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Iyo inoshandiswa zvakanyanya simbi isina tsvina uye shanduro dzayo dzakagadzirwa dzinoshingirira mukuora mumamiriro ekunze nekuda kwepassivation layer inosanganisira chromium oxide. Kuora uye kuputika kwesimbi kunowanzobatanidzwa nekuparadzwa kwezvikamu izvi, asi kashoma nechitarisiko chepamusoro inhomogeneities, zvichienderana nehuwandu hwe microscopic. Mubasa iri, nanoscale kemikari yepamusoro heterogeneity, yakaonekwa ne spectroscopic microscopy uye chemometric ongororo, zvisingatarisirwi inotonga kuputsika uye kuora kweinotonhora yakakungurutswa cerium yakagadziridzwa super duplex Stainless simbi 2507 (SDSS) panguva yekupisa kwayo. Kunyange zvazvo X-ray photoelectron microscopy yakaratidza kufukidzwa kwakafanana kweiyo Cr2O3 layer, iyo passivation performance yechando yakakungurutswa SDSS yakanga isina kunaka nekuda kwekugoverwa kwenzvimbo kweFe3+ rich nanoislands paFe/Cr oxide layer. Ruzivo urwu rweatomiki rwechiyero runopa kunzwisisa kwakadzama kwekuora kwesimbi isina tsvina uye inotarisirwa kubatsira kurwisa kuora kwesimbi dzakafanana dzepamusoro-alloy.
Kubva pakatangwa simbi isina tsvina, anti-corrosion properties yeferrochrome yakanzi ndeye chromium, iyo inoumba yakasimba oxides/oxyhydroxides uye inoratidza hunhu husingaite munzvimbo zhinji. Zvichienzaniswa neyakajairwa (austenitic uye ferritic) simbi isina simbi 1, 2, 3, super duplex Stainless simbi (SDSS) ine zvirinani kuonda kwekupokana uye yakanakisa michina zvivakwa. Kuwedzera kwesimba remagetsi kunobvumira kureruka uye mamwe compact magadzirirwo. Mukupesana, iyo yehupfumi SDSS ine yakakwira kuramba kugomba uye kukoromoka, zvichikonzera hupenyu hurefu hwesevhisi, nekudaro ichiwedzera kushanda kwayo kukudzora kusvibiswa, midziyo yemakemikari, uye indasitiri yemafuta negasi yekumahombekombe4. Nekudaro, iyo nhete yemhando yetembiricha yekurapa kupisa uye kusaita zvakanaka kunokanganisa kushanda kwavo kwakakura. Naizvozvo, SDSS inogadziridzwa kuti ivandudze mashandiro ari pamusoro. Semuenzaniso, iyo Ce modification yakaunzwa muSDSS 2507 (Ce-2507) ine yakakwira nitrogen content6,7,8. Iyo isingawanzo yepasi chinhu (Ce) pane yakakodzera kuunganidzwa kwe0.08 wt.% ine mhedzisiro inobatsira pane mechanical zvinhu zveDSS, sezvo inonatsiridza kukwenenzverwa kwezviyo uye simba remuganho wezviyo. Kupfeka uye corrosion kuramba, kusimba simba uye goho simba, uye kupisa kushanda kunovandudzwa9. Huwandu hwakakura hwenitrogen hunogona kutsiva zvinodhura nickel zvemukati, zvichiita kuti SDSS iwedzere kudhura-10.
Munguva ichangopfuura, SDSS yakashongedzwa mupurasitiki pane tembiricha dzakasiyana (cryogenic, kutonhora uye kupisa) kuti iwane yakanakisa mechaniki zvivakwa6,7,8. Nekudaro, iyo yakanakisa corrosion resistance yeSDSS nekuda kwekuvapo kwefirimu yeoxyde yakaonda pamusoro inobatwa nezvinhu zvakawanda senge inherent heterogeneity nekuda kwekuvapo kwezvikamu zvakasiyana zvine miganhu yezviyo zvakasiyana, mvura isingadikanwi uye mhinduro dzakasiyana. deformations ye austenitic uye ferritic phases7. Naizvozvo, kudzidza kweiyo microscopic domain zvimiro zvemafirimu akadaro kusvika padanho remagetsi chimiro kunova kwakakosha pakunzwisisa SDSS corrosion uye inoda akaomesesa maitiro ekuyedza. Kusvika pari zvino, nzira dzepamusoro-soro dzakaita seAuger electron spectroscopy11 uye X-ray photoelectron spectroscopy12,13,14,15 uye yakaoma X-ray photoemission microscopy (HAX-PEEM)16 yakambotadza kuona kusiyana kwemakemikari muzvikamu zvepamusoro. makemikari mamiriro echinhu chimwe munzvimbo dzakasiyana dze nanoscale space. Ongororo dzinoverengeka dzichangoburwa dzakabatanidza oxidation yemuno yechromium neyakacherechedzwa corrosion maitiro eaustenitic Stainless steels17, martensitic steels18 uye SDSS19,20. Nekudaro, zvidzidzo izvi zvakanyanya kutarisisa mhedzisiro yeCr heterogeneity (semuenzaniso, Cr3 + oxidation state) pakuramba kwecorrosion. Lateral heterogeneity mu oxidation state yezvinhu zvinogona kukonzerwa neakasiyana makomisheni ane akafanana constituent elements, senge iron oxides. Izvi zvinosanganiswa, izvo zvakagara nhaka diki diki semugumisiro wekurapa thermomechanical, zviri pedyo nepedyo kune mumwe nemumwe, asi zvakasiyana mukuumbwa uye oxidation state16,21. Naizvozvo, kuti uone kuputika kwemafirimu eoxide uye kuteedzera gomba, zvinodikanwa kuti unzwisise heterogeneity yepasi padanho remicroscopic. Pasinei nezvinodiwa izvi, fungidziro dzehuwandu hwakadai se lateral heterogeneity mu oxidation, kunyanya yeFe pa nano- uye atomic scale, ichiri kushaikwa, uye kuwirirana kwayo nekudzivisa kuora kunoramba kusati kwaongororwa. Kusvika nguva pfupi yadarika, chimiro chemakemikari yezvinhu zvakasiyana-siyana, seFe uye Ca22, pamasampure esimbi aive akasarudzika achishandiswa yakapfava X-ray photoelectron microscopy (X-PEEM) mune nanoscale synchrotron radiation zvivako. Yakasanganiswa nekemikari inonzwa X-ray absorption spectroscopy (XAS), X-PEEM inogonesa kuyerwa kweXAS nepamusoro-soro yepasi uye spectral resolution, ichipa ruzivo rwemakemikari nezve kuumbwa kwezvinhu uye chimiro chazvo chemakemikari nekugadziriswa kwenzvimbo kusvika pamakumi maviri nematatu nanometer pachiyero. . Iyi spectromicroscopic yekucherechedza kwekutanga inofambisa kuongororwa kwemakemikari emunharaunda uye inogona kuratidza kuchinja kwemakemikari munzvimbo yesimbi isina kumboongororwa.
Ichi chidzidzo chinowedzera zvakanakira PEEM mukuona kusiyana kwemakemikari pananoscale uye inopa inonzwisisika-yepamusoro-soro yeatomu yekuongorora nzira yekunzwisisa maitiro ekuora kweCe-2507. Inoshandisa nzira yakabatana yeK-means24 chemometric kumepu kemikari yepasi rose (hetero) homogeneity yezvinhu zvinobatanidzwa, izvo zvimiro zvemakemikari zvinoratidzwa mukumiririra kwenhamba. Kusiyana nekuora kwakatangwa nekuparadzwa kwe chromium oxide firimu mune yechinyakare nyaya, kushoma passivation uye kuderera kwekushomeka kwekushomeka ikozvino kunonzi kune localized Fe3 + rich nanoislands pedyo neFe / Cr oxide layer, iyo inogona kuva inodzivirira. Iyo oxide inoparadza firimu rine madoti uye inokonzera ngura.
Hunhu hwekuora hwekuremara SDSS 2507 hwakatanga kuongororwa pachishandiswa zviyero zve electrochemical. Pamusoro pemuonde. Mufananidzo 1 unoratidza Nyquist uye Bode curves kune dzakasarudzwa samples mune acidic (pH = 1) aqueous solution yeFeCl3 pakamuri tembiricha. Iyo yakasarudzwa electrolyte inoshanda seyakasimba oxidizing agent, inoratidza maitiro eiyo passivation firimu kuputsa. Kunyangwe izvo zvinyorwa hazvina kudzika kudzika kwegomba patembiricha yekamuri, ongororo yakapa nzwisiso yezvingangoitika zviitiko zvekutadza uye nekuora kwakatevera. Iyo yakaenzana yedunhu (Fig. 1d) yakashandiswa kuenderana ne electrochemical impedance spectroscopy (EIS) spectrum, uye migumisiro inoenderana nayo inoratidzwa muTebhu 1. Semicircles isina kukwana inooneka mumhinduro-yakagadziriswa uye inopisa-yakashandiswa zvienzaniso, nepo semicircles yakamanikidzwa inoratidzika mune inotonhora-yakaputika.1b. MuEIS spectroscopy, radius ye semicircle inogona kuonekwa sepolarization resistance (Rp) 25,26. Iyo Rp yemhinduro-yakagadziriswa runway muTafura 1 ingangoita 135 kΩ cm-2, zvisinei, kukosha kweinopisa-yakatenderedzwa uye inotonhora-yakatenderedzwa runway yeruzha yakadzikira zvakanyanya, 34.7 uye 2.1 kΩ cm-2, zvichiteerana. Uku kuderedzwa kwakakosha muRp kunoratidza kukanganisa kwepurasitiki deformation pane passivation uye corrosion kuramba, sezvakaratidzwa mumishumo yapfuura27,28,29,30.
a Nyquist, b, c Bode impedance uye dhizaini yechikamu, uye d inoenderana akaenzana edunhu mamodheru, uko RS iri electrolyte kuramba, Rp ndiyo polarization kuramba, uye QCPE ndiyo oxide yeinogara chikamu chechikamu chinoshandiswa kuenzanisira isina-ideal capacitance (n). Zviyero zveEIS zvinogadzirwa pakushama kwedunhu.
Izvo zvinogara panguva imwe chete zvinoratidzwa muBode plot, ine bani riri pakakwirira frequency renji inomiririra kupikisa kwe electrolyte RS26. Sezvo frequency inoderera, iyo impedance inowedzera uye yakashata chikamu angle inowanikwa, ichiratidza capacitance kutonga. Chikamu chechikamu chinowedzera, kuchengetedza huwandu pamusoro pehuwandu hwehuwandu hwehuwandu, uye hunoderera (Fig. 1c). Zvisinei, muzviitiko zvose zvitatu, iyi yepamusoro ichiri pasi pe90 °, ichiratidza kusaita zvakanaka capacitive maitiro nekuda kwe capacitive dispersion. Nokudaro, iyo QCPE inoramba iine chikamu chechikamu (CPE) chinoshandiswa kumiririra interfacial capacitance distributions inobva kune pamusoro pehutsinye kana inhomogeneity, kunyanya paatomic scale, fractal geometry, electrode porosity, non-uniform potential, uye geometry ine chimiro che electrodes31,32. CPE impedance:
apo j ndiyo nhamba yekufungidzira uye ω ndiyo frequency yeakona. QCPE inguva yakazvimirira yakazvimirira nguva dzose iyo yakaenzana neyakavhurika nzvimbo ye electrolyte. n inhamba yesimba isina dimensionless inotsanangura kutsauka kwecapacitor kubva pakugona kwakaringana, kureva kuti padhuze n ndeye 1, iri padyo neCPE ndeyekungoita capacitive, nepo n kana n iri pedyo ne zero, inoita seinopikisa. Kutsauka kudiki kwen, padhuze ne1, kunoratidza iyo isiri-yakanaka capacitive maitiro epamusoro mushure mebvunzo dzepolarization. Iyo QCPE yechando yakakungurutswa SDSS yakakwira zvakanyanya kupfuura mamwe ayo, zvichireva kuti iyo yepamusoro mhando haina yunifomu.
Zvinoenderana neakawanda corrosion kuramba zvivakwa zvesimbi isina tsvina, iyo yakakwira Cr yemukati meSDSS kazhinji inokonzeresa yakanakisa corrosion kuramba kweSDSS nekuda kwekuvapo kweinopfuura inodzivirira oxide firimu pamusoro17. Mafirimu akadaro anodarika anowanzo kupfuma muCr3+ oxides uye/kana hydroxides, kunyanya pamwe chete neFe2+, Fe3+ oxides uye/kana (oxy)hydroxides33. Pasinei nekufanana kwepamusoro, passivating oxide layer, uye pasina inocherechedzwa kuputika kwepasi zvichienderana nezviyero zve microscopic6,7, maitiro ekuora kweiyo inopisa-inoshanda uye inotonhora-yakakungurutswa SDSS yakasiyana, saka kudzidza kwakadzama kweiyo microstructural maitiro inodiwa kuti simbi deformation.
Iyo microstructure yeyakaremara simbi isina tsvina yakadzidzwa zvakanyanya uchishandisa intrinsic uye synchrotron yakakwirira-simba X-rays (Supplementary Figures 1, 2). Ongororo yakadzama inopiwa muSupplementary Information. Kunyange zvazvo kune kubvumirana kwakawanda pamusoro pemhando yechikamu chikuru, kusiyana kwezvikamu zvezvikamu zvakawanda zvakawanikwa, izvo zvakanyorwa muSupplementary Table 1. Iyi misiyano inogona kunge yakakonzerwa ne-inhomogeneous phase fractions pamusoro uye muhuwandu, iyo inokonzerwa ne-X-ray diffraction (XRD) yakasiyana-siyana yekuona zvakadzama. ) ine simba rakasiyana siyana rechiitiko photons34. Zvikamu zvakakwirira zve austenite mumienzaniso inotonhora yakatenderedzwa yakatemwa neXRD kubva murabhoritari sosi inoratidza kufambisa kuri nani uyezve zvirinani kuramba kwecorrosion35, nepo kunyatso uye nenhamba mhedzisiro inoratidza maitiro akasiyana muzvikamu zvikamu. Mukuwedzera, kupikisa kwekuora kwesimbi kunoenderanawo nehuwandu hwekunatswa kwezviyo, kuderedza kukura kwezviyo, kuwedzera kwe microdeformations uye dislocation density inoitika panguva yekurapa thermomechanical36,37,38. Zvienzaniso zvinopisa zvakaratidza hutsika huzhinji, hunoratidza zviyo zve micron-size, asi zvindori zvakatsetseka zvakaonekwa mumifananidzo inotonhora (Supplementary Fig. 3) yairatidza kukosha kwekunatswa kwezviyo kune nanosize mubasa rekare. Izvi zvinofanirwa kufarira iyo passive firimu. kuumbwa uye kuwedzera kwekusagadzikana kwecorrosion. Higher dislocation density inowanzobatanidzwa nekushomeka kwakadzika kugomba, iyo inobvumirana nemayero e electrochemical.
Shanduko mumamiriro emakemikari eiyo microdomain yezvinhu zvikuru zvakadzidzwa zvakarongeka uchishandisa X-PEEM. Kunyangwe paine mamwe maalloying zvinhu, Cr, Fe, Ni uye Ce39 vanosarudzwa pano, sezvo Cr chiri chinhu chakakosha pakugadzira iyo passive firimu, Fe ndicho chinhu chikuru chesimbi, uye Ni inosimudzira passivation uye kuenzanisa chikamu cheferrite-austenitic. Chimiro uye shanduko ndicho chinangwa cheCe. Nekugadzirisa iyo synchrotron beam simba, XAS yakatora maitiro makuru eCr (L2.3 edge), Fe (L2.3 edge), Ni (L2.3 edge), uye Ce (M4.5 edge) kubva pamusoro. -2507 SDSS. Ongororo yedata yakakodzera yakaitwa nekubatanidza simba rekuenzanisa nedata rakaburitswa (semuenzaniso XAS paFe L2, 3 ribs40,41).
Pamusoro pemuonde. Mufananidzo 2 unoratidza mifananidzo yeX-PEEM yekupisa-yakashanda (Fig. 2a) uye inotonhora (Fig. 2d) Ce-2507 SDSS uye inowirirana XAS Cr uye Fe L2,3 mitsetse pane imwe neimwe yakanyorwa nzvimbo. Mupendero weL2,3 XAS unoongorora zvisingagadzike 3d nyika dzemaerekitironi mushure mephotoexcitation pa 2p3/2 (L3 edge) uye 2p1/2 (L2 edge) spin-orbit splitting levels. Ruzivo nezve valence mamiriro eCr akawanikwa kubva kuX-ray diffraction kuongororwa kweL2,3 kumucheto muFig. 2b, d. Link kuenzanisa. 42, 43 yakaratidza kuti nhongonya ina A (578.3 eV), B (579.5 eV), C (580.4 eV), uye D (582.2 eV) dzakaonekwa pedyo nekumucheto kweL3, zvichiratidza octahedral Cr3+ ions, inoenderana neCr2O3. Maonero ekuedza ari kubvumirana nekuverenga kwe theoretical, sezvinoratidzwa mumapuranga b uye e, akawanikwa kubva kune dzakawanda crystal field calculations paCr L2.3 interface uchishandisa crystal field ye2.0 eV44. Maviri ese ari maviri anopisa-akashanda uye anotonhora-akakungurutswa SDSS akaputirwa neyakafanana yunifomu layer yeCr2O3.
a Thermal image of X-PEEM inopisa-yakaumbwa SDSS inoenderana nechekumucheto b Cr L2.3 uye mupendero c Fe L2.3, d Thermal mufananidzo X-PEEM yechando-yakakungurutswa SDSS inoenderana nechekumucheto e Cr L2.3 uye f Fe L2.3 yedivi (e) . Iyo XAS spectra yakarongwa munzvimbo dzakasiyana siyana dzakamisikidzwa pamifananidzo inopisa (a, d) nemitsetse yeorenji ine madoti mu(b) uye (e) inomiririra yakatedzerwa XAS spectra yeCr3+ ine crystal field value ye2.0 eV. Pamifananidzo ye-X-PEEM, palette inopisa inoshandiswa kuvandudza kuverenga kwemufananidzo, apo mavara kubva kubhuruu kusvika kune tsvuku akaenzana nehukuru hwe X-ray absorption (kubva pasi kusvika kumusoro).
Pasinei nemamiriro emakemikari ezvimedu zvesimbi izvi, chimiro chemakemikari chekuwedzera kweNi uye Ce alloying zvinhu zvemasamples ese ari maviri anoramba akafanana. Kuwedzera kudhirowa. Pamusoro pemuonde. 5-9 inoratidza mifananidzo yeX-PEEM uye inofananidzwa neXAS spectra yeNi naCe panzvimbo dzakasiyana-siyana pamusoro pezvienzaniso zvinopisa-zvakashanda uye zvinotonhora. Ni XAS inoratidza iyo oxidation mamiriro eNi2+ pamusoro peiyo yese yakayerwa pamusoro peanopisa-akashanda uye anotonhora-akakungurutswa emuenzaniso (Supplementary Discussion). Zvinokosha kucherechedza kuti munyaya yezvienzaniso zvinopisa-zvakashanda, chiratidzo cheXAS cheCe hachionekwe, nepo spectrum yeCe3 + yezviyero zvinotonhorera zvinoonekwa pane imwe nguva. Kucherechedzwa kwenzvimbo dzeCe mumasampuli anotonhora-akatenderedzwa kwakaratidza kuti Ce inonyanya kuvepo muchimiro chemvura.
Mune thermally deformed SDSS, hapana shanduko yenzvimbo yeXAS yakaonekwa paFe L2.3 kumucheto (Fig. 2c). Zvisinei, sezvinoratidzwa mumufananidzo. 2f, iyo Fe matrix microscopically inoshandura chimiro chayo chemakemikari pamapoinzi manomwe akasarudzwa zvisina tsarukano mune inotonhora yakakungurutswa SDSS. Mukuwedzera, kuitira kuti uwane pfungwa yakarurama yekuchinja kwehurumende yeFe panzvimbo dzakasarudzwa muFig. 2f, zvidzidzo zvepanyika zvepanyika zvakaitwa (Fig. 3 uye Supplementary Fig. 10) umo maduku maduku akatenderera akasarudzwa. Iyo XAS spectra yeFe L2,3 mupendero we α-Fe2O3 masisitimu uye Fe2+ octahedral oxides akaenzanisirwa achishandisa multiplet crystal field calculations achishandisa crystal fields ye1.0 (Fe2+) uye 1.0 (Fe3+)44. Tinocherechedza kuti α-Fe2O3 uye γ-Fe2O3 vane symmetries yakasiyana yemunharaunda45,46, Fe3O4 ine musanganiswa wezvose Fe2+ & Fe3+, 47, uye FeO45 seyakarongeka divalent Fe2+ oxide (3d6). Tinocherechedza kuti α-Fe2O3 uye γ-Fe2O3 vane symmetries yakasiyana-siyana yemunharaunda45,46, Fe3O4 ine musanganiswa wezvose Fe2+ & Fe3+,47, uye FeO45 seyakarongeka divalent Fe2+ oxide (3d6).Ziva kuti α-Fe2O3 uye γ-Fe2O3 dzine symmetries dzemuno dzakasiyana45,46, Fe3O4 inosanganisa zvese Fe2+ neFe3+,47 uye FeO45 muchimiro cheformally divalent oxide Fe2+ (3d6).Ziva kuti α-Fe2O3 uye γ-Fe2O3 dzine symmetries dzemunharaunda dzakasiyana45,46, Fe3O4 ine misanganiswa yeFe2+ neFe3+,47 uye FeO45 inoita seyakarongeka divalent Fe2+ oxide (3d6). Ese Fe3+ ions mu α-Fe2O3 ane chete Oh zvinzvimbo, ukuwo γ-Fe2O3 inowanzo ratidzwa seFe3+ t2g [Fe3+5/3V1/3] eg O4 spinel ine vacancy mune eg zvinzvimbo. Naizvozvo, iyo Fe3+ ions muγ-Fe2O3 ine zvese Td uye Oh zvinzvimbo. Sezvakataurwa mubasa rakapfuura, kunyange zvazvo kusimba kwehuwandu hwezviviri zvakasiyana, kusimba kwavo kwehuwandu eg / t2g ndeye ≈1, asi munyaya iyi kucherechedzwa kwehuwandu hwehuwandu hwehuwandu eg / t2g inenge 1. Izvi zvinobvisa mukana wekuti Fe3 + chete iripo munyaya iyi. Tichifunga nezvenyaya yeFe3O4 ine misanganiswa yeFe2 + uye Fe3 +, inozivikanwa kuti isina simba (yakasimba) yekutanga muL3 mupendero weFe inoratidza kudiki (kukuru) kusagara munzvimbo yet2g. Izvi zvinoshanda kuFe2 + (Fe3 +), iyo inoratidza kuwedzera kwechiratidzo chekutanga chinoratidza kuwedzera kwezvinyorwa zveFe2 + 47. Mhedzisiro iyi inoratidza kuti Fe2+ uye γ-Fe2O3, α-Fe2O3 uye/kana Fe3O4 inotungamira pane inotonhora-yakakungurutswa nzvimbo dzemacomposites.
Yakawedzerwa photoemission electron thermal mifananidzo ye (a, c) uye (b, d) XAS spectra mhiri kweFe L2,3 kumucheto munzvimbo dzakasiyana-siyana mukati mematunhu akasarudzwa 2 uye E mumaFig. 2d.
Iyo yakawanikwa data yekuedza (Fig. 4a uye Supplementary Fig. 11) yakarongwa uye yakaenzaniswa neayo emakemikari akachena 40, 41, 48. Chaizvoizvo, marudzi matatu akasiyana ekuedza akacherechedza Fe L-edge XAS spectra (XAS-1, XAS-2 uye XAS-3: Fig. 4a) yakaonekwa panzvimbo yakasiyana-siyana. Kunyanya, mutsara wakafanana ne2-a (unonzi XAS-1) muFig. 3b yakaonekwa pamusoro penharaunda yose yekufarira, yakateverwa ne2-b spectrum (yakanyorwa XAS-2), nepo mutsara wakafanana neE-3 wakaonekwa mufig. 3d (inonzi XAS-3) yakaonekwa mune dzimwe nzvimbo dzenzvimbo. Kazhinji, maparamendi mana anoshandiswa kuzivisa nyika dzevalence dziripo mumuenzaniso wekuongorora: (1) L3 neL2 spectral features, (2) nzvimbo dzesimba dzeL3 neL2 features, (3) L3-L2 simba musiyano, (4) L2 intensity ratio / L3. Maererano nekuona kwekuona (Fig. 4a), zvose zvitatu zvikamu zveFe, zvinoti Fe0, Fe2 +, uye Fe3 +, zviripo pamusoro peiyo SDSS yakadzidza. Iyo yakaverengerwa intensity ratio L2/L3 yakaratidzawo kuvepo kwezvinhu zvese zvitatu.
a Akacherechedzwa akasiyana matatu ekuedza data (yakasimba mitsetse XAS-1, XAS-2 uye XAS-3 inoenderana ne2-a, 2-b uye E-3 muFig. 2 neFig. 3) zvichienzaniswa neyakafananidzirwa XAS Comparison spectra, octahedrons Fe2+, Fe3+, crystal field values ​​​​ye1. data yekuedza (XAS-1, XAS-2, XAS-3) uye inopindirana yakagadziridzwa LCF data (yakasimba mutema mutsetse), uye kuenzanisa XAS-3 spectra neFe3O4 (yakasanganiswa mamiriro eFe) uye Fe2O3 (yakachena Fe3+) zviyero.
Musanganiswa wemutsara (LCF) wakakodzera wezviyero zvitatu40,41,48 yakashandiswa kuyera kuumbwa kwesimbi oxide. LCF yakashandiswa kune matatu akasarudzwa Fe L-edge XAS spectra inoratidza musiyano wepamusoro-soro, unoti XAS-1, XAS-2 uye XAS-3, sezvinoratidzwa mumufananidzo 4b-d. Nezve LCF fittings, 10% Fe0 yakatariswa mune zvese zviitiko nekuda kwediki diki yatakaona mune ese data uye chokwadi chekuti ferrous simbi ndicho chinhu chikuru chesimbi. Zvechokwadi, kudzika kwekuedzwa kweX-PEEM yeFe (~ 6 nm) 49 yakakura kudarika inofungidzirwa oxidation layer thickness (zvishoma> 4 nm), zvichibvumira kuonekwa kwechiratidzo kubva kune iron matrix (Fe0) pasi pepasi passivation layer. Zvechokwadi, kudzika kwekuedzwa kweX-PEEM yeFe (~ 6 nm) 49 yakakura kudarika inofungidzirwa oxidation layer thickness (zvishoma> 4 nm), zvichibvumira kuonekwa kwechiratidzo kubva kune iron matrix (Fe0) pasi pepasi passivation layer. Действительно, пробная глубина X-PEEM для Fe (~ 6 нм)49 больше, чем предполагаемая толщина слоя окисления (немного > 4 нзбина сигнал от железной матрицы (Fe0) под пассивирующим слоем. Zvechokwadi, iyo probe X-PEEM yakadzika yeFe (~ 6 nm) 49 yakakura kudarika inofungidzirwa ukobvu hweiyo oxidation layer (zvishoma> 4 nm), izvo zvinoita kuti zvikwanise kuona chiratidzo kubva kune iron matrix (Fe0) pasi pepasi passivation layer.Muchokwadi, X-PEEM inoona Fe (~ 6 nm) 49 yakadzika kupfuura iyo inotarisirwa ukobvu hweiyo oxide layer (inongopfuura 4 nm), ichibvumira kuona zviratidzo kubva kune iron matrix (Fe0) pasi pepasi passivation layer. Musanganiswa wakasiyana-siyana weFe2+ neFe3+ wakaitwa kuti uwane mhinduro yakanakisa yedata rekuyedza rakacherechedzwa. Pamusoro pemuonde. Mufananidzo 4b unoratidza kusanganiswa kweFe2 + uye Fe3 + muXAS-1 spectrum, uko zviyero zveFe2 + uye Fe3 + zviri pedyo, inenge 45%, iyo inoratidza kusanganiswa kweoxidation mamiriro eFe. Nepo kune iyo XAS-2 spectrum, iyo muzana yeFe2+ neFe3+ inova ~ 30% uye 60%, zvichiteerana. Zviri muFe2+ zvakaderera pane zveFe3+. Chiyero cheFe2+ kusvika kuFe3 che1:2 zvinoreva kuti Fe3O4 inogona kuumbwa pachiyero chimwe cheFe ions. Mukuwedzera, kune XAS-3 spectrum, zvikamu zveFe2 + uye Fe3 + zvakachinja kusvika ~ 10% uye 80%, zvichiratidza kutendeuka kwepamusoro kweFe2 + kusvika kuFe3 +. Sezvataurwa pamusoro apa, Fe3+ inogona kubva ku-α-Fe2O3, γ-Fe2O3 kana Fe3O4. Kuti unzwisise zvingangobva kuFe3 +, XAS-3 spectra inorongwa pamwe chete nemhando dzakasiyana-siyana dzeFe3 + muFig. Zvisinei, kusimba kwepfudzi (A: kubva kuFe2 +) uye kuwedzera kwehuwandu B/A kunoratidza kuti spectrum yeXAS-3 iri pedyo asi kwete yakafanana neyo γ-Fe2O3. Kuenzaniswa nehuwandu γ-Fe2O3, iyo Fe 2p XAS kusimba kweA SDSS peak yakakwirira zvishoma (Fig. 4e), iyo inoratidza yakakwirira Fe2 + simba. Kunyangwe iyo spectrum yeXAS-3 yakafanana neye γ-Fe2O3, uko Fe3 + iripo mune ese maOh uye Td zvinzvimbo, kuzivikanwa kweakasiyana valence nyika uye kurongeka chete neL2,3 mupendero kana L2/L3 intensity ratio ichiri dambudziko. musoro unodzokororwa wehurukuro nekuda kwekuoma kwezvinhu zvakasiyana-siyana zvinobatanidzwa mumakwikwi ekupedzisira41.
Pamusoro perusarura rusarura rwemakemikari enyika ematunhu akasarudzwa anofarira anotsanangurwa pamusoro, iyo yepasi rose kemikari heterogeneity yezvinhu zvakakosha Cr uye Fe yakaongororwa nekurongedza ese XAS spectra yakawanikwa pane sampuli yepasi uchishandisa nzira yeK-kureva kusanganisa. Iwo emupendero profiles Cr L akaiswa nenzira yekuti agadzire masumbu maviri akakwana akagovaniswa munzvimbo inopisa-yakashanda uye inotonhora-yakatenderedzwa mienzaniso inoratidzwa muFigs. 5. Zviri pachena kuti hapana kuchinja kwemaitiro emunharaunda kwakaonekwa, sezvo maviri centroids e XAS Cr spectra akafanana zvikuru. Aya ma spectral maumbirwo emasumbu maviri anenge akafanana neaya anoenderana neCr2O342, zvinoreva kuti iwo Cr2O3 maseru akagoverwa zvakafanana pamusoro peSDSS.
sumbu reK-kureva L-kumucheto Cr matunhu, b anoenderana XAS centroids. Mhedzisiro yeK-zvinoreva X-PEEM kuenzanisa kweinotonhora-yakakungurutswa SDSS: clusters of K-zvinoreva edge matunhu eCr L2,3 uye d anowirirana XAS centroids.
Kuenzanisira yakawedzera kuomarara mepu yeFeL, mana uye mashanu akakwenenzverwa masumbu uye anoenderana masendimita (spectral distributions) anoshandiswa kune inopisa-inoshanda uye inotonhora-yakakungurutswa mienzaniso, zvichiteerana. Nokudaro, chikamu (%) cheFe2 + uye Fe3 + chinogona kuwanikwa nekugadzirisa LCF inoratidzwa muFig.4. Iyo pseudoelectrode inogona kuita Epseudo sebasa reFe0 yakashandiswa kuratidza iyo microchemical inhomogeneity yepamusoro oxide film. Epseudo inofungidzirwa nemutemo wekusanganisa,
apo \(\rm{E}_{\rm{Fe}/\rm{Fe}^{2 + (3 + )}}\) yakaenzana \(\rm{Fe} + 2e^ – \to\rm { Fe}^{2 + (3 + )}\), inova 0.440 uye 0.036 V, zvichiteerana. Nzvimbo dzine mukana wakaderera dzine huwandu hwepamusoro hweFe3 + makomponi. Iyo inogona kugoverwa mumuenzaniso we thermally deformed ine hunhu hwakatsetseka hune shanduko yakakura inenge 0.119 V (Fig. 6a,b). Izvi zvinogona kugovera zvakabatana zvakanyanya nepamusoro pepamusoro (Fig. 6a). Hapana dzimwe shanduko dzine chokuita nechinzvimbo dzakaonekwa mukati memukati we lamellar (Fig. 6b). Pane zvinopesana, nokuda kwekubatanidzwa kweokisidhi yakasiyana nemhando dzakasiyana dzeFe2 + uye Fe3 + muSDSS inotonhora, chimiro chisina kufanana chepseudopotential chinogona kuonekwa (Fig. 6c, d). Fe3+ oxides uye/kana (oxy) hydroxides ndizvo zvinonyanya kuita ngura musimbi uye zvinopinda muokisijeni nemvura50. Muchiitiko ichi, zvinogona kuonekwa kuti zvitsuwa zvakapfuma muFe3 + zvakagoverwa munharaunda uye zvinogona kuonekwa senzvimbo dzinopisa. Muchiitiko ichi, gradient mundima inogona kuitika, panzvimbo yehutano hwakakwana hwezvinogona, inogona kuonekwa sechiratidzo chekugara kwenzvimbo dzinoshanda dzakaora51. Iyi inhomogeneous kugovera kweFe2 + neFe3 + pamusoro peiyo inotonhora yakakungurutswa SDSS inogona kushandura enzvimbo yemakemikari enzvimbo uye inopa yakanyanya kushanda pamusoro penzvimbo muoxyde film cracking and corrosion reactions, nokudaro zvichibvumira iyo iri pasi pesimbi matrix kuti irambe ichiita ngura, zvichikonzera inhomogeneity yemukati. uye kuderedza hunhu hwekudzivirira hweiyo passivating layer.
K-kureva masumbu eFe L2,3 kumucheto matunhu uye anoenderana XAS centroids ye-c inopisa-yakashanda X-PEEM uye d-f inotonhora-yakakungurutswa SDSS. a, d K-zvinoreva cluster plot yakafukidzwa pamufananidzo weX-PEEM. Inofungidzirwa pseudoelectrode mikana (epseudo) inotaurwa pamwe chete neK-zvinoreva cluster diagrams. Kupenya kwechifananidzo che X-PEEM chakaita semuvara muFig.
Zvine yunifomu Cr asi akasiyana kemikari mamiriro eFe anotungamira kune kwakasiyana kwakabva oxide firimu kuparuka uye corrosion mapatani mune inopisa-yakakungurutswa uye inotonhora-yakakungurutswa Ce-2507. Ichi chivakwa chechando chakakungurutswa Ce-2507 chinozivikanwa. Nezvekuumbwa kwemaokisi uye mahydroxides eFe mumhepo yemuchadenga, zvinotevera zvinovharika mubasa iri sekusarerekera kwazvakarerekera:
Zvichienderana nechiyero cheX-PEEM, mhinduro iri pamusoro yakaitika muzviitiko zvinotevera. Badzi diki rinoenderana neFe0 rinosanganiswa neiyo pasi pesimbi yesimbi. Kuita kwesimbi Fe nemhoteredzo kunotungamira mukuumbwa kweFe(OH)2 layer (equation (5)), iyo inokudza Fe2+ chiratidzo muXAS yeL kumucheto kweFe. Kugara kwenguva refu kumhepo kuchaita kuti pave nekuumbwa kweFe3O4 uye / kana Fe2O3 oxides mushure meFe (OH) 252,53. Mhando mbiri dzeFe, Fe3O4 uye Fe2O3 dzakagadzikana, dzinogonawo kuumba muCr3 + hupfumi hwekudzivirira, uko Fe3O4 inofarira yunifomu uye yakabatana. Kuvapo kwezvose zviri zviviri zvinoguma mumisanganiswa oxidation nyika (XAS-1 spectrum). Iyo XAS-2 spectrum inonyanya kuenderana neFe3O4. Nepo iyo XAS-3 spectra yakacherechedzwa panzvimbo dzinoverengeka yakaratidza kutendeuka kwakazara ku γ-Fe2O3. Sezvo maX-ray asina kuputirwa ane hudzamu hwekupinda hunosvika 50 nm, chiratidzo chinobva pazasi chinoguma nekusimba kwepamusoro kweA peak.
Iyo XRD spectrum inoratidza kuti chikamu cheFe mufirimu reoxide chine dhizaini yakarongeka, iyo inosanganiswa neCr oxide layer. Kusiyana neiyo passivation hunhu hwekuora nekuda kweiyo inhomogeneity yeCr2O317, kunyangwe iyo yunifomu layer yeCr2O3 muchidzidzo ichi, kushomeka kwekushomeka kwakaonekwa mune ino kesi, kunyanya kune inotonhora-yakakungurutswa samples. Maitiro akacherechedzwa anogona kunzwisiswa sehterogeneity yekemikari oxidation mamiriro eiyo yepamusoro layer (Fe) inokanganisa corrosion performance. Kufamba zvishoma nezvishoma kwesimbi kana okisijeni ions mulatisi nekuda kweiyo stoichiometry yekumusoro (Fe oxide) uye yakadzika zvidimbu (Cr oxide) 52,53 inotungamirira kukubatana kuri nani (kunamatira) pakati pavo. Izvi, zvakare, zvinovandudza corrosion resistance. Naizvozvo, continuous stoichiometry, kureva one oxidation state yeFe, inodiwa pane abrupt stoichiometric shanduko. Thermally deformed SDSS ine yakawedzera yunifomu pamusoro uye denser yekudzivirira layer, iyo inopa zvirinani kuonda kwekudzivirira. Zvisinei, kune SDSS inotonhora, kuvapo kweFe3 + -rich zvitsuwa pasi pechidziviriro chekudzivirira kunoparadza kutendeseka kwepamusoro uye kunokonzera galvanic corrosion ye substrate iri pedyo, iyo inotungamirira kuderera kweRp (Table 1) muEIS spectra uye kuparara kwayo. resistance. Naizvozvo, zvitsuwa zvakagoverwa munharaunda zvakapfuma muFe3+ nekuda kwekushanduka kwepurasitiki zvinonyanya kupesvedzera kuita kwekushomeka kwecorrosion, inova budiriro mubasa iri. Naizvozvo, chidzidzo ichi chinopa spectromicrographs yekudzikisira mukuora kwekudzivirira nekuda kwepurasitiki deformation yeakadzidza SDSS samples.
Uyezve, nepo pasi risingawanzo kusanganiswa mumasimbi maviri echikamu chichiita zvirinani, kudyidzana kwechinhu ichi chakawedzerwa nesimbi yega matrix maererano nemaitiro ekuora kunoramba kusinganzwisisike zvichienderana nekuona kwe spectroscopic microscopy. Iyo Ce siginecha (pamwe neXAS M-mupendero) inoonekwa chete panzvimbo shoma panguva yekutonhora kukunguruka, asi inonyangarika panguva yekupisa deformation yeSDSS, ichiratidza yemuno kuiswa kweCe mune simbi matrix pachinzvimbo chehomogeneous alloying. Kunyange zvazvo michina yeSDSS isina kuvandudzwa6,7, kuvapo kweREE kunoderedza hukuru hwezvibatanidzwa uye inofungidzirwa kudzvinyirira gomba pamavambo54.
Mukupedzisa, basa iri rinoburitsa mhedzisiro yepasi pehterogeneity pakuora kwe2507 SDSS yakagadziridzwa necerium nekuenzanisa kemikari yemukati me nanoscale components. Isu takapindura mubvunzo wekuti nei simbi isina tsvina inoodza kunyangwe yakaputirwa neinodzivirira oxide layer nekuverenga zvakanyanya iyo microstructure, kemikari mamiriro epamusoro maficha uye masaini kugadzirisa uchishandisa K-zvinoreva kubatanidza. Yakatarwa kuti zvitsuwa zveFe3+-rakapfuma, kusanganisira kurongeka kwadzo octahedral uye tetrahedral mukati mechimiro chemusanganiswa Fe2+/Fe3+, ndiko kunobva oxide yekuparadza firimu uye sosi yekuora kwechando-yakakungurutswa SDSS. Nanoislands inodzorwa neFe3 + inotungamira kune yakashata corrosion kuramba kunyangwe pamberi peiyo yakakwana stoichiometric Cr2O3 passivating layer. Pamusoro pekufambira mberi kwemethodological kunoitwa mukuona mhedzisiro ye nanoscale kemikari heterogeneity pakuora, basa razvino rinotarisirwa kukurudzira maitiro einjiniya kuvandudza kushora kwesimbi yesimbi panguva yekugadzira simbi.
Kugadzirira maCe-2507 SDSS ingots anoshandiswa muchidzidzo ichi, zvakasanganiswa zvikamu, zvinosanganisira Fe-Ce master alloy yakavharwa nemachubhu esimbi akachena, akanyungudutswa muchoto che 150 kg yepakati frequency induction kuti ibudise simbi yakanyungudutswa ndokudururirwa muforoma yekukanda. Maumbirwo emakemikari akayerwa (wt %) akanyorwa muSupplementary Table 2. Ingot inotanga kupisa kuita mabhuroko. Zvadaro simbi yakanyungudutswa pa 1050 ° C kwemaminitsi makumi matanhatu kusvika kune imwe sarudzo yakasimba, ndokuzodzimwa mumvura kusvika kune tembiricha. Sampuli dzakadzidzwa dzakadzidzwa zvakadzama uchishandisa TEM neDOE kudzidza zvikamu, saizi yezviyo uye morphology. Ruzivo rwakadzama nezve masampuli uye maitiro ekugadzira anogona kuwanikwa mune mamwe masosi6,7.
Maitiro ecylindrical samples (φ10 mm × 15 mm) yekutsikirira inopisa neaxis yecylinder parallel kune deformation direction ye block. Kutsikirira kwepamusoro-soro kwakaitwa pahutano hunogara huri muhuwandu hwe 0.01-10 s-1 pamhando dzakasiyana-siyana dzekushisa muhuwandu hwe1000-1150 ° C uchishandisa Gleeble-3800 thermal simulator. Pamberi pekushandurwa, masampuli aipiswa patembiricha yakasarudzwa pamwero we10 ° C s-1 kwemaminetsi maviri kubvisa tembiricha. Mushure mekuwana kuenzana kwetembiricha, masampuli akaremara kusvika kune yechokwadi strain kukosha kwe0.7. Mushure me deformation, inobva yadzimwa nemvura kuti ichengetedze chimiro chakaremara. Zvadaro zvienzaniso zvakaomeswa zvakachekwa zvakaenderana negwaro rekumanikidza. Pachidzidzo ichi, takasarudza chienzaniso chakaremara pa1050°C, 10 s-1 nekuda kwehukukutu hwakacherechedzwa hwakanyanya kupfuura humwe hunhu7.
Kuwanda (80 × 10 × 17 mm3) samples dzeCe-2507 yakasimba mhinduro yakaedzwa pachikamu chetatu-asynchronous two-roll deformation muchina LG-300, iyo yakapa yakanakisa michina zvivakwa pakati pemamwe ese deformation makirasi6. The strain rate uye kukora kuderedzwa kwaive 0.2 m·s-1 uye 5% yenzira imwe neimwe, zvichiteerana.
Iyo Autolab PGSTAT128N electrochemical workstation yakashandiswa kuyera electrochemically SDSS mushure mekutonhora kukunguruka kusvika 90% kudzikisa ukobvu (1.0 yakaenzana dhizaini yechokwadi) uye inopisa kudzvanya kusvika 0.7 chaiyo dhiri pa1050 oC uye gumi s-1. Nzvimbo yekushandira ine matatu-electrode cell ine saturated calomel electrode sereferensi electrode, graphite counter electrode, uye SDSS sampuro seye electrode inoshanda. Mienzaniso yacho yakatemwa kuva masilinda ane dhayamita ye11.3 mm, kumativi ayo waya dzemhangura dzakatengeswa. Ipapo sampu yakadirwa ne epoxy resin, ichisiya nzvimbo yakavhurika ye1 cm2 seye electrode inoshanda (iyo yepasi peiyo cylindrical sample). Shandisa hanya panguva yekurapa epoxy uye panguva inotevera sanding uye kupukuta kuti usatsemuka. Nzvimbo yekushanda inoputirwa uye yakakwenenzverwa nedhaimondi yekupuruzira kumiswa ne particle size ye 1 micron, yakacheneswa nemvura yakasvibiswa uye ethanol uye yakaomeswa mumhepo inotonhora. Pamberi pezviyero zve electrochemical, masampula akapukutwa akaiswa kumhepo kwemazuva akati wandei kuti agadzire firimu reoxyde chaiyo. Mushonga wemvura weFeCl3 (6.0 wt.%), wakagadzikana neHCl kusvika pH = 1.0 ± 0.01, wakashandiswa kukurumidza kuora kwesimbi isina tsvina55, sezvo inowanikwa munzvimbo dzine hutsinye umo maion chloride aripo nesimba rakasimba reoxidizing uye yakaderera pH sezvakatsanangurwa neASTM. Miyero yakarongwa ndeye G48 neA923. Iwo masampula akanyudzwa muyedzo mhinduro kweawa imwe isati yatorwa chero kuyerwa kuitira kuti isvike kudunhu riri padyo nekumira. Kune yakasimba mhinduro, inopisa-yakashanda uye inotonhora-yakatenderedzwa mienzaniso, iyo impedance kuyerwa frequency renji yaive 1 × 105 ~ 0.1 Hz, uye yakavhurika-yedunhu mukana (OPS) yaive 5 mV, yaive 0.39, 0.33, uye 0.25 VSCE, zvichiteerana. Yese electrochemical bvunzo yechero sampuli yakadzokororwa kanokwana katatu pasi pemamiriro akafanana kuti ave nechokwadi chekuberekazve data.
Kune HE-SXRD zviyero, 1 × 1 × 1.5 mm3 rectangular duplex simbi zvidhinha zvakayerwa pa-high-energy Brockhouse wiggler line paCLS, Canada kuyera chikamu chekuumbwa56. Kuunganidzwa kwedata kwakaitwa pakamuri tembiricha muDebye-Scherrer geometry kana yekutakura geometry. Hurefu hwemasaisai eX-rays akaiswa kuLaB6 calibrant i0.212561 Å, inofambirana ne58 keV, iyo yakakwira zvakanyanya kupfuura yeCu Kα (8 keV) inowanzoshandiswa serabhoritari X-ray source. Muenzaniso unoiswa chinhambwe che 740 mm kubva pa detector. Kuonekwa kwevhoriyamu yemuenzaniso wega wega ndeye 0.2 × 0.3 × 1.5 mm3, iyo inotarirwa nehukuru hwedanda uye sampuli ukobvu. Imwe neimwe yedata iyi yakaunganidzwa pachishandiswa Perkin Elmer area detector, flat panel X-ray detector, 200 µm pixels, 40 × 40 cm2, uchishandisa nguva yekuratidzwa yemasekonzi 0.3 uye 120 mafuremu.
X-PEEM zviyero zvemamodhi maviri akasarudzwa akaitwa paPEEM yekupedzisira chiteshi cheBeamline MAXPEEM mutsetse muMAX IV murabhoritari (Lund, Sweden). Samples dzakagadzirirwa nenzira imwechete neye electrochemical zviyero. Sampuli dzakagadzirirwa dzakachengetwa mumhepo kwemazuva akati wandei uye dzakabviswa mukamuri ye ultrahigh vacuum isati yapiswa ne synchrotron photons. Kugadziriswa kwesimba kwedanda kunowanikwa nekuyera iyo ion inobuda spectrum kubva kuN 1 s kusvika 1 \ (\ pi _g ^ \st\) yenharaunda yekunakidzwa nehv = 401 eV muN2 uye kuvimba kweiyo photon simba paE3 / 2.57. Spectral fit yakapa ΔE (spectral linewidth) ~ 0.3 eV pamusoro pechiyero chesimba rakayerwa. Naizvozvo, iyo beamline simba rekugadzirisa yakafungidzirwa kuve E/∆E = 700 eV/0.3 eV > 2000 uye flux ≈1012 ph/s nekushandisa yakagadziridzwa SX-700 monochromator ine Si 1200-line mm-1 grating yeFe 2p, L2, Cr32pdge, Cr32 edge, L2, Cr32 edge. L2,3 mupendero, uye Ce M4,5 mupendero. Naizvozvo, iyo beamline simba rekugadzirisa yakafungidzirwa kuve E/∆E = 700 eV/0.3 eV > 2000 uye flux ≈1012 ph/s nekushandisa yakagadziridzwa SX-700 monochromator ine Si 1200-mutsara mm-1 grating yeFe 2p, L2.32pdge L2. L2.3 mupendero, uye Ce M4.5 mupendero. Таким образом, энергетическое разрешение канала пучка было оценено как E/∆E = 700 эВ/0,3 эВ > 2000 и поток ≈1012 модифицированного монохроматора SX-700 с решеткой Si 1200 штрихов/мм для Fe кромка 2p L2,3, кромка Cr 2p L2,3, кромка Ni 2p L2, кромка Ni 2p L2, 3, кромка Ni 2p L2,3 Nokudaro, kugadziriswa kwesimba kwebheji chiteshi kwakafungidzirwa seE / ∆E = 700 eV / 0.3 eV > 2000 uye flux ≈1012 f / s uchishandisa yakagadziridzwa SX-700 monochromator ine Si grating ye1200 mitsara / mm yeFe edge 2p L2, 3p Cr2 edge. uye Ce edge M4.5.因此，光束线能量分辨率估计為E/ΔE = 700 eV/0.3 eV > 2000 和通量≈1012 ph/s 通过用改进00 1200 线mm−1 光栅用于Fe 2p L2,3 边缘、Cr 2p L2,3 边缘、Ni 2p L2,3 边缘和Ce M4,5 边缘.因此 , 光束线 能量 分辨率 為 為 為 δe = 700 EV/0.3 EV> 2000 和 ≈1012 PH/S 通过 和改进0 的 SX-70 . 1200 线 mm-1 光栅 于 Fe 2P 2P 2P L2.3 边缘、Cr 2p L2.3 边缘、Ni 2p L2.3 边缘和Ce M4.5 边缘.Saka, kana uchishandisa yakagadziridzwa SX-700 monochromator uye 1200 mutsara Si grating. 3, Cr edge 2p L2.3, Ni edge 2p L2.3 uye Ce edge M4.5.Wedzera iyo photon simba mu 0.2 eV matanho. Pasimba rega rega, mifananidzo yePEEM yakarekodhwa pachishandiswa TVIPS F-216 CMOS detector ine 2 x 2 binning fiber optic connection inopa 1024 × 1024 pixels mu20 µm ndima yekuona. Nguva yekuratidzwa kwemifananidzo ndeye 0.2 masekondi, avhareji 16 mafuremu. Iyo photoelectron image simba inosarudzwa nenzira yekupa iyo yepamusoro yechipiri electron chiratidzo. Yese kuyerwa kunoitwa pane yakajairika chiitiko che linearly polarized photon beam. Kuti uwane rumwe ruzivo nezvezviyero, ona chidzidzo chakapfuura58. Mushure mekudzidza iyo yakazara electron goho (TEY) 59 yekuongorora maitiro uye kushandiswa kwayo mu X-PEEM, kudzika kwekuona kweiyi nzira kunofungidzirwa pa ~ 4-5 nm yechiratidzo cheCr uye ~ 6 nm yechiratidzo cheFe. Iyo Cr kudzika iri padyo zvakanyanya neiyo oxide firimu ukobvu (~ 4 nm) 60,61 ukuwo Fe kudzika kwakakura kupfuura iyo oxide firimu ukobvu. Iyo XAS yakaunganidzwa pedyo neFe L mupendero musanganiswa we iron oxide XAS uye FeO kubva kumatrix. Muchiitiko chekutanga, kusimba kwemaerekitironi akabudiswa kunokonzerwa nemhando dzose dzemaerekitironi dzinopa TEY. Nekudaro, chiratidzo chesimbi chakachena chinoda yakakwirira kinetic simba kuti maerekitironi apfuure nepakati peiyo oxide layer, isvike pamusoro, uye inounganidzwa neanalyzer. Muchiitiko ichi, chiratidzo cheFe0 chinonyanya kukonzerwa neLVV Auger maerekitironi uye maerekitironi echipiri anobudiswa navo. Pamusoro pezvo, kusimba kweTEY kunopihwa neaya maerekitironi kuora panguva yekubuda kweelectron49 zvichiwedzera kudzikisa siginecha yeFe0 mumepu yesimbi XAS.
Kubatanidza migodhi yedata mu data cubes (X-PEEM data) inhanho yakakosha mukutora ruzivo rwakakodzera (kemikari kana zvinhu zvemuviri) nenzira yakawanda. K-kureva kubatanidza kunoshandiswa zvakanyanya munzvimbo dzinoverengeka, kusanganisira kuona muchina, kugadzirisa mifananidzo, kusatariswa kucherechedzwa kwemaitiro, hungwaru hwekugadzira, uye ongororo yemhando24. Semuyenzaniso, K-zvinoreva clustering inonyatso shandiswa kune clustering hyperspectral image data62. Mumusimboti, kune akawanda-zvinhu data, iyo K-inoreva algorithm inogona nyore kuaunganidza maererano neruzivo nezve hunhu hwavo (photon simba maitiro). K-zvinoreva clustering is an iterative algorithm yekugovanisa data muK asiri-kuwandirana mapoka (masumbu), uko pixel yega yega inova yeboka chairo zvichienderana nekugoverwa kwenzvimbo kwekemikari inhomogeneity musimbi microstructural kuumbwa. Iyo K-zvinoreva algorithm ine nhanho mbiri: nhanho yekutanga inoverengera K centroids, uye danho rechipiri rinopa poindi imwe neimwe kusumbu rine macentroid akavakidzana. Pakati pesimba regiravhiti resumbu rinotsanangurwa searithmetic zvinoreva nzvimbo dze data (XAS spectra) yesumbu iroro. Kune madaro akasiyana ekutsanangura macentroid akavakidzana seEuclidean madaro. Pamufananidzo wekupinza we px,y (x uye y zvinogadziriswa mumapikisesi), CK ndiyo nzvimbo yepakati yegiravhiti yesumbu; mufananidzo uyu unogona kuzopatsanurwa (kubatanidzwa) kuita K masumbu uchishandisa K-zvinoreva63. Matanho ekupedzisira eK-kureva kusanganisa algorithm ndeaya:
Danho 2. Verenga dhigirii yenhengo yepixels yose maererano necentroid iripo. Semuenzaniso, inoverengerwa kubva paEuclidean chinhambwe d pakati pepakati nepixel yega yega:
Nhanho 3 Isa pixel yega yega kune iri pedyo centroid. Wobva waverengera zvakare K centroid zvinzvimbo sezvinotevera:
Danho 4. Dzokorora maitiro (equations (7) uye (8)) kusvikira macentroids asangana. Mhedzisiro dzemhando dzemasumbu dzekupedzisira dzakabatana zvakanyanya nesarudzo yakakwana yekutanga centroids63. Kune iyo PEEM data chimiro chemifananidzo yesimbi, kazhinji X (x × y × λ) icube ye3D array data, nepo x uye y axes inomiririra ruzivo rwenzvimbo (pixel resolution) uye iyo λ axis inoenderana neiyo simba spectral mode yemafotoni. Iyo K-zvinoreva algorithm yakashandiswa kuongorora matunhu anofarira muX-PEEM data nekuparadzanisa mapixels (masumbu kana madiki-mabhuru) zvinoenderana neawo spectral maitiro uye kubvisa yakanakisa centroid (XAS spectral curve) kune yega yega analyte (cluster). Inoshandiswa kudzidza kugovera kwenzvimbo, shanduko yenzvimbo yekutarisa, maitiro e oxidation uye chimiro chemakemikari. Semuenzaniso, iyo K-zvinoreva clustering algorithm yakashandiswa kuFe L-kumucheto uye Cr L-kumucheto munzvimbo dzinopisa-inoshanda uye inotonhora-yakakungurutswa X-PEEM. Nhamba dzakasiyana dzeK-masumbu (microstructural regions) dzakaedzwa kuti dziwane akanakisa masumbu uye centroids. Kana iyo girafu inoratidzwa, mapixels anopihwa kune iyo chaiyo cluster centroids. Kugoverwa kwemavara kwega kwega kunoenderana nepakati pesumbu, kuratidza kurongeka kwenzvimbo yemakemikari kana zvinhu zvemuviri. Iwo akabviswa centroids mutsetse musanganiswa we pure spectra.
Data inotsigira zvakabuda muchidzidzo ichi inowanika kubva kumunyori weWC pane chikumbiro chine musoro.
Sieurin, H. & Sandström, R. Kutyoka kwekuomarara kwesimbi yakasungwa duplex isina tsvina. Sieurin, H. & Sandström, R. Kutyoka kwekuomarara kwesimbi yakasungwa duplex isina tsvina. Sieurin, H. & Sandström, R. Вязкость разрушения сварной дуплексной нержавеющей стали. Sieurin, H. & Sandström, R. Kutsemuka kuomarara kwe welded duplex stainless steel. Sieurin, H. & Sandström, R. 焊接双相不锈钢的断裂韧性. Sieurin, H. & Sandstrom, R. 焊接双相不锈钢的断裂韧性. Sieurin, H. & Sandström, R. Вязкость разрушения сварных дуплексных нержавеющих сталей. Sieurin, H. & Sandström, R. Kutsemuka kuomarara kwesimbi dzakasungwa duplex dzisina tsvina.project. fractal. fur. 73, 377–390 (2006).
Adams, FV, Olubambi, PA, Potgieter, JH & Van Der Merwe, J. Corrosion resistance ye duplex stainless steels mune zvakasarudzwa organic acids uye organic acid / chloride environments. Adams, FV, Olubambi, PA, Potgieter, JH & Van Der Merwe, J. Corrosion resistance ye duplex stainless steels mune zvakasarudzwa organic acids uye organic acid / chloride environments.Adams, FW, Olubambi, PA, Potgieter, J. Kh. uye Van Der Merwe, J. Corrosion resistance ye duplex stainless steels munzvimbo dzine mamwe organic acids uye organic acids/chlorides. Adams, FV, Olubambi, PA, Potgieter, JH & Van Der Merwe, J. 双相不锈钢在选定有机酸和有机酸/氯化物环境中的耐腐蚀性. Adams, FV, Olubambi, PA, Potgieter, JH & Van Der Merwe, J. 双相stainless steel在特定organic酸和Organic酸/chlorinated environment的耐而性性.Adams, FW, Olubambi, PA, Potgieter, J. Kh. uye Van Der Merwe, J. Corrosion resistance ye duplex stainless steels munzvimbo dzine mamwe organic acids uye organic acids/chlorides.anticorrosive. Method Mater 57, 107–117 (2010).
Barella S. et al. Corrosion-oxidizing zvimiro zveFe-Al-Mn-C duplex alloys. Zvishandiso 12, 2572 (2019).
Levkov, L., Shurygin, D., Dub, V., Kosyrev, K. & Balikoev, A. Chizvarwa chitsva che super duplex steels yemidziyo gasi nekugadzirwa kwemafuta. Levkov, L., Shurygin, D., Dub, V., Kosyrev, K. & Balikoev, A. Chizvarwa chitsva che super duplex steels yemidziyo gasi nekugadzirwa kwemafuta.Levkov L., Shurygin D., Dub V., Kosyrev K., Balikoev A. Chizvarwa chitsva che super duplex simbi yemafuta uye gasi zvigadzirwa zvekugadzira.Levkov L., Shurygin D., Dub V., Kosyrev K., Balikoev A. Chizvarwa chitsva che super duplex simbi dzegasi nemafuta ekugadzira michina. E3S webinar. 121, 04007 (2019).
Kingklang, S. & Uthaisangsuk, V. Kuongorora kwekupisa deformation maitiro e duplex Stainless steel giredhi 2507. Metall. Kingklang, S. & Uthaisangsuk, V. Kuongorora kwekupisa deformation maitiro e duplex Stainless steel giredhi 2507. Metall. Kingklang, S. & Uthaisangsuk, V. Исследование поведения горячей деформации дуплексной нержавеющей стали марки 2507. Metall. Kingklang, S. & Uthaisangsuk, V. Chidzidzo cheHot Deformation Behavior yeType 2507 Duplex Stainless Steel. Metall. Kingklang, S. & Uthaisangsuk, V. 2507 级双相不锈钢的热变形行為研究. Kingklang, S. & Uthaisangsuk, V. 2507Kingklang, S. uye Utaisansuk, V. Kuongorora kweHot Deformation Behavior yeType 2507 Duplex Stainless Steel. Metal.alma mater. trance. A 48, 95–108 (2017).
Zhou, T. et al. Mhedzisiro yekudzora kutonhora kutenderedza pane iyo microstructure uye michina zvimiro zvecerium-modified super-duplex SAF 2507 simbi isina tsvina. alma mater. sainzi. project. A 766, 138352 (2019).
Zhou, T. et al. Kupisa-deformation-induced dhizaini uye michina zvimiro zvecerium-modified super-duplex SAF 2507 simbi isina tsvina. J. Alma mater. tangi yekuchengetedza. teknolojia. 9, 8379–8390 (2020).
Zheng, Z., Wang, S., Long, J., Wang, J. & Zheng, K. Mhedzisiro yezvinhu zvisingawanzoitiki zvepasi pane yakanyanya tembiricha oxidation maitiro eaustenitic simbi. Zheng, Z., Wang, S., Long, J., Wang, J. & Zheng, K. Mhedzisiro yezvinhu zvisingawanzoitiki zvepasi pane yakanyanya tembiricha oxidation maitiro eaustenitic simbi.Zheng Z., Wang S., Long J., Wang J. naZheng K. Pesvedzero yezvinhu zvisingawanzoitiki zvepasi pamaitiro eaustenitic simbi pasi pekupisa tembiricha oxidation. Zheng, Z., Wang, S., Long, J., Wang, J. & Zheng, K. 稀土元素对奥氏体钢高温氧化行為的影响. Zheng, Z., Wang, S., Long, J., Wang, J. & Zheng, K.Zheng Z., Wang S., Long J., Wang J. naZheng K. Pesvedzero yezvisingawanzoitiki zvinhu zvepasi pamafambiro eaustenitic simbi pakupisa tembiricha oxidation.ngura. sainzi. 164, 108359 (2020).