ground to obtain & plane surface. Subsequently, the coupons were mechanically polished With silicon carbide papers of different grades up to 1200 grit, ultra: sonically cleaned in acetone, and dried and stored in a desiccator for 24h before being subjected to the cartosion test, The coupons were immersed in a beaker of capacity 11 as shown in Fig. 2. The samples were positioned in the solution such that they leaned against the beaker wal, and the sample surfaces were 40mm below the surface of the solution. No additional aeration (such as using an ai cylinder) and agitation were performed during the experiment (except for that ne- cesitated by the change of solution). Six exposure times were chosen ~ 2,7, 14,21, 28, and 35 days and seven specimens were tested foreach Period. The temperature of the solution was controlled using a ther rmostat water bath (HE.S2I-8) as shown in Fig. 2. The solution was changed cvery day. Both the dissolved oxygen and pH ofthe solution were detected and recorded when it was fresh and after one day (eyele) of exposure using a dissolved oxygen meter (AZ 8403) and pH gaugeig. 2. Schematic of tet et up (LS21 8, (C6322), The corresponding values are listed in Table 2 After exposure, some of the test coupons were used to characterize the corroded morphology of the sample surface using SEM (CLSU1510), ‘and some coupons were used to analyze the composition of the corro- sion product using XRD (Rigaku diffractometer). To obtain the statls- tical characteristic of the pitting, six coupons of each group were ‘leaned using chemical cleaning procedures according to ASTM Gl-02 E [24] for the removal of corrosion product, and thereafter tra sonically cleaned with distilled water for 10min, dried with warm a and stored in a desicator until ready for pit depth measurements and Corrosion morphology analysis. 3. Results 3.1. Corrosion morphology As shown in Fig. 3, the surfaces of the samples were covered with @ relatively adherent thick rust layer for wet-dy eyclie corcosion. They were not easily delaminated and ther thicknesses were up to 1 mm. The nist layer was visible after 2days (cycle). Moreover, double rust layers were formed in tis ease. The outer rust layer was a porous black solid, ‘whereas the inner layer was a thin and dense taveny solid. The test results of XRD indicated that lepidocrocite and magnetite were the ‘main components ofthe corrosion product. In contrast to the wet-dry cyclic condition, no obvious visible rust layer was formed during the corrosion process ~ only a thin layer of black solid was formed on the sample surface, which was easily re moved. Note that the tawny rust formed on the sample surfaces (ig. 0) appeared immediately inthe fnal drying process. Further vestigation using XRD indicated that the components ofthe rst layer in full immersion corrosion were hematite and magnetite After removing the rust layer, the sample surface was observed via SEM (Fig. 4a-d). The corrosion processes of X65 steel by following wet-dry cyclic and full immersion conditions were very different, Which resulted in dstint corrosion morphology as shown in Fig. 4.1 ‘as evident that pitting corrosion occurred under wet-dry eyeli con dition, whereas the corrosion behavior tinder full immersion was si- milar to general corrosion, Two distinct phases could be observed in the fall immersion test: one phase was highly corrosion resistant, and the oration Soe 13 2018) 275-287 other was vulnerable to corrosion. Moreover, crystal grain flaking was observed (Fig. 4(b)) for wel-dry cyclic condition, which indicated that the sample surfaces suffered from intergranular corrosion, The cavity shown in Fig. 4(b) may have been caused by the dissolution of inel sion, such as magnesium sulfide [15], which should be further in- vestigated 3.2, Corrosion damage kinetics Pitting corrosion is one of the main fale mechanisms of pipelines and other engineering structures (2,35]. Mass loss is the most widely ‘wed method to determine corrosion kinetis [3,25-25]; however, Its not applicable for the assessment of pitting corrosion, which may result jn an underestimation of the corrosion damage. ‘To overcome such a problem, 3D measuring laser microscope (Olympus OLS4100) with display resolution up to Tam in the vertical direction and 120 nm in the horizontal diction was used to obtain the three-dimensional topography of the sample surface. To obtain the pit depth, aline-scan ofthe sample surface shown in Fig. 5 was used, The corresponding pit depth was measured by focusing the bottom and lowest surface around the pit, and subsequently considering the dif ference berween the two postions as the pit depth. Each pit with a depth greater than Sym was measured and recorded (both surfaces were recorded), and the pits near the specimen edges were discarded during the measurements. Subsequently, the entire pit depth and die meter dataset recorded for six exposed times were analyzed statist cally. The maximum pit depth for each coupon was sereened to abtain the maximum pit depth distribution and the Gumbel distribution was fitted to the maxima datasets using the maximum likelihood estimator. “The corresponding statistical distribution of pit depth is show in Fig. 6 According tothe staistieal result shown in Fig. 6, the pitting depth follows lognormal distribution, which is different from the conclusion Araven by Valor (96), whose research indicated that the pitting depth obeys a normal distribution. The limitation of using normal distribution to desribe the pit depth is evident ~ especially when the Monte-Carlo method! Is used to obtain the sample of corrosion depth, which may result in negative simulation results according to the’ distribution parameter, and conflict with the real situation, whereas using log- ‘normal distribution can avoid such a problem. Fig. 7 shows the plot of the mean and standard deviation of the lognormal distribution versus time. The increase in mean pit depth is suppressed as exposure proceeds. Tis is eaused by the formation of a protective rust layer on X65 steel [23]. A power function is widely used to describe the dependence of pit depth on time, which can be ex: pressed as follows [171: @ ‘The value off and a can be obtained according to the experiment data, and the value ofc has been reported to be within the range of 0.3-0.5 U7 Based on (1), the time dependence of the mean pit depth ean be fied to the power funetion d= 5.874 x", with the mean pit depth d expressed in jm and the ime ¢ expressed in days. The fitting expressions and correlation coefficient (R?) are shown in Tig. 7. How- ever, the standard deviation of the lognorinal distribution linearly in- creases for Immersion periods shorter than 20 days. However, ater mi Disab aaenem) Staion Tempentare (6) A Temperate CC) ROW) Fe satudon Alter one cycle ‘sth soluion After ne eeeSeine 1992018) 276-28720 days of immersion, the standard deviations remained constant. This may correspond to the period when equiibsium in the pit grovth conditions is established [36] ‘As shown in Figs 6 and 7, Its evident that the pit depth distribution varied with exposure time, ‘To obtain the time-dependent pit depth distribution, the time evolution law of mean pit depth and standard ‘deviation should be considered, which is expressed as follows: a ov Gul. 200) @ ‘The values of y and o of lognormal distribution with mean m and var fance v can be obtained as jog + (0 = login ONT m @ According to the SEM results shown in Fi. 4, itis evident that no pitting occured in the case of fll immersion. The corrosion behavior of oration Soe 13 2018) 275-287 Fle, 5. Comin pit aberved on specimen surat tere sectonal sree (35 43) Sie ew X65 stel under full immersion was similar to general corrosion rather than pitting corrosion. In order to obtain a quantitative evaluation of corrosion damage, the groove depth of diferent coupons was also ‘measured using 3D measuring laser microscope as ilustrated in Fig. 5, tnd the results are shown in Fi. 8, As shown in Fg. 8, the groove depth distribution also follows log- ‘normal distribution. The time dependence of the mean groove depth can be fitted to the power function d = 8.948 x £!"*, as shown in Fig. 9 along with the fitting expressions and correlation coefficient () In contrast to the ease shown in wet-dryeyelic, the standard deviation of the lognormal distribution almost linearly Increased for exposure Lime shorter than 35 days, and no saturation was observed forthe test exposure time (Fig 9), which could be due tothe fac thatthe rust layer formed on the sample surface under full immersion had not reached @ steady state yet, For comparison, the est corrosion damage under wet-dry eylic and full immersion conditions was compared (Fig. 10), and the difference Rete = ig 6. Minoan fhe measured pi depth for diferent expo tines 2, 7, 1,21, 28, and 35 day) erp theTanae oration Soe 13 2018) 275-287 Fig, 7. (0) Tie lon of mean and stun ‘je, (0) Fite oso dsrbuton fens or Spm] te meas pit depths “Be ee \ eee A — f\ PE] frat exeowe time, 7, 16 21, 28 od | samosas Se rb i A oe soo} \ i i t TH e = —- e ° was evident: For exposure time less than 7 days (eyes), the corrosion ‘damage of fll immersion was greater than that of wet-dry cyclic cor ‘osion owing to the longer exposure time in electrolyte; However, the corrosion damage of wet-dry cyclic corrosion exceeded that of full immersion corrosion after exposure for 7 days. This difference could be ‘caused by the difference inthe rust layer, aeration, and chloride con centration during the drying process under the two conditions, Even though the exposure time in NaCI solution for full immersion was twice that for wet-dry cyclic condition, the effect of high chloride con- ‘entration and aeration on the corrosion velocity caused by drying process was more significant. As shown in Fig. 3, @ porous nist layer ‘as formed on the sample surface, which could act asa container and 29 > Mesa Ph depth + Stndand deviation a8 9s 10, S30 Expt tity) 33 adsorbent, lock water jn, and enhance the transportation of oxygen to the metal surface, thus aeeelerating the adsorption and dissolution of sulfur dioxide and chloride fon [29], which resulted in higher corrosion velocity. Note thatthe relationship showin in Fi. 10 is applicable for the condition where a porous rust layer s formed on the sample surface under wet-dry condition and the wetting time is sufficiently long (© 9h), whereas for a much shorter wetting time (< 9h), the mean pitting depth may always be less than the mean groove depth caused by full immersion [20]. It was confirmed that a higher frequency of wet/ Ary eycles with WDR = 1 has a deleterious effect on the falure of or sganie coatings [37]. However, such an effect on the corrosion behavior Of steel has never Been studied. Far more rapid eyeles, the drying Fig. 9. (2) Tne cooition of men a stndrd {evanon ofthe prove dey dstbuten for ‘Bess corse Lorna station Fines forte meted goa depts25 Mean pit/groove depth * Full immersion + Wetatry cycle 0152025 Exposure time(Day) Fig 10. Time evn of mean nl standard devition of te pit depth sition for 3035 process of the sample surface could! not be fully developed, which hindered the initiation of the pits [21] and salt deposition and the formation of the rust layer. For extreme conditions, the sample surface is always wet, and the corrosion damage (both morphology and eor- rosion depth) is similar to that of full immersion, 3.3. Maximum pt depth ‘The ste with maximum pit depth is most concerned for the relia bility assessment of pipes, which may result in the leakage of crude ‘and environment pollution. Block maxima (BM), peak over threshold, ‘and generalized lambda distribution methods are the most widely used ‘exireme-value statistic methods [36,37.38,39) to deseribe the max: 1m pit depth distribution of a localized corrsion process. To obtain the propagation law of maximum pit depth, the BM method was used, the maximum pit depth of each specimen on both sides was sereened, ‘and the maximum pit depth distribution was obtained. The probability density function for the extreme-value distribution with location parameter and scale parameter o can be expressed as follows [40} Jes(-eo(S4)) ‘This form ofthe probability density function is suitable for modeling, ; aroma Leo(? oration Soe 13 2018) 275-287 {he minimum value, The negative ofthe original values should be used ‘to model the maximum value [40]. The corresponding Gumbel prob- ability plot of the maximum pit depth is shown in Fg. 1. Note that the straight line corresponding to the experiments conducted for 28 and '35 days was based only on 10 pit depth readings. This is duc tothe loss of to samples during the experiment. Thus, all further analyses on the experiments conducted for 28 and 35 days were based on 10 coupons. As shown in Fig. 11, the Gumbel distribution is applicable for the description of maximum pit depth in most cases, except for 2 and 14days. Note that the straight lines shift to the right and rotate clockwise withthe increase in exposure time, indiating that the loca- tion and seale parameter increase with time. The inconsistent trends shown in Fig. 12(@) may be caused by the random nature of pitting Corrosion and the different salt depositions during the drying proces. ig. 120) shows the time evolution of mean and standard deviation of the Gumbel distributions, which ean be fitted tothe power law function Age = 17-89 % 02 (due expressed in ym and ¢ expressed in days). “The value of the exponent was les than one, whieh indicated thatthe corrosion process was decelerated by the protective rust layer. 3.4, Diameter-to-depth ratio (DDR) Previous studies stated that dhe diameter-to- > To {45}. The integral of Eq. (8) over time yields vo ® Fig, 15. Hogans of the DOR fr difeeot ex varies (2,7, 21, 28and 3s) compared ‘othe fited logan dbs, 4 j i ioration Soe 13 2018) 275-287 Fig. 14, elatnsip betwen DOR ad pl deh, o ‘where Vo, and Ty are constants. The corresponding coefficients ofthe IE model were a = 0.4003, Ty = 0.001, and a = 0.3905 according to the experiment data of wet-dry cyelic exposure, which yield Vo = 186.32 ym/lay Pg. 17 shows the comparison between the power law model and IE model, The value of R* of both models indicated that the IE model fitting was better than that of the power law model Pusthermore, a non-physial limit will not appear for the IE model when £0, which indicated that the IZ model has better applicability 4.2. Comparison of corrosion morphology In order to determine the effect of wet-dry eyeling and full im- mersion on the cotrosion morphology of X65 ste!, the surface and ‘cross-section mocphology ofthe rust layers were examined, a shown in Figs, 18 and 19. The outer rust layer formed on the samples exposed to ‘wer-dry cyclic testing was loose and porous, where many eracks could be observed (Pig. 18(a), whereas the inner rust layer formed on the samples exposed to full immersion was more compact. The existence of ‘racks facilitated the penetration of the electrolyte into the substrate, which, in tur, promoted the corrosion proces, As shown in Fig, 19, is evident that, in the double rust layers formed under wet~iry cyclic ‘condition, the inner layer was dense and adherent to steel, and the 09 Mean corrosion rate Va (tum lay) 1520 25 Exposure time(Day) 3035 Fig. 16, Vataon of average nrsion vl (V7) 055 els function oeposue ‘outer layer was porous. However, the rust layers were not evident in fall immersion condition. Fig. 20 shows the morphology ofthe sample surfaces after removing the corrosion products, The difference between wet-dry eyelie coro: sion and full immersion corrosion was significant; the sample surface exposed to wet-dry cycling suffered from pitting corrasion, whereas Mean aspest a Fiz 15. Time cvltion of DDR for wet-dry xtc ‘en, [Sundar deviation) 3 Aspet ratio 0 isa Epc unetDas)