The influence of Sr2+ on the formation of calcareous deposits on freely corroding low carbon steel in seawater
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- Gordon Egbert Russell
- 5 years ago
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1 Sy h flu f S2+ h fm f lu d fly dg lw b l w by H. Möll* d.c. u* h bhvu f lw b l w vgd yh w wh d whu S2+. I w fud h um ubu f lum g, h h g d (SCO 3 ). h g d h fmd h f S2+ w f h h h fmd h b f S2+. I blvd h h um f g du d lubly, whh u ul hgh ul f h. Fuhm, h gwh f g dd by h f S2+ h lu. I ludd h S2+ l gd y fl w wh lu d vgd l. Kywd:, w, lu d, um, g. Idu Sw ly muld h lby f -g u1,2. Ev hugh h mj hml u f w wldwd, h v f w ffd by vu h f. h lud h f dlvd xyg, ly, f m d blgl vy. I kw h h f ug w, ully C2+ d Mg2+, h gf flu h bhvu f l3. h hd du f xyg du ll lkl uf d, whh CCO 3 d Mg(OH) 2 by Equ [1] d [2]: [1] Clum b lu d x h yll fm f l g8. I h b f Mg2+, lum b d l d/ g4,8. Clum b fmd h f Mg2+ xluvly h fm f g5,8. h du mgum hbg ff l ul d gwh9. h Mg(OH) 2 lu d fmd dug hd dd h yll fm f bu5. I h b hw, hwv, h ll bu fmd l ud fly dg d1,8,10,11. Afl lu mmly ud mul h bhvu f ml w. I vu wk by f h uh1, w hw h h g d h fmd dug mm ul w hd f mhlgy h h h fmd dug mm MBL (M Blgl Lby) d ASM D1141 (Am Sy f g d Ml) yh w. I w d h h f d ud h lghly lw bd h ul w. Oly mud wh 0.1 g/l w ud h f h MBL d ASM D1141 lu h vu wk. hf, h fllwg w h lu: N+, Mg2+, C2+, K+, Cl -, SO 4 2-, HCO 3 - d B -. Oh h mmly l u h m vu mb fl w lu. F xml4 6, lu d hdlly d l h b udd ug lu g mxu f N+, C2+, Mg2+, Cl -, CO 3 2-, HCO 3 - d SO Al, Elbk d wk10 udd h fm f lu [2] h lu d hugh m hyl b g h dffu f xyg d hby d h. Chd f l mmd w kw m h fm f h lu d4 7. * Dm f Ml S d Mllugl Egg, Uvy f,, Suh Af. h Suh Af Iu f Mg d Mllugy, SA ISSN X/ vd Jul. 2006; vd vd Fb h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 107 REFEREED AER MARCH
2 h flu f S2+ h fm f lu d d fly dg l (z ld u) fl lu g ly N+, Mg2+, C2+, Cl - d SO h f mhlgy f h g d fmd ul w md h fl lu mu hf b du h f h u (g g) h w ludd y f h yh lu md h. h m bl m ll f h fl lu S2+. I ug h h ylly b fm fl lu, gv lw w. h S2+ fd ASM D1141 ubu w12 ly 158 μm (13.8 m). h ml h f vy S2+ dlvd ASM D1141 yh w, h 346 Mg2+ d 66 C2+. O h h hd, um md (lg wh lum d mgum) fw xbk d bg bfl u w g I blvd h ludd h lu d b, hby g lmg dffu f xyg h l uf. Lmd lubly fm vlbl f (SCO 3 ). Adg H d -wk11, CCO 3 l lubl h SCO 3. Hwv, dg Bubg d lumm16, h lw lubly h g d l17 ( bl I). I h l b hw h f S2+ u wh g18. Subu f lum by um kw u m dly g h l19. Fuhm, h b uggd h ubu f mll mu f um g u d lubly ( bly)20. h flg vw lu bu g ld lu (S x C 1-x CO 3 ). Adg lumm d Bubg20, mbly g u v h ml g x C. Hwv, Lu-G d -wk21 hv ly uggd h ubu f lum by um uu fm g (x = 0) (x = 1). hy fud h h vlu f h hhmb ll m fu f x w l f h vll dm (0 x 1). If mbly g dd, h lu d g CCO 3 d SCO 3 h uld b bl wh h lubly lvl f um ubud g xdd. O h h hd, f uu ld lu x bw g d, ly h huld b h lu d. I h f l, dff whh S2+ dly ubu f C2+, whh u 22. Wh lu d l dd, f um h d wh h l dg bl I Slubly du f CCO3 d SCO3 Fm -lg K ( 25 C) Rf S (SCO 3 ) Cl (CCO 3 ) Ag (CCO 3 ) fly11,14. Sum m u ly h d (bw d 0.14 %) wh hd ld11. I l l fm lu whh h um lu d ly ubud h g uu f u d 11, Gujh d -wk23 hv hw h S2+ u gf du h gwh d dlu f g. h w bud vbl d f S2+ gwh (kk). h bjv f h udy w hf dm h flu f um h fm f lu d fly dg l. Svl ff bl. Fly, f SCO 3 bf CCO 3, mgh ul f h d f h CCO 3. Sdly, f um ubu f lum g, h lw lubly f h S2+-g g mgh ld hgh ul h wuld b fud S2+-f g (du g uu). A hgh ul, gh wh lw gwh f g yl h f S2+, wuld ul h fm f lu d g f f. Flly, f h mhlgy f h lu d flud by um, mgh hv ff h f h l. Exml Slu h m f h fl w lu ud h udy hw bl II. h mu f h vu mud ddd h lu bd h qu fd ASM D1141 ubu w12. Slu 1 d ly NCl, CCl 2, MgCl 2 d NHCO 3. h fu mud h mmum umb f u dd fm lum b g8 d w ud bl dm h ff f h h mhlgy f h d. Slu 2 d ll h mud h ASM D1141 f wh qul lg h 0.1 g/l ( w ud h vu 1). Flly, lu 3 hd h m m lu 2, x h SCl 2 w l ddd. h duv f ll h lu w ml xmly 54 ms/m. bl II Chml m ( g/l) f h yh w lu ud h udy Cmud Slu 1 Slu 2 Slu 3 NCl MgCl CCl NHCO N 2 SO KCl KB SCl MARCH 2007 VOLUME 107 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy
3 h flu f S2+ h fm f lu d Ml Lw b l (SAE 1006 [UNS G10060]) w ud f h xm. h hml m f h l gv bl III. h l w u 50 x 25 x 2 mm ml. h uf f h ml w gud l ug l bd gdg g wh g 180 d fhg wh g 800. h ml w h d dlld w d dd wh hl mv dul w. h lg du w fmd qukly vd mu. h ml w wghd uly ( f 1 mg) bf h mm d du wgh l xm. Imm Imm w fmd uuly d lu ug h ml lu. h vlum f h lu w 2500 ml. A w hvd by ug mll um, whh l bud ufm xml d by g. All xm w dud m mu (20 C). h ml w mmd h vu lu f h 3 hu, 5 dy 21 dy. h w h ll w fhd vy 7 dy f h lg xu m. Bf xm g l m (SEM), h ml w d wh ud ly f gld d du hgg ff. h du h ml ud f h wgh l xm w mvd wh Clk lu24 wghg. A l-f ml w l d Clk lu vfy h mml ml l ud dug h m. () CCO 3 CCO 3 Rul d du Chz f lu d Fgu 1 hw mg f mll h fmd l dug mm f 3 hu lu 1 (Fgu 1), lu 2 (Fgu 1b) d lu 3 (Fgu 1). h d Fgu 1 d Fgu 1b w dfd by EDS (Egy dv y) lum b. Obvuly, um-g d uld b fmd h um-f lu (1 d 2). Hwv, h Fgu 1 w dfd lum b g m um ( Fgu 2 f EDS ul). h d h fdg d by h h11,14 wh fud um lu d h fmd fly dg l. N (SCO 3 ) w dd h ml. I hf m h um w ubud h g yl, h h g. C 1-x S x CO 3 bl III Chml m ( w%) f SAE 1006 (UNS G10060) l C M S Al C N V F Bl () Fgu 1 () SEM mg hwg g d h fmd dug mm f 3 hu lu 1, SEM mg hwg g d h fmd dug mm f 3 hu lu 2, () SEM mg hwg g d h fmd dug mm f 3 hu lu 3 h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 107 REFEREED AER MARCH
4 h flu f S2+ h fm f lu d fuh h hyh, ml w mmd f 3 hu lu wh ml m lu 3, x h h S2+ w d 10 m (lu 10S). Ag, ly S-g g w bvd by SEM ( SCO 3 ), bu, h EDS ul Fgu 2b d, um ubu f lum ud g x h lu. h ff f S2+ h mhlgy f g b Fgu 3. Fgu 3 hw mg f h lu d h fmd h l dug mm f 5 dy lu 1 (Fgu 3), lu 2 (Fgu 3b) d lu 3 (Fgu 3). h mhlgy f h g d h fmd lu 2 mglly f h h h fmd lu 1. h ml h h mb f K+, SO 4 2- d B - d hv gf ff h mhlgy f dd g fly dg l. Hwv, h f g d w fmd h S2+-g lu (Fgu 3). h lu d h fmd h lu m m fvubly wh h h w fmd ul w1. h bv h f g d fmd h S2+-g lu b bud mb f w f. Fly, h ul f g w d by ubu f S2+, du h lw lubly f S2+-g g20. h hgh ul f g lu 3 vd wh mg Fgu 3 wh Fgu 3 d b, hwg h muh lg dy f b l f lu 3. h d f h flu f S2+ h gwh f g. Gujh d -wk23 hv dmd h dvl, uh S2+, B2+, Z2+ d Cu2+ u dbl d h gwh f () () () Fgu 2 () EDS ly f g h fmd l f mm lu 3 hwg k dg h f um h, EDS ly f g h fmd l f mm lu 10S (lu g 10 m h dd quy f S 2+ ) Fgu 3 ():SEM mg hwg g d h fmd dug mm f 5 dy lu 1, SEM mg hwg g d h fmd dug mm f 5 dy lu 2, () SEM mg hwg f g d h fmd dug mm f 5 dy lu MARCH 2007 VOLUME 107 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy
5 h flu f S2+ h fm f lu d g yl. h ml (Cu2+, Z2+) hw g hb h S2+, bu h w lw hv h m dvdul ff um. bl IV hw h f h h dd u 50% du h gwh f g (C 50% ), wll h f h ASM D1141 yh w (C D1141 ). bl V hw h xm % du gwh f g ud by h h ASM D1141 yh w. I fm bl V h S2+ ( yl w ) du h gwh f g by muh 65%. I d fuh vg h ff f um ubu h mhlgy f g, ml w l mmd f 5 dy h lu g 10 m h dd quy f S2+ (.. lu 10S). h lu d fmd h lu (Fgu 4) w muh f h y f h h lu f 5 dy ( h dff mgf ud Fgu 3 d Fgu 4). Ag, w bvd h ml. I fm bl V h h S2+- f h lu du h gwh f g yl by 95%. Igly, fw mll g S d S w bvd h Sg g ( Fgu 5 d b). h vly dfd SSO 4 (l). I ug h l w fmd h l h lu m m gm (uh h) u l kl25. I kw h l ud-ud w (xmly 30% f u26), bu mu b mmbd h h f lu d d f mgud lg S2+ h w. Fgu 4 SEM mg hwg f g d h fmd dug mm f 5 dy lu 10S bl IV I dd u 50% du h gwh f g 23, md wh h m f ASM D1141 yh w 12 I CD1141 C50% CD1141 : C50% C C f ASM D1141 hlvg gwh lu 12 (μm) 23 (μm) S Cu Z B Mg x () bl V Cluld du g gwh (bd lu d 23 ) by dvl h ASM D1141 yh w I CD1141 % Rdu g gwh 23 S2+ 65 Cu2+ 15 Z2+ 5 B2+ 3 Mg x S2+ 95 Fgu 5 () SEM mg hwg bl l h S-g g d h fmd dug mm f 5 dy lu 10S; EDS ly f h mll Fgu 5() dg h bly f l fm f mm lu 10S f 5 dy. h f CCO3 du h mll z f h l h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 107 REFEREED AER MARCH
6 h flu f S2+ h fm f lu d whh dvdul SCO 3 uld b dd wh g w h l uf, ml w l mmd S2+-g lu whu y C2+. h f lu w ml m lu 3 (g h dd quy f S2+), bu whu y C2+ (dgd lu 1S_0C). h d lu w ml lu 10S, bu whu y lum (dgd lu 10S_0C). N SCO 3 uld b bvd by SEM v f mm f u 18 dy lu 1S_0C. h ugg h h S2+ f w lw llw h f fly dg l (l h qulbum lul blw). Hwv, SCO 3 w bvd f mm f 5 dy lu 10S_0C ( Fgu 6 d b), v hugh f h d w dd h quvl C2+g lu 10S (Fgu 4 d 5). All h ul hf gly ugg h um wuld h b ubud f lum h g uu h h f C2+ (fuh u f h lu gv blw bd qulbum lul). Su f h ul h l vlbl lu l g. I h b uggd h h um l xd h hmdym lubly lvl f um ubud g20,27. F h, Gg d -uh28 uggd h m l kl mgh um d SCO 3 d S ubud f C g. Hwv, Fh d wk ud XRD d S K-dg Exdd X-y Ab F Suu (EXAFS) ul h vy f l mbl, um-uud g wh blw d lvl27,29,30 (v f h m ml ud vuly by Gg d -wk27,28). Fuhm, hy uggd h h dffu k f h mbl g lw h dffu-ld dm wll u wh glgl mfm27. F xml, by ug h dffuvy f um l, d umg ml dffuvy g, hy md h h ul f m-z dm g wuld qu m d f xmly 1017 y. Flly, d l, Lu-G d -wk21 hv ly uggd h x f uu ld lu bw d g. h uld l b lubl xl f h b f d l d lu d. Fgu 7 hw mg f h lum b d h fmd l mmd f 21 dy lu 1 (Fgu 7), lu 2 (Fgu 7b) d lu 3 (Fgu 7). Ag, h g d f h S2+-g lu 3 h h h w lu. h d h fmd lu 1 d 2 g ml, fmg h ul fud f mm f 5 dy. Equlbum lul () Fgu 6 () SEM mg hwg SCO3 h fmd dug mm f 5 dy lu 10S_0C, EDS ly f SCO3 Fgu 6 () h fmd l f mm lu 10S_0C lmy qulbum lul w fmd wh FSg 5.431, vlu h bl ff f um g fm. A z quu lu mdl (FAC-IZ) w ud, gh wh u ld fm h gl FAC db. All bl ld h (b, xd, d hld) w ludd h lul, wh h x f dlm d MgCO 3, whh lly bvd (v hugh hy dd b bl wh w h f dlm, d f lghly lklzd w h f MgCO 3 ). h m f lu 2 d 3 (bl II) w ud, f mu f 25 C ( h h mu whh h z mdl vld). h ff f lklz hd w muld by ddg vu ddl mu f NOH. Fgu 8 hw h ul f lu 2, whh um. A h fgu d, g dd b h f fm; bu fm h H xmly 9.3 (d bu fm h buff h H l h vlu f fuh dd f NOH). h d f lu 3 w dl f SCO 3 w dd h: h, dd h SCO 3 d h, l wh h xml bv. I h b f y d h SCO 3 -CCO 3 ld lu, h w mdlld dl lu. h d wh h dl ld lu w dd bl h, f w g um (lu 3), gv Fgu 9. h mu f 172 MARCH 2007 VOLUME 107 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy
7 h flu f S2+ h fm f lu d () ml h f h S2+-f lu (Fgu 8), bu wh h dff h h g w dd SCO 3 ld lu hw by h lw gh Fgu 9. Wh mmdly bvu fm m f Fgu 8 d 9 h f h um-g g dd u lghly lw H h h um-f g. h llud by Fgu 10, whh l h ul f Fgu 8 d 9 fu f H. h umg g fm lghly lw H, whh llu h g bly f h md wh SCO 3 -f g. C f SAE 1006 l h vu lu h f h ml w luld by ug vg wgh l mum f mm f 21 dy h dff fl w lu f bl II. h vg lmg u dy f xyg du h l uf ( L ) w l md fm h wgh l mum by umg h h u dy f h l ( ) qul L. h ul hw bl VI. h f h l mmd h vu lu b ml, bu mwh lw h um-g lu. Clu h lu f h udy : Sum h lu d h w fmd fly dg l dug mm S2+-g fl w. h d h fdg d by h h l ud. N (SCO 3 ) w dd y f h ml h w mmd lu g bh C2+ d S2+. () Fgu 7 () SEM mg hwg g d h fmd dug mm f 21 dy lu 1, SEM mg hwg g d h fmd dug mm f 21 dy lu 2, () SEM mg hwg g d h fmd dug mm f 21 dy lu 3 Fgu 8 Cluld hg mu f ld d H, f dff lvl f dd f NOH lu 2 h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 107 REFEREED AER MARCH
8 h flu f S2+ h fm f lu d bl VI C d u d bd f h f SAE 1006 l bd wgh l f mm f 21 dy Slu1 Slu 2 Slu 3 (μa/m2) R (mm/y) h mb f hgh ul (lw lubly) d lw gwh f g yl S2+-g lu ul h fm f f lu. h lu ly h bd h S2+g fl w lu (lu 3) m v ( m f m d mhlgy) f wh fud wh l mmd ul w. Sum hf y u y fl w wh lu d l udd. h f h lw b l mmd h vu fl w lu w flud gfly by h dff lum b mhlg h udy. Fgu 9 Cluld hg mu f ld d H, f dff lvl f dd f NOH lu 3 (g S 2+ ), dg dl lu CCO3-SCO3 bl h; h lw gh hw h dd m f h ld lu Fgu 10 Cluld mu f g (u CCO3 f lu 2, d CCO3-SCO3 dl ld lu f lu 3) fu f H (ld ul f Fgu 8 d 9) I m f um ly ubu f lum g, whh umbly d lubly. h gwh f g yl kw b dd gfly lu g S2+. Rf 1. MÖLLER, H., BOSHOFF, E.., d FRONEMAN, H. h bhvu f lw b l ul d yh w. Jul f h Suh Af Iu f Mg d Mllugy, vl. 106, ASM Ml Hdbk, vl. 13: C, 9h d. Ml k, OH, ASM Il, JONES, D.A. l d v f C. U Sddl Rv, NJ, Hll, DESLOUIS, C., FESY, D., GIL, O., RIUS, S., OUZAIN, S., d RIBOLLE, B. Ch f lu d fl w by md hqu I. Elhm A, vl. 43, BARCHICHE, C., DESLOUIS, C., FESY, D., GIL, O., REFAI,., OUZAIN, S., d RIBOLLE, B. Ch f lu d fl w by md hqu III. Elhm A, vl. 48, BARCHICHE, C., DESLOUIS, C., GIL, O., REFAI,., d RIBOLLE, B. Ch f lu d by lhml mhd: l f ulh, lum d mu. Elhm A, vl. 49, CHEN, S., HAR, W.H., d WOLFSON, S. D w hd. C, vl. 59, MÖLLER, H. h flu f Mg2+ h fm f lu d fly dg lw b l w. C S, vl. 49, MANEL, K.E., HAR, W.H., d CHEN,.-Y. Sub, uf fh, d flw flu lu d uu, C, vl. 48, ELBEIK, S., SEUNG, A.C.C., d MACKAY, A.L. h fm f lu d dug h f mld l w. C S, vl. 26, HAR, W.H., CULBERSON, C.H., d SMIH, S.W. Clu d ml uf w A l vw. C, vl. 40, ASM D1141. Sdd f h f Subu O W. W Chhk, A, ASM Il LAQUE, F.L. M. Ld, Jh Wly d S, MELCHERS, R.E. bbl mdl f uul lbly m 2. Jul f ffh mh d gg, vl. 125, MARCH 2007 VOLUME 107 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy
9 h flu f S2+ h fm f lu d 15. LIN, S.H. d DEXER, S.C. Eff f mu d mgum lu d. C, vl. 44, BUSENBERG, E.,d LUMMER, L.N. h lubly f CO 2 -H 2 O lu bw 2 d 91 C, h f SHCO + 3 (q) d SCO 3 (q) bw 5 d 80 C, d vlu f h hmdym f S2+(q) d SCO 3 () 25 C d 1 m l u. Ghm Cmhm A, vl. 48, GAL, J.Y., BOLLINGER, J.C., OLOSA, H., d GACHE, N. Clum b lubly: l f l fm d hb. l, vl. 43, KINSMAN, D.J.J. d HOLLAND, H.D. h - f wh CCO 3 IV. h - f S2+ wh g bw 16 d 96 C. Ghm Cmhm A, vl. 33, SCHROEDER, J.H. Exml dlu f lum, mgum d um fm bg b: mdl f dg. Jul f dmy lgy, vl. 39, LUMMER, L.N. d BUSENBERG, E. hmdym f g ld lu: Rul fm hm lubly 25 d 76 C. Ghm Cmhm A, vl. 51, LUCAS-GIRO, A., HERNANDEZ, O., d OUDADESSE, H. R-xm f h uul f ld lu S x C 1-x CO 3. Ml Rh Bull, Al, d: /j.mbull FALLON, S.J., MCCULLOCH, M.., d ALIBER, C. Exmg w mu x l fm h G B Rf: hlf m. Cl Rf, vl. 22, GUJAHR, A., DABRINGHAUS, H., d LACMANN, R. Sud f h gwh d dlu k f h CCO 3 lymh l d g II. h flu f dvl ddv h gwh d dlu. Jul f Cyl Gwh, vl. 158, WRANGLEN, G. A Idu C d f Ml. Nw Yk, Chm d Hll, BERNSEIN, R.E., BYRNE, R.H., BEZER,.R., d GERCO, A.M. Mhlg d fm f l w: h l f h um d bum ghmy. Ghm Cmhm A, vl. 65, RUSHDI, A.I., MCMANUS, J., d COLLIER, R.W. M b d l u w. M Chmy, vl. 69, FINCH, A.A. d ALLISON, N. Sum l g: S d d h lg-m bly f l vml d. Ghm Cmhm A, vl. 67, GREEGOR, R.B., INGIORE, N.E., d LYLE, F.W. S l kll g. S, vl. 275, FINCH, A.A., ALLISON, N., SUON, S.R., d NEWVILLE, M. Sum l g: Ch f S d by EXAFS. Ghm Cmhm A, vl. 67, ALLISON, N., FINCH, A.A., NEWVILLE, M., d SUON, S.R. Sum l g: S d d ghmy l kll hu. Ghm Cmhm A, vl. 69, BALE, C.W., CHARRAND,., DEGEROV, S.A., ERIKSSON, G., HACK, K., MAHFOUD, R.B., MELANCON, J., ELON, A.D., d EERSEN, S. FSg hmhml fw d db. Clhd, vl. 26, h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 107 REFEREED AER MARCH
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