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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 pane microscopic level, zvichienderana nekwakabva kwepamusoro inhomogeneity.Mubasa iri, iyo nanoscale yepamusoro kemikari heterogeneity yakaonekwa ne spectroscopic microscopy uye chemometric ongororo inotonga zvisingatarisirwi kuora uye kuora kweinotonhora yakakungurutswa cerium yakagadziridzwa super duplex Stainless simbi 2507 (SDSS) panguva yayo inopisa deformation maitiro.rumwe rutivi.Kunyange zvazvo X-ray photoelectron microscopy yakaratidza kufukidzwa kwakafanana kweiyo Cr2O3 layer, inotonhora yakakungurutswa SDSS yakaratidza kusasimba kwekuita nekuda kwekugoverwa kwenzvimbo kweFe3+ rich nanoislands paFe/Cr oxide layer.Ruzivo urwu padanho reatomu runopa kunzwisisa kwakadzama kwekuora kwesimbi isina tsvina uye kunotarisirwa kubatsira kurwisa kukoromoka kwesimbi dzakafanana dzakakwirira-alloy.
Kubva pakatanga kugadzirwa simbi isina tsvina, kushorwa kwe ferrochromium alloys kwave kunzi kune chromium, iyo inoumba yakasimba oxide/oxyhydroxide inoratidza hunhu hwekupfuura munzvimbo zhinji.Zvichienzaniswa neyakajairwa (austenitic uye ferritic) simbi isina tsvina, super duplex Stainless simbi (SDSS) ine zvirinani corrosion resistance ine superior mechanical properties1,2,3.Kuwedzera kwesimba remagetsi kunobvumira kureruka uye mamwe compact magadzirirwo.Mukupesana, iyo yehupfumi SDSS ine yakanyanya kuramba kugomba uye kukoromoka, zvichikonzera hupenyu hurefu hwesevhisi uye mashandisirwo akafara mukudzora kusvibiswa, midziyo yemakemikari, uye indasitiri yemafuta negasi yekumahombekombe4.Nekudaro, iyo nhete yemhando yetembiricha yekurapa kupisa uye kushata kuumbwa kunotadzisa iyo yakakura inoshanda kushanda.Naizvozvo, SDSS yakagadziridzwa kuti ivandudze zvivakwa zviri pamusoro.Semuenzaniso, kugadziridzwa kweCe uye kuwedzera kwepamusoro kweN 6, 7, 8 kwakaunzwa mu2507 SDSS (Ce-2507).Mushonga wakakodzera we0.08 wt.% rare earth element (Ce) ine simba rinobatsira pane mechanical properties yeDSS, sezvo inovandudza zviyo zvekugadzirisa uye simba remuganhu wezviyo.Kupfeka uye kusagadzikana kwekuora, kusimba simba uye goho simba, uye kupisa kushanda kwakavandudzwa9.Huwandu hwakakura hwenitrogen hunogona kutsiva zvinodhura nickel zvemukati, zvichiita kuti SDSS iwedzere kudhura-10.
Nguva pfupi yadarika, SDSS yakashongedzwa mupurasitiki patembiricha dzakasiyana (tembiricha yakaderera, kutonhora uye kupisa) kuti iwane yakanakisa mechaniki zvivakwa6,7,8.Nekudaro, iyo yakanakisa corrosion resistance yeSDSS imhaka yekuvapo kwefirimu yakaonda oxide pamusoro, iyo inokanganiswa nezvinhu zvakawanda, sekuvapo kwezvikamu zvakawanda zvine miganhu yezviyo zvakasiyana, mvura isingadiwe uye maitiro akasiyana.iyo yemukati inhomogeneous microstructure yezvikamu zvakasiyana-siyana zve austenitic uye ferritic zvakakanganiswa 7.Naizvozvo, kudzidza kweiyo microdomain zvimiro zvemafirimu akadaro padanho reiyo yemagetsi chimiro kwakakosha kwakakosha kuti unzwisise SDSS corrosion uye inoda yakaoma nzira dzekuyedza.Kusvika iye zvino, nzira dzinotarisa pamusoro-soro dzakadai seAuger electron spectroscopy11 uye X-ray photoelectron spectroscopy12,13,14,15 pamwe chete neiyo yakaoma X-ray photoelectron photoelectron system inosiyanisa, asi kazhinji inokundikana kupatsanura, kemikari inotaura yechinhu chimwe chete munzvimbo dzakasiyana munzvimbo pane nanoscale.Ongororo dzinoverengeka dzichangoburwa dzakabatanidza oxidation yemuno yechromium kune yakacherechedzwa corrosion maitiro e17 austenitic stainless steels, 18 martensitic stainless steels, uye SDSS 19, 20. Zvisinei, zvidzidzo izvi zvakanyanya kutarisisa pamusoro pemhedzisiro yeCr heterogeneity (semuenzaniso, Cr3 + corrosion state) pane oxidation state.Lateral heterogeneity mu oxidation state yezvinhu zvinogona kukonzerwa neakasiyana makomisheni ane akafanana constituent elements, senge iron oxides.Aya makomisheni anogara nhaka thermomechanically processed saizi diki padhuze padhuze nemumwe, asi akasiyana mukuumbwa uye oxidation state16,21.Naizvozvo, kuburitsa kuparadzwa kwemafirimu eoxide uye ipapo gomba kunoda kunzwisisa kwepamusoro inhomogeneity padanho remicroscopic.Pasinei nezvinodiwa izvi, kuongororwa kwehuwandu hwakadai se lateral oxidation heterogeneity, kunyanya yesimbi pane nano / atomic scale, ichiri kushayikwa uye kukosha kwavo kwekudzivirira kuora kunoramba kusingatarisirwi.Kusvika nguva pfupi yadarika, chimiro chemakemikari yezvinhu zvakasiyana-siyana, seFe neCa, chakatsanangurwa zvakanyanya pamasampuli esimbi uchishandisa yakapfava X-ray photoelectron microscopy (X-PEEM) mune nanoscale synchrotron radiation zvivako.Yakasanganiswa nemakemikari anonzwa X-ray absorption spectroscopy (XAS) maitiro, X-PEEM inogonesa XAS kuyerwa nepamusoro penzvimbo uye spectral resolution, ichipa ruzivo rwemakemikari nezve elemental kuumbwa uye mamiriro ayo emakemikari ane spatial resolution pasi kusvika nanometer scale 23.Iyi spectroscopic yekutarisa kwenzvimbo yekutanga pasi pemaikorosikopu inogonesa kuedza kwemakemikari emunharaunda uye inogona kuratidza munzvimbo yaimbove isina kuongororwa shanduko yekemikari muFe layer.
Ichi chidzidzo chinowedzera zvakanakira PEEM mukuona kusiyana kwemakemikari pananoscale uye inopa inonzwisisika-yepamusoro-soro yeatomu yekuongorora nzira yekunzwisisa maitiro ekuora kweCe-2507.Inoshandisa K-zvinoreva cluster chemometric data24 kumepu yepasi rose kemikari inoumbwa (heterogeneity) yezvinhu zvinosanganisirwa, nemakemikari ayo anounzwa mukumiririrwa kwenhamba.Kusiyana nekuora kwakajairika kunokonzerwa nekuparara kwe chromium oxide firimu, iyo yazvino yakashata passivation uye yakashata corrosion resistance inonzi inonzi localized Fe3 + rich nanoislands pedyo neFe / Cr oxide layer, iyo inogona kunge iri kurwiswa neinodzivirira oxide.Inoumba firimu panzvimbo uye inokonzera kuora.
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 mhinduro dzeFeCl3 pakamuri tembiricha.Iyo yakasarudzwa electrolyte inoshanda seyakasimba oxidizing agent, inoratidza maitiro eiyo passivation firimu kuputsa.Kunyangwe izvo zvinyorwa zvisina kudzika kudzika kwekushisa kwekamuri, ongororo idzi dzakapa nzwisiso yezvingangoitika zviitiko zvekutadza uye post-corrosion maitiro.Iyo yakaenzana yedunhu (Fig. 1d) yakashandiswa kuti ienderane ne electrochemical impedance spectroscopy (EIS) spectra, uye mhedzisiro inoenderana inoratidzwa muTebhu 1. Zvisina kukwana hafu denderedzwa zvakaonekwa pakuedza mhinduro yakabatwa uye inopisa yakashanda samples, nepo inofananidzwa compressed hafu madenderedzwa akanga anotonhora akakungurutswa (Fig. 1b).MuEIS spectrum, iyo semicircle radius inogona kutorwa seye polarization resistance (Rp) 25,26.Iyo Rp yemhinduro yakabatwa SDSS muTable 1 ingangoita 135 kΩ cm-2, zvisinei kune inopisa inoshanda uye inotonhora yakatenderedzwa SDSS tinogona kuona yakaderera tsika dze34.7 uye 2.1 kΩ cm-2 zvakateerana.Uku kudzikira kwakakosha kweRP kunoratidza kukanganisa kwepurasitiki deformation pane passivation uye corrosion kuramba, sezvakaratidzwa mumishumo yapfuura 27, 28, 29, 30.
a Nyquist, b, c Bode impedance uye chikamu madhayagiramu, uye yakaenzana yedunhu modhi ye d, uko RS iri electrolyte kuramba, Rp ndiyo polarization resistance, uye QCPE ndiyo inogara iri chikamu element oxide inoshandiswa kuenzanisira isina-ideal capacitance (n) .Iwo EIS zviyero zvakaitwa pasina-mutoro mukana.
Maodha ekutanga anogara achiratidzwa mudhayagiramu yeBode uye yakakwirira frequency plateau inomiririra kupikisa kwe electrolyte RS26.Sezvo frequency inoderera, iyo impedance inowedzera uye yakashata chikamu angle inowanikwa, ichiratidza capacitance kutonga.Chikamu chekona chinowedzera, chichichengetedza kukosha kwayo kukuru muhuwandu hwehuwandu hwehuwandu, uye zvino inoderera (Fig. 1c).Zvisinei, muzviitiko zvose zvitatu izvi zvakakosha zvakanyanya zvichiri pasi pe90 °, zvichiratidza maitiro asina kunaka capacitive nekuda kwe capacitive dispersion.Nokudaro, iyo QCPE inoramba iine chikamu chechikamu (CPE) chinoshandiswa kumiririra interfacial capacitance distribution yakabva kune roughness yepamusoro kana inhomogeneity, kunyanya maererano neatomic scale, fractal geometry, electrode porosity, non-uniform potential, uye pamusoro inoenderana nekugovera ikozvino.Electrode geometry31,32.CPE impedance:
apo j ndiyo nhamba yekufungidzira uye ω ndiyo frequency yeakona.QCPE ndeye frequency yakazvimirira inogara yakaenzana nenzvimbo yakavhurika ye electrolyte.n inhamba yesimba isina dimensionless inotsanangura kutsauka kubva kune yakanaka capacitive maitiro e capacitor, kureva iyo padyo n ndeye 1, iyo iri padyo CPE ndeye yakachena capacitance, uye kana n iri pedyo ne zero, iko kuramba.Kutsauka kudiki kwen, padhuze ne1, kunoratidza iyo isiri-yakanaka capacitive maitiro epamusoro mushure mekuedzwa kwepolarization.Iyo QCPE yechando yakakungurutswa SDSS yakakwira zvakanyanya kupfuura zvigadzirwa zvakafanana, izvo zvinoreva kuti mhando yepamusoro haina yunifomu.
Zvinoenderana neakawanda corrosion kuramba zvivakwa zvesimbi isina tsvina, iyo yakakwira Cr yemukati meSDSS kazhinji inokonzeresa yepamusoro corrosion kuramba kweSDSS nekuda kwekuvapo kweinodzivirira oxide firimu pamusoro17.Iyi firimu inofamba inowanzopfuma muCr3+ oxides uye/kana hydroxides, kunyanya kubatanidza Fe2+, Fe3+ oxides uye/kana (oxy)hydroxides 33.Pasinei nekufanana kwepamusoro, passivating oxide layer, uye pasina kukuvara kunoonekwa pamusoro, sekutsanangurwa nemifananidzo midiki,6,7 maitiro ekuora kweiyo inopisa-inoshanda uye inotonhora-yakakungurutswa SDSS yakasiyana uye nekudaro inoda ongororo yakadzama ye deformation microstructure uye chimiro chesimbi.
Iyo microstructure yeakaremara simbi isina tsvina yakaongororwa zvakanyanya uchishandisa mukati uye synchrotron yakakwirira-simba X-rays (Supplementary Figures 1, 2).Ongororo yakadzama inopiwa muSupplementary Information.Kunyange zvazvo ivo vanonyanya kufanana nemhando yechikamu chikuru, kusiyana kwezvikamu zvezvikamu zvechikamu zvinowanikwa, izvo zvakanyorwa muSupplementary Table 1. Iyi misiyano inogona kusanganiswa ne-inhomogeneous phase fractions pamusoro, pamwe chete nezvikamu zvezvikamu zve volumetric zvakaitwa pakadzika kwakasiyana.kuonekwa ne X-ray diffraction.(XRD) ine akasiyana emagetsi masosi emafotoni echiitiko.Chikamu chakanyanya chepamusoro che austenite mune inotonhora yakakungurutswa zvienzaniso, yakatemwa neXRD kubva murabhoritari sosi, inoratidza zvirinani kupasa uye zvichizotevera zviri nani kusaora kwecorrosion35, nepo kunyatso uye nenhamba mhedzisiro inoratidza akasiyana maitiro muchikamu chechikamu.Mukuwedzera, kupikisa kwekuora kwesimbi kunoenderanawo nehuwandu hwekunatswa kwezviyo, kuderedza kukura kwezviyo, kuwedzera kwe microdeformations uye dislocation density inoitika panguva yekurapa thermomechanical36,37,38.Mienzaniso inopisa-yakashandiswa inoratidza humwe hunyoro, hunoratidza zviyo zve micron-size, asi zvindori zvakatsetseka zvakaonekwa mumifananidzo inotonhora (Supplementary Fig. 3) inoratidza kugadziridzwa kwezviyo zvakakosha kune nanoscale mubasa rekare6, iyo inofanira kubatsira pakufambisa firimu.kuumbwa uye kuwedzera kwekusagadzikana kwecorrosion.Higher dislocation density inowanzobatanidzwa nekushomeka kwakadzika kugomba, iyo inobvumirana nemayero e electrochemical.
Shanduko mumakemikari ezvimiro zvemicrodomain zvekutanga zvinhu zvakadzidzwa zvakarongeka uchishandisa X-PEEM.Pasinei nekuwanda kwezvinhu zvealloying, Cr, Fe, Ni uye Ce39 vakasarudzwa pano, sezvo Cr chiri chinhu chakakosha pakuumbwa kwefirimu rekuita, Fe ndicho chinhu chikuru musimbi, uye Ni inosimudzira passivation uye kuenzanisa ferrite-austenitic chikamu chimiro uye chinangwa cheCe shanduko.Nekugadzirisa simba reiyo synchrotron radiation, iyo RAS yakaputirwa kubva pamusoro neiyo huru maficha eCr (kumucheto L2.3), Fe (kumucheto L2.3), Ni (kumucheto L2.3) uye Ce (kumucheto M4.5).kupisa kuumba uye kutonhora kukungurutsa Ce-2507 SDSS.Ongororo yedata yakakodzera yakaitwa nekubatanidza kuenzanisa kwesimba nedata rakaburitswa (semuenzaniso XAS 40, 41 paFe L2, 3 micheto).
Pamusoro pemuonde.Mufananidzo 2 unoratidza mifananidzo ye-X-PEEM ye-hot-worked (Fig. 2a) uye inotonhora-yakaputirwa (Fig. 2d) Ce-2507 SDSS uye inowirirana XAS edges yeCr uye Fe L2,3 pane imwe neimwe yakanyorwa nzvimbo.Iyo L2,3 mupendero weXAS inoongorora iyo isingagarike 3d inoti mushure meelectron photoexcitation pa-spin-orbit splitting levels 2p3/2 (L3 edge) uye 2p1/2 (L2 edge).Ruzivo nezve valence state yeCr yakawanikwa kubva kuXAS paL2,3 kumucheto muFig. 2b, e.Kuenzanisa nevatongi.42,43 yakaratidza kuti nhongonya ina dzakaonekwa pedyo neL3 kumucheto, inonzi A (578.3 eV), B (579.5 eV), C (580.4 eV) uye D (582.2 eV), inoratidzira octahedral Cr3+, inoenderana neCr2O3 ion.Mucherechedzo wekuedza unobvumirana nekuverenga kwe theoretical kunoratidzwa mumapuranga b uye e, anowanikwa kubva kune akawanda macalculation e crystal field 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 X-PEEM thermal image of thermally deformed SDSS inoenderana ne b Cr L2.3 edge uye c Fe L2.3 edge, d X-PEEM thermal image of cold rolled SDSS inoenderana e Cr L2.3 edge uye f Fe L2 .3 edge side ( f).Iyo XAS spectra yakarongerwa munzvimbo dzakasiyana dzakamisikidzwa pamifananidzo inopisa (a, d), mitsara yeorenji ine madoti mu (b) uye (e) inomiririra yakafananidzwa XAS spectra yeCr3+ ine crystal munda kukosha kwe2.0 eV.Pamifananidzo yeX-PEEM, shandisa palette inopisa kuti uvandudze kuverenga kwemifananidzo, apo mavara kubva pabhuruu kusvika kune tsvuku anoenderana nekusimba kwekutorwa kweX-ray (kubva pasi kusvika kumusoro).
Pasinei nemamiriro emakemikari ezvinhu izvi zvesimbi, chimiro chemakemikari chekuwedzera kweNi uye Ce alloying zvinhu zvemasamples ose maviri hazvina kuchinjwa.Kuwedzera kudhirowa.Mifananidzo 5-9 inoratidza mifananidzo yeX-PEEM uye inofananidzwa neXAS spectra yeNi uye Ce panzvimbo dzakasiyana-siyana pamusoro pezvienzaniso zvinopisa-zvakashanda uye zvinotonhora.Ni XAS inoratidza iyo oxidation mamiriro eNi2+ pamusoro peiyo yese yakayerwa nzvimbo yekupisa-yakashanda uye inotonhora-yakakungurutswa mienzaniso (Supplementary Discussion).Izvo zvinofanirwa kucherechedzwa kuti, mune yekupisa-yakashanda samples, iyo XAS chiratidzo cheCe haina kucherechedzwa, nepo mune inotonhora-yakakungurutswa samples, iyo spectrum yeCe3 + yakaonekwa.Kucherechedzwa kwenzvimbo dzeCe mumasampuli anotonhora-akatenderedzwa kwakaratidza kuti Ce inonyanya kuoneka muchimiro chemvura.
Mune thermally deformed SDSS, hapana kuchinja kwemaitiro emunharaunda muXAS paFe L2,3 kumucheto kwakaonekwa (Fig. 2c).Zvisinei, iyo Fe matrix micro-regionally inoshandura chimiro chayo chemakemikari pane zvinomwe zvakasarudzwa zvakasarudzwa zveSDSS inotonhora, sezvinoratidzwa mumufananidzo 2f.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 wea-Fe2O3 masisitimu uye Fe2+ octahedral oxides akateedzerwa neakawanda crystal field macalculation 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 dzakasiyana dzemunharaunda45,46, Fe3O4 ine musanganiswa weFe2+ uye Fe3+,47 uye FeO45 inoshanda seyakarongeka divalent Fe2+ oxide (3d6).Ese Fe3+ ions mu α-Fe2O3 ane chete Oh zvinzvimbo, ukuwo γ-Fe2O3 kazhinji inomiririrwa neFe3+ 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 mune imwe pepa yapfuura, 45 kunyange zvazvo chiyero chekusimba chezviviri zvakasiyana, chiyero chavo chekusimba eg / t2g chiri ≈1, asi munyaya iyi kucherechedzwa kwehuwandu hwehuwandu eg / t2g inenge 1. Izvi hazvibatanidzi mukana wekuti mumamiriro ezvinhu epanguva ino chete Fe3 + iripo.Tichifunga nezvenyaya yeFe3O4 nezvose zviri zviviri Fe2+ uye Fe3+, chinhu chekutanga chinozivikanwa kuva chine simba (chakasimba) L3 mupendero weFe chinoratidza chidiki (chikuru) chisina kubatwa t2g.Izvi zvinoshanda kuFe2 + (Fe3 +), iyo inoratidza kuti chinhu chekutanga chekuwedzera chinoratidza kuwedzera kwezvinyorwa zveFe2 + 47.Mhedzisiro iyi inoratidza kuti kugarisana kweFe2+ uye γ-Fe2O3, α-Fe2O3 uye/kana Fe3O4 inotonga pane inotonhora-yakakungurutswa pamusoro pezviumbwa.
Yakawedzerwa photoelectron thermal imaging mifananidzo yeXAS spectra (a, c) uye (b, d) ichiyambuka Fe L2,3 kumucheto munzvimbo dzakasiyana-siyana mukati mematunhu akasarudzwa 2 uye E muFigs.2d.
Iyo yakawanikwa data yekuedza (Fig. 4a uye Supplementary Fig. 11) inorongwa uye inofananidzwa nedheta yemishonga yakachena 40, 41, 48. Mhando mitatu yakasiyana-siyana yekuedza yakacherechedza Fe L-edge XAS spectra (XAS- 1, XAS-2 uye XAS-3: Fig. 4a).Kunyanya, spectrum 2-a (inotaridzirwa se XAS-1) muFig. 3b yakateverwa ne spectrum 2-b (yakanyorwa XAS-2) yakaonekwa pamusoro penzvimbo yose yekuona, nepo spectra yakafanana neE-3 yakaonekwa mumufananidzo 3d (yakanyorwa XAS-3) yakaonekwa pane dzimwe nzvimbo.Semutemo, ma paramita mana akashandiswa kuratidza iripo valence nyika mumuenzaniso uri pasi pechidzidzo: (1) spectral maitiro L3 uye L2, (2) nzvimbo dzesimba dzehunhu L3 uye L2, (3) mutsauko wesimba L3-L2., ( 4) L2/L3 intensity ratio.Maererano nekuona kwekuona (Fig. 4a), zvose zvitatu zveFe components, zvinoti, Fe0, Fe2 +, uye Fe3 +, zviripo pane SDSS pamusoro pekudzidza.Iyo yakaverengerwa intensity ratio L2/L3 yakaratidzawo kuvepo kwezvinhu zvese zvitatu.
Simulated XAS spectra yeFe ine yakacherechedzwa matatu akasiyana ekuyedza data (yakasimba mitsetse XAS-1, XAS-2 uye XAS-3 inoenderana ne2-a, 2-b uye E-3 muFig. 2 uye 3) Kuenzanisa, Octahedrons Fe2+, Fe3+ ine crystal munda tsika dze1.0 eV, 1 eV yakayerwa, 1. 2, XAS-3) uye inoenderana yakagadziridzwa data yeLCF (yakasimba nhema mutsara), uye zvakare mune fomu XAS-3 spectra ine Fe3O4 (yakasanganiswa mamiriro eFe) uye Fe2O3 (yakachena Fe3+) zviyero.
Mutsetse musanganiswa wakakodzera (LCF) weatatu zviyero 40, 41, 48 yakashandiswa kuyera iyo iron oxide kuumbwa.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 yakaverengerwa muzviitiko zvese nekuda kwekuti takaona diki diki mune ese data, uye zvakare nekuda kwekuti simbi yesimbi ndiyo inonyanya kukosha yesimbi. 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 на песни), 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.事实上， X-PEEM 对Fe（~6 nm）49的检测深度大于估计的氧化层厚度（略> 4 nm） （Fe0）的信号.事实上 , X-PEEM 对 Fe （~ 6 nm） 49 的 检测 深度 大于 的 氧化层 厚度 略 略> 4 nm） 允方 允斋 4 nm铁基体 （fe0） 的。 信号 信号 信号 忡号Фактически, глубина обнаружения Fe (~ 6 нм) 49 с помощью X-PEEM больше, чем предполагаемая толщина оксидного слоя (немного слоя (немного > 4) нал от железной матрицы (Fe0) ниже пассивирующего слоя. Kutaura zvazviri, kudzika kwekuonekwa kweFe (~ 6 nm) 49 ne X-PEEM yakakura kudarika iyo inotarisirwa ukobvu hwe oxide layer (zvishoma> 4 nm), iyo inobvumira kuonekwa kwechiratidzo kubva kune iron matrix (Fe0) pasi pepasi passivation layer. .Musanganiswa wakasiyana-siyana weFe2+ neFe3+ wakaitwa kuti uwane mhinduro yakanakisa yedata rekuyedza rakacherechedzwa.Pamusoro pemuonde.4b inoratidza XAS-1 spectrum yemusanganiswa weFe2+ neFe3+, uko zviyero zveFe2+ neFe3+ zvakafanana ne45%, zvichiratidza zvakasanganiswa oxidation nyika dzeFe.Nepo yeXAS-2 spectrum, iyo muzana yeFe2+ neFe3+ inova ~ 30% uye 60%, zvichiteerana.Fe2+ ​​ishoma pane Fe3+.Chiyero cheFe2+ kusvika kuFe3, chakaenzana ne1: 2, zvinoreva kuti Fe3O4 inogona kuumbwa pachiyero chakafanana pakati peFe ions.Mukuwedzera, kune XAS-3 spectrum, chikamu cheFe2 + uye Fe3 + chinova ~ 10% uye 80%, iyo inoratidza kutendeuka kwepamusoro kweFe2 + kusvika kuFe3 +.Sezvataurwa pamusoro apa, Fe3+ inogona kubva ku-α-Fe2O3, γ-Fe2O3 kana Fe3O4.Kuti unzwisise kunobva kwanyanya kunobva Fe3+, iyo XAS-3 spectrum yakarongerwa nemhando dzakasiyana dzeFe3+ muFigure 4e, ichiratidza kufanana nezviyero zvese kana uchifunga nezveB peak.Zvisinei, kusimba kwepamusoro pemapfudzi (A: kubva kuFe2 +) uye B / A intensity ratio inoratidza kuti iyo spectrum yeXAS-3 iri pedyo, asi haipindirani nehuwandu hwe γ-Fe2O3.Kuenzaniswa nehuwandu γ-Fe2O3, iyo Fe 2p XAS peak yeA SDSS ine zvishoma zvishoma zvakanyanya (Fig. 4e), iyo inoratidza hukuru hwepamusoro hweFe2 +.Kunyangwe iyo spectrum yeXAS-3 yakafanana neye γ-Fe2O3, uko Fe3+ iripo paOh uye Td zvinzvimbo, kuzivikanwa kweakasiyana valence nyika uye kurongeka chete padivi peL2,3 kumucheto kana L2/L3 intensity ratio inoramba iri nyaya yekuenderera mberi kwekutsvaga.nhaurirano nekuda kwekuoma kwezvinhu zvakasiyana-siyana zvinobata chikamu chekupedzisira41.
Pamusoro pekusiyana kwechimiro chemakemikari ematunhu akasarudzwa anofarirwa anotsanangurwa pamusoro apa, iyo yepasi rose kemikari heterogeneity yezvinhu zvakakosha Cr uye Fe yakaongororwawo nekurongedza ese XAS spectra yakawanikwa pane sampuli yepasi uchishandisa nzira yeK-kureva kusanganisa.Iwo Cr L edge profiles anoumba maviri akagovaniswa epamhepo masumbu mune inopisa-yakashandwa uye inotonhora-yakatenderedzwa mienzaniso inoratidzwa muFigs.5. Zviri pachena kuti hapana shanduko yemaitiro emunharaunda inoonekwa seyakafanana, sezvo maviri masendindi eXAS Cr spectra anofananidzwa.Aya ma spectral maumbirwo emasumbu maviri anenge akafanana neaya anoenderana neCr2O342, zvinoreva kuti iwo Cr2O3 akaturikidzana akaenzana zvakaenzana paSDSS.
Cr L K-inoreva kumucheto kwedunhu masumbu, uye b ndiyo inoenderana XAS centroids.Mhedzisiro yeK-zvinoreva X-PEEM kuenzanisa kweiyo inotonhora-yakakungurutswa SDSS: c Cr L2.3 kumucheto kwedunhu reK-kureva masumbu uye d inoenderana XAS centroids.
Kuenzanisira mamwe mamepu akaoma eFeL edge, mana uye mashanu akakwenenzverwa masumbu uye akabatana centroids (spectral profiles) akashandiswa kune inopisa-yakashandwa 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 \(\rm{Fe} + 2e^ – \ ku \rm { Fe}^{2 + (3 + )}\), 0.440 uye 0.036 V, zvichiteerana.Matunhu ane mukana wakaderera ane huwandu hwepamusoro hweFe3+ komputa.Iyo inogona kugoverwa mumasampuri akaremara ane thermally hunhu ane akaturikidzana shanduko yeanosvika 0.119 V (Fig. 6a, b).Izvi zvinogona kugovera zvakabatana zvakanyanya nepamusoro pepamusoro (Fig. 6a).Hapana imwe nzvimbo-inotsamira shanduko mune yepasi laminar yemukati yakaonekwa (Fig. 6b).Pane zvinopesana, nokuda kwekubatana kwemaokisidhi akasiyana-siyana ane zvinyorwa zvakasiyana zveFe2 + uye Fe3 + muSDSS inotonhora, munhu anogona kuona chimiro chisina kufanana chepseudopotential (Fig. 6c, d).Fe3+ oxides uye/kana (oxy) hydroxides ndizvo zvinoumba ngura musimbi uye zvinopinda muokisijeni nemvura50.Muchiitiko ichi, zvitsuwa zvakapfuma muFe3 + zvinoonekwa sezvakagoverwa munharaunda uye zvinogona kutorwa senzvimbo dzine ngura.Panguva imwecheteyo, gradient mundima inogona kuitika, panzvimbo yehutano hwakakwana hwezvinogona, inogona kushandiswa sechiratidzo chekugadziriswa kwenzvimbo dzinoshanda dzakaora.Uku kugoverwa kusina kuenzana kweFe2+ neFe3+ pamusoro peiyo inotonhora yakakungurutswa SDSS inogona kushandura kemikari yemunharaunda uye inopa inonyanya kushanda inoshanda nzvimbo panguva yeoxide film breakdown uye corrosion reactions, zvichiita kuti pasi pesimbi matrix ienderere mberi nekuora, zvichiita kuti mukati mehterogeneity.zvivakwa uye kuderedza zvidziviriro zvekudzivirira kweiyo passivating layer.
K-inoreva masumbu uye anoenderana XAS centroids muFe L2.3 kumucheto nharaunda yekupisa-yakaremara X-PEEM ac uye df yechando-yakakungurutswa SDSS.a, d K-zvinoreva mapoka emapoka akafukidzwa pamifananidzo yeX-PEEM.Iyo yakaverengerwa pseudoelectrode inogona (Epseudo) inotaurwa pamwe chete neK-zvinoreva cluster plot.Kupenya kwechifananidzo cheX-PEEM, semuvara muFig. 2 yakaenzana ne-X-ray absorption intensity.
Zvine yunifomu Cr asi akasiyana kemikari mamiriro eFe anotungamira kune akasiyana oxide firimu kukuvadzwa uye ngura mapatani mune inopisa-inoshanda uye inotonhora-yakakungurutswa Ce-2507.Ichi chivakwa chechando chakakungurutswa Ce-2507 chakadzidziswa zvakanaka.Nezvekuumbwa kwemaokisi uye hydroxides eFe mumhepo yakadzika mune iri basa rinenge risina kwarakarerekera, maitiro anotevera:
Maitiro ari pamusoro apa anoitika mune zvinotevera zviitiko zvichibva pakuongorora kweX-PEEM.Badzi diki rinoenderana neFe0 rinosanganiswa neiyo pasi pesimbi yesimbi.Kuita kwesimbi Fe nemhoteredzo kunoguma nekuumbwa kweFe(OH)2 layer (equation (5)), iyo inosimudzira Fe2+ chiratidzo muFe L-edge XAS.Kugara kwenguva refu kumhepo kunogona kukonzera kuumbwa kweFe3O4 uye / kana Fe2O3 oxides mushure meFe (OH) 252,53.Mhando mbiri dzakagadzikana dzeFe, Fe3O4 uye Fe2O3, dzinogonawo kuumba muCr3 + hupfumi hwekudzivirira hutanda, iyo Fe3O4 inofarira yunifomu uye inonamira chimiro.Kuvapo kwezvose zviri zviviri zvinoguma mumisanganiswa oxidation nyika (XAS-1 spectrum).Iyo XAS-2 spectrum inonyanya kuenderana neFe3O4.Nepo kutariswa kweXAS-3 spectra munzvimbo dzinoverengeka kwakaratidza kutendeuka kwakazara ku γ-Fe2O3.Sezvo kudzika kwekupinda kweX-rays yakavhurwa inenge 50 nm, chiratidzo chinobva pazasi chinoguma nekukwirira kwepamusoro kweA peak.
Iyo XPA spectrum inoratidza kuti chikamu cheFe mufirimu reoxide chine dhizaini yakasanganiswa neCr oxide layer.Kusiyana nezviratidzo zvepasi nekuda kwekusagadzikana kwenzvimbo yeCr2O3 panguva yekuora, pasinei neyunifomu yeCr2O3 mubasa iri, kushomeka kwekudzivirira kunowanikwa munyaya iyi, kunyanya kune zvienzaniso zvinotonhora.Maitiro akacherechedzwa anogona kunzwisiswa sehterogeneity yekemikari oxidation state munzvimbo yepamusoro (Fe), iyo inokanganisa corrosion performance.Pamusana peiyo stoichiometry imwechete yepamusoro (iron oxide) uye yakadzika pasi (chromium oxide) 52,53 zviri nani kuwirirana (kunamatira) pakati pavo kunotungamirira kunonoka kutakura kwesimbi kana okisijeni ions mu lattice, iyo, iyo, inokonzera kuwedzera kwekudzivirira kwekuora.Naizvozvo, kuenderera kwe stoichiometric reshiyo, kureva imwe oxidation state yeFe, inodiwa pane abrupt stoichiometric shanduko.Iyo inopisa-yakaremara SDSS ine yakawedzera yunifomu yepamusoro, denser inodzivirira layer, uye nani kudzivirira ngura.Nepo kune inotonhora-yakakungurutswa SDSS, kuvapo kweFe3 +-yakapfuma zvitsuwa pasi pechidziviriro chekudzivirira kunokanganisa kutendeseka kwepamusoro uye kunokonzera galvanic corrosion neiyo substrate iri pedyo, iyo inotungamira kudonhedza kwakapinza muRp (Table 1).Iyo EIS spectrum uye yayo corrosion resistance yakaderedzwa.Zvinogona kuonekwa kuti kugoverwa kwepanzvimbo kweFe3 + zvitsuwa zvakapfuma nekuda kwepurasitiki deformation inonyanya kukanganisa kushorwa kwekuora, iyo inobudirira mubasa iri.Nekudaro, chidzidzo ichi chinopa spectroscopic microscopic mifananidzo yekudzikisira mukuora kwekupokana kweSDSS samples dzakadzidzwa nepurasitiki deformation nzira.
Pamusoro pezvo, kunyangwe isingawanzo kusanganiswa kwepasi mumasimbi maviri echikamu chinoratidza kushanda kuri nani, kupindirana kwechinhu ichi chekuwedzera nesimbi yemunhu matrix maererano nemaitiro ekuora zvinoenderana nespectroscopic microscopy kunoramba kusinganzwisisike.Kuonekwa kwezviratidzo zveCe (kuburikidza neXAS M-edges) inongoonekwa munzvimbo shoma panguva yekutonhora, asi inonyangarika panguva yekupisa kweSDSS, ichiratidza kunaya kwenzvimbo yeCe mune simbi matrix, pane homogeneous alloying.Kunyange zvazvo zvisinganyanyi kuvandudza michina ye SDSS6,7, kuvapo kwezvinhu zvisingawanzoitiki pasi pano kunoderedza ukuru hwezvibatanidzwa uye zvinofungidzirwa kuti zvinodzivisa pitting munharaunda yekutanga54.
Mukupedzisa, basa iri rinoburitsa mhedzisiro yepasi pehterogeneity pakuora kwe2507 SDSS yakagadziridzwa necerium nekuenzanisa kemikari yemukati me nanoscale components.Isu tinopindura mubvunzo wekuti sei simbi isina tsvina ichiora kunyangwe pasi pechidziviriro oxide layer nekuenzanisa microstructure yayo, pamusoro chemistry, uye masaini kugadzirisa uchishandisa K-zvinoreva clustering.Zvakatarwa kuti zvitsuwa zvakapfuma muFe3+, kusanganisira kurongeka kwadzo octahedral uye tetrahedral pamwe chete nechinhu chose chemusanganiswa Fe2+/Fe3+, ndizvo zvinokonzeresa kukuvara nekuora kweiyo inotonhora-yakakungurutswa oxide firimu SDSS.Nanoislands inodzorwa neFe3 + inotungamira kune yakashata corrosion kuramba kunyangwe pamberi peiyo yakakwana stoichiometric Cr2O3 passivating layer.Pamusoro pekufambira mberi kwemethodical mukuona mhedzisiro yenanoscale kemikari heterogeneity pane corrosion, basa rinoenderera mberi rinotarisirwa kukurudzira maitiro einjiniya kuvandudza kushora kwesimbi yesimbi panguva yekugadzira simbi.
Kugadzirira Ce-2507 SDSS ingot inoshandiswa muchidzidzo ichi, musanganiswa wakagadzirwa unosanganisira Fe-Ce master alloy yakavharwa nechubhu yesimbi yakachena yakanyungudutswa muchoto che 150 kg yepakati frequency induction kuti ibudise simbi yakanyungudutswa ndokudururwa muforoma.Maumbirwo emakemikari akayerwa (wt%) akanyorwa muSupplementary Table 2. Ingots dzinotanga dzichipisa dzakaumbwa kuita mabhuroko.Zvadaro yakanyungudutswa pa 1050 ° C kwemaminetsi makumi matanhatu kuti iwane simbi mumamiriro ekugadzirisa kwakasimba, 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.
Cylindrical samples (φ10 mm × 15 mm) yekutsikirira inopisa yakagadziriswa kuitira kuti axis ye cylinder ienderane kune deformation direction ye block.Kutsikirira kwepamusoro-soro kwakaitwa pamhando dzakasiyana-siyana dzekushisa mukati me 1000-1150 ° C uchishandisa Gleeble-3800 thermal simulator panguva yenguva dzose yekushungurudza muhuwandu hwe 0.01-10 s-1.Pamberi pekushandurwa, masampuli akapiswa pamwero we10 ° C s-1 kwemaminetsi maviri patembiricha yakasarudzwa kuti abvise tembiricha.Mushure mekuwana kufanana kwekushisa, sampuli yakakanganiswa kusvika kune yechokwadi strain value ye 0.7.Mushure me deformation, samples dzakabva dzadzimwa nemvura kuchengetedza chimiro chakaremara.Iyo yakaomeswa specimen inozochekwa ichienderana neiyo compression nzira.Pachidzidzo ichi, takasarudza muenzaniso une mamiriro ekupisa anopisa e1050 ° C, 10 s-1 nekuti iyo yakaonekwa microhardness yaive yakakwira kupfuura mimwe mienzaniso7.
Massive (80 × 10 × 17 mm3) samples dzeCe-2507 yakasimba mhinduro yakashandiswa mu LG-300-phase three-phase asynchronous two-roll mill ine yakanakisa mechanical properties pakati pemamwe ese deformation level6.The strain rate uye ukobvu kuderedza nzira imwe neimwe i 0.2 m·s-1 uye 5%, zvichiteerana.
An Autolab PGSTAT128N electrochemical workstation yakashandiswa SDSS electrochemical measurements mushure mekutonhora kukunguruka kusvika pa90% kudzikiswa kwehukobvu (1.0 yakaenzana true strain) uye mushure mekudzvanya pa1050°C kwe10 s-1 kune yechokwadi strain ye0.7.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.Iwo masampuli akabva agadziriswa ne epoxy, achisiya nzvimbo yakavhurika ye1 cm2 seye electrode inoshanda (pazasi peiyo cylindrical sample).Chenjerera panguva yekurapa epoxy uye kunotevera jecha nekupukuta kuti usatsemuka.Nzvimbo dzekushanda dzaive dzakavhuvhuta uye dzakakwenenzverwa nedhaimondi yekupuruzira kumisa nehukuru hwe1 μm, yakashambidzwa 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 kupH = 1.0 ± 0.01 neHCl maererano neASTM mazano, unoshandiswa kukurumidza kuora kwesimbi isina tsvina55 nekuti inoparadza pamberi peioni yechloride ine oxidizing yakasimba uye yakaderera pH8 Environmental standards G2.Nyura sample muyedzo mhinduro kweawa imwe kuti usvike padyo nenzvimbo yakadzikama usati waita chero zviyero.Kune solid-solution, inopisa-yakaumbwa, uye inotonhora-yakakungurutswa samples, kuyerwa kwe impedance kwakaitwa payakavhurika yedunhu mikana (OPC) ye0.39, 0.33, uye 0.25 V, zvichiteerana, mu frequency renji kubva 1 105 kusvika 0.1 Hz ine amplitude ye5 mV.Yese makemikari bvunzo akadzokororwa kanenge 3 nguva pasi pemamiriro akafanana kuti ave nechokwadi chekuberekazve data.
Kune HE-SXRD zviyero, rectangular duplex simbi mabhuroko anoyera 1 × 1 × 1.5 mm3 akayerwa kuyera danda rechikamu cheBrockhouse high-energy wiggler paCLS, Canada56.Kuunganidzwa kwedata kwakaitwa muDebye-Scherrer geometry kana kutapurirana geometry pane tembiricha yekamuri.Iyo X-ray wavelength yakaenzaniswa neLaB6 calibrator i0.212561 Å, inofambirana ne58 keV, iyo yakakwirira kudarika yeCu Kα (8 keV) inowanzoshandiswa serabhoritari X-ray source.Sample yaive iri 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.Yese data yakaunganidzwa pachishandiswa Perkin Elmer area detector, flat panel X-ray detector, 200 µm pixels, 40×40 cm2 uchishandisa nguva yekuratidzwa ye0.3 s uye 120 mafuremu.
X-PEEM zviyero zviviri zvakasarudzwa masisitimu akaitwa paBeamline MAXPEEM PEEM end station 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 remutsetse wedanda rakawanikwa nekuyera ion goho spectrum munharaunda yekunakidzwa kubva kuN 1 s kusvika 1 \ (\pi _g ^ \st\) pedyo nehv = 401 eV muN2 nekutsamira kweiyo photon simba paE3 / 2, 57. Approximation spectral inotaridzirwa . Naizvozvo, iyo beamline simba rekugadzirisa yaifungidzirwa 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, L2, Cr3pdge2, Cr3pdge2 edge2, L2 edge2 edge2 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-line mm−1 grating yeFe 2p, L3 edge2, L2.3 edge2, L2. 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 нохроматора SX-700 с решеткой Si 1200 штрихов/мм для Fe кромка 2p L2,3, кромка Cr 2p L2,3, кромка Ni 2p L2,3 uye кромка Ce M4,5. Nokudaro, kugadziriswa kwesimba kwechani yedanda 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, 3, Cep 2 edge, 3, CEP Cr2 edge uye CEP edge. 4.5.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,通过使用带有1 Si 120mm -700 单色器用于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 , 使用带有 带有 12 mm . SX-700 单色器 于 于 用 用 用Fe 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 ine 1200 mutsara Si grating.3, Cr edge 2p L2.3, Ni edge 2p L2.3 uye Ce edge M4.5.Skena photon simba mumatanho 0.2 eV.Pasimba rega rega, mifananidzo yePEEM yakanyorwa pachishandiswa TVIPS F-216 fiber-coupled CMOS detector ine 2 x 2 mabhini, inopa sarudzo ye1024 × 1024 pixels mune 20 µm ndima yekuona.Nguva yekuratidzwa kwemifananidzo yaive 0.2s, avhareji 16 mafuremu.Iyo photoelectron image simba inosarudzwa nenzira yekupa iyo yepamusoro yechipiri electron chiratidzo.Zviyero zvese zvakaitwa panguva yakajairika pachishandiswa linearly polarized photon beam.Ruzivo rwakawanda pamusoro pezviyero runogona kuwanikwa muchidzidzo chakapfuura.Mushure mekudzidza iyo yakazara maerekitironi goho (TEY) yekuona maitiro uye mashandisirwo ayo muX-PEEM49, kudzika kwekuedza kweiyi nzira kunofungidzirwa kuva 4-5 nm yechiratidzo cheCr uye ingangoita 6 nm yeFe.Iyo Cr kudzika iri padyo zvakanyanya neukobvu hweiyo oxide firimu (~ 4 nm) 60,61 nepo Fe kudzika kwakakura kupfuura ukobvu.XRD yakaunganidzwa kumucheto kweFe L musanganiswa weXRD yesimbi okisidi uye Fe0 kubva kumatrix.Muchiitiko chekutanga, kusimba kwemaerekitironi anoburitswa kunobva kune ese angangoita marudzi emaerekitironi anobatsira kuTEY.Nekudaro, chiratidzo chesimbi chakachena chinoda yakakwirira kinetic simba kuti maerekitironi apfuure nepakati peiyo oxide layer kusvika pamusoro uye inounganidzwa neanalyzer.Muchiitiko ichi, chiratidzo cheFe0 chinonyanya kukonzerwa neLVV Auger electrons, pamwe chete nemagetsi echipiri anobudiswa navo.Pamusoro pezvo, kusimba kweTEY kunopihwa neaya maerekitironi kuora panguva yekutiza kweelectron, zvichiwedzera kudzikisira mhinduro yeFe0 mumepu yesimbi XAS.
Kubatanidza migodhi yedata mu data cube (X-PEEM data) inhanho yakakosha mukutora ruzivo rwakakodzera (makemikari kana emuviri zvivakwa) mune yakawanda-dimensional nzira.K-kureva kubatanidza kunoshandiswa zvakanyanya mundima dzinoverengeka, kusanganisira kuona muchina, kugadzirisa mifananidzo, kusatariswa kucherechedzwa kwemaitiro, hungwaru hwekugadzira, uye ongororo yemhando.Semuenzaniso, K-kureva kusanganisa kwaita zvakanaka mukubatanidza hyperspectral data data.Mumusimboti, kune akawanda-maficha data, iyo K-inoreva algorithm inogona nyore kuvaunganidza zvichienderana neruzivo nezve hunhu hwavo (photon simba zvivakwa).K-zvinoreva clustering is an iterative algorithm yekukamura data muK asiri-apiringanisa mapoka (masumbu), apo pixel yega yega inova yeboka chairo zvichienderana nekugoverwa kwenzvimbo kwekemikari inhomogeneity musimbi microstructural kuumbwa.Iyo K-zvinoreva algorithm inosanganisira nhanho mbiri: muchikamu chekutanga, K centroids inoverengwa, uye muchikamu chechipiri, imwe neimwe poindi inopihwa sumbu rine vavakidzani centroids.Pakati pesimba regiravhiti resumbu rinotsanangurwa searithmetic zvinoreva nzvimbo dzedata (XAS spectrum) yesumbu iroro.Kune madaro akasiyana ekutsanangura centroids akavakidzana seEuclidean chinhambwe.Pamufananidzo wekuisa we px,y (apo x na y arikugadziriswa mumapikisi), CK ndiyo nzvimbo yepakati pesimba regiravhiti resumbu;mufananidzo uyu unogona kuzopatsanurwa (kubatanidzwa) kuita K masumbu uchishandisa K-zvinoreva63.Matanho ekupedzisira eK-kureva kusanganisa algorithm ndeaya:
Danho 2. Verengai nhengo 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 yemhando yekuunganidza yemhando yakanyatsoenderana nesarudzo yakanakisa yekutanga centroids.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 λ axis inoenderana nephoton.simba spectral mufananidzo.Iyo K-zvinoreva algorithm inoshandiswa kuongorora matunhu anofarira muX-PEEM data nekuparadzanisa mapixels (masumbu kana madiki-mabhuru) zvinoenderana neawo maficha uye kutora akanakisa centroids (XAS spectral profiles) kune yega yega analyte.sumbu).Inoshandiswa kudzidza kugovera kwenzvimbo, shanduko yenzvimbo yekutarisa, maitiro e oxidation, uye makemikari nyika.Semuenzaniso, iyo K-zvinoreva clustering algorithm yakashandiswa kuFe L-kumucheto uye Cr L-kumucheto munzvimbo dzinopisa-inoshanda uye inotonhora-yakakungurutswa X-PEEM.Huwandu hwakasiyana-siyana hwemasumbu eK (nzvimbo dze microstructure) dzakaedzwa kuti dziwane akakwana masumbu uye centroids.Kana nhamba idzi dzichiratidzwa, mapixels anopihwa kune anoenderana 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 mhedzisiro yechidzidzo ichi inowanika pakukumbira zvine musoro kubva kumunyori weWC.
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.Britannia.Chikamu chechikamu.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. 双相不锈钢在选定的有机酸和有机酸/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在特定的organic酸和organic酸/chlorinated environment的耐过性性.Adams, FW, Olubambi, PA, Potgieter, J. Kh.uye Van Der Merwe, J. Corrosion resistance ye duplex stainless steels munzvimbo dzakasarudzwa dze organic acids uye organic acids/chlorides.kuchengetedza.Zvishandiso Nzira 57, 107-117 (2010).
Barrera, S. et al.Corrosion-oxidative maitiro eFe-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.Webinar E3S 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. 双相不锈钢2507 级热变形行為的研究. Kingklang, S. & Uthaisangsuk, V. 2507 级热变形行為的研究.Kingklang, S. uye Utaisansuk, V. Kuongorora kweHot Deformation Behavior yeType 2507 Duplex Stainless Steel.Metal.alma mater.Trance.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.Britannia.A 766, 138352 (2019).
Zhou, T. et al.Zvimiro uye zvemuchina zvivakwa zvinokonzereswa nekupisa kwekupisa kwecerium-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.koros.sainzi.164, 108359 (2020).
Li, Y., Yang, G., Jiang, Z., Chen, C. & Zuva, S. Migumisiro yeCe pane microstructure uye zvivakwa zve27Cr-3.8Mo-2Ni super-ferritic stainless steels. Li, Y., Yang, G., Jiang, Z., Chen, C. & Zuva, S. Migumisiro yeCe pane microstructure uye zvivakwa zve27Cr-3.8Mo-2Ni super-ferritic stainless steels.Li Y., Yang G., Jiang Z., Chen K. uye Zuva S. Kufurira kweSe pane microstructure uye zvivakwa zve superferritic Stainless steels 27Cr-3,8Mo-2Ni. Li, Y., Yang, G., Jiang, Z., Chen, C. & Sun, S. Ce 对27Cr-3.8Mo-2Ni 超铁素体不锈钢的显微组织和性能的影响. Li, Y., Yang, G., Jiang, Z., Chen, C. & Zuva, S. Mhedzisiro yeCe pane microstructure uye zvivakwa zve27Cr-3.8Mo-2Ni super-simbi isina tsvina. Li, Y., Yang, G., Jiang, Z., Chen, C. & Sun, S. Влияние Ce на микроструктуру и свойства суперферритной нержавеющей стали 27Cr-3,8Mo-2Ni. Li, Y., Yang, G., Jiang, Z., Chen, C. & Zuva, S. Mhedzisiro yeCe pane microstructure uye zvivakwa zve superferritic Stainless simbi 27Cr-3,8Mo-2Ni.Chiratidzo chesimbi.Steelmak 47, 67–76 (2020).