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Icyuma gikoreshwa cyane hamwe n’uburyo bwacyo bukozwemo birwanya ingese mu bihe biri hagati bitewe n’urwego rw’ingufu rugizwe na chromium oxyde. Ingese n’ingufu by’icyuma bisanzwe bifitanye isano no kwangirika kw’izi ngingo, ariko gake cyane ku rwego rwa mikorosikopi, bitewe n’inkomoko y’ubuso butari bumwe. Muri iki gikorwa, heterogeneity y’ubuso bwa nanoscale chemical yabonetse hakoreshejwe microscopy ya spectroscopic na chemometric analysis yiganje mu buryo butunguranye ihinduka no kwangirika kw’icyuma gikonje cya cerium modified super duplex stainless steel 2507 (SDSS) mu gihe cy’imyitwarire yacyo yo gushyuha. Nubwo microscopy ya X-ray photoelectron yagaragaje uburyo bumwe bwo gutwikira urwego rw’umwimerere rwa Cr2O3, SDSS ikozwe mu buryo bukonje yagaragaje ingaruka mbi zo kwangirika bitewe n’uko ibirwa bya nanois bikungahaye kuri Fe3+ biri ku urwego rwa oxide rwa Fe/Cr. Ubu bumenyi ku rwego rwa atome butanga ubumenyi bwimbitse ku ngese y’icyuma gikonje kandi byitezwe ko bizafasha kurwanya ingese y’ibyuma bisa nabyo bifite alloy nyinshi.
Kuva aho icyuma gishyushye cyavumbuwe, ubushobozi bwo kurwanya ingese bwa ferrochromium alloys bwatewe na chromium, ikora okiside/oksihidrokiside ikomeye igaragaza imyitwarire yo kudakora mu bidukikije byinshi. Ugereranyije n'ibyuma bisanzwe (austenitic na ferritic) bitagize ingese, ibyuma bishyushye bya super duplex (SDSS) bifite ubushobozi bwo kurwanya ingese neza bifite imiterere myiza ya mekanike1,2,3. Imbaraga nyinshi za mekanike zemerera imiterere yoroheje kandi mito. Mu buryo bunyuranye, SDSS ihendutse ifite ubushobozi bwo kurwanya ingese zo mu mwobo n'imisokoro, bigatuma iramba kandi ikoreshwa mu kugenzura umwanda, ibikoresho bya shimi, n'inganda za peteroli na gaze zo mu mazi4. Ariko, ubushyuhe buke bwo gutunganya ubushyuhe n'imiterere mibi bibangamira ikoreshwa ryayo mu buryo bufatika. Kubwibyo, SDSS yahinduwe kugira ngo inonosore imiterere yavuzwe haruguru. Urugero, guhindura Ce no kongeramo N 6, 7, 8 byashyizwe mu 2507 SDSS (Ce-2507). Ikigereranyo gikwiye cya 0.08 wt.% rare earth element (Ce) bigira ingaruka nziza ku miterere ya DSS, kuko yongera ubushobozi bwo kunoza ibinyampeke no gukomera k'umupaka w'ibinyampeke. Ubudahangarwa bw'ubushyuhe n'ingufu, imbaraga zo gukurura no gutanga umusaruro, hamwe n'ubushobozi bwo gukora mu bushyuhe nabyo byarazamutse9. Azote nyinshi ishobora gusimbura nikeli ihenze, bigatuma SDSS irushaho kuba nziza10.
Vuba aha, SDSS yahinduwe plastike ku bushyuhe butandukanye (ubushyuhe buke, ubukonje n'ubushyuhe) kugira ngo igere ku miterere myiza ya mekanike6,7,8. Ariko, ubushobozi bwiza bwo kurwanya ingese bwa SDSS buterwa no kuba hari agahu gato ka oxide ku buso, gaterwa n'ibintu byinshi, nko kuba hari ibice byinshi bifite imipaka itandukanye y'ingano, imiterere idakenewe n'ingaruka zitandukanye. Imiterere y'imbere y'ibice bitandukanye bya austenitic na ferritic irahinduka 7. Kubwibyo, kwiga imiterere ya microdomain ya bene ayo mafilime ku rwego rw'imiterere ya elegitoroniki ni ingenzi cyane kugira ngo dusobanukirwe ingese ya SDSS kandi bisaba ubuhanga bugoye bwo kugerageza. Kugeza ubu, uburyo bworoshye bwo kwitabwaho n'ubuso nka Auger electron spectroscopy11 na X-ray photoelectron spectroscopy12,13,14,15 ndetse na sisitemu ikomeye ya photoelectron photoelectron X-ray bitandukanya, ariko akenshi ntibishobora gutandukanya, imiterere ya shimi y'ikintu kimwe mu ngingo zitandukanye mu mwanya kuri nanoscale. Ubushakashatsi bwinshi buherutse bwagaragaje ko ogisijeni ya chromium mu gace runaka yahuye n’imyitwarire ya corruption yagaragaye mu byuma 17 bita austenitic stainless, 18 bita martensitic stainless steels, na SDSS 19, 20. Ariko, ubu bushakashatsi bwibanze cyane cyane ku ngaruka za Cr heterogeneity (urugero, Cr3+ oxidation state) ku kurwanya corruption. Ubudasa bw’inyuma mu miterere ya ogisijeni y’ibintu bushobora guterwa n’ibintu bitandukanye bifite ibintu bimwe bigize, nka ogisijeni y’icyuma. Ibi bintu biragwa ingano ntoya itunganywa mu buryo bwa thermomechanically yegeranye cyane, ariko bitandukanye mu miterere n’imiterere ya ogisijeni16,21. Kubwibyo, kugaragaza isenyuka rya oxide films hanyuma hagashyirwamo imyanda bisaba gusobanukirwa ubusumbane bw’ubuso ku rwego rwa microscopic. Nubwo hari ibi bisabwa, isuzuma ry’imibare nk’ubusumbane bw’ubusumbane bw’ubusumbane, cyane cyane icyuma ku gipimo cya nano/atomic, riracyari hasi kandi akamaro kabyo mu kurwanya corruption ntikaramenyekana. Kugeza vuba aha, imiterere y’ibinyabutabire by’ibintu bitandukanye, nka Fe na Ca, byasobanuwe mu buryo bw’ingano ku byuma hakoreshejwe mikorosikopi yoroshye ya X-ray photoelectron (X-PEEM) mu bikoresho by’imirasire ya nanoscale synchrotron. Hamwe n’ubuhanga bwo gupima X-ray absorption spectroscopy (XAS) bukoresha imiti, X-PEEM yemerera gupima XAS ifite ubushobozi bwo kureba ahantu hanini no kureba aho ibintu biherereye, itanga amakuru y’ibinyabutabire ku miterere y’ibintu n’imiterere yabyo hamwe n’imiterere y’ahantu kugeza ku gipimo cya nanometer 23. Uku kureba ahantu hatangiriye hakoreshejwe mikorosikopi byorohereza igerageza rya shimi ryo mu gace kandi bishobora kwerekana impinduka za shimi zitari zarigeze ziboneka mu gice cya Fe.
Ubu bushakashatsi bwongera inyungu za PEEM mu kubona itandukaniro rya shimi kuri nanoscale kandi butanga uburyo bwo gusesengura ubuso bwa atome mu gusobanukirwa imyitwarire ya corruption ya Ce-2507. Bukoresha K-means cluster chemometric data24 kugira ngo bugaragaze imiterere y’ibinyabutabire ku isi (heterogeneity) y’ibintu biyigize, hamwe n’imiterere yabyo ya shimi igaragazwa mu buryo bw’ibarurishamibare. Bitandukanye n’ikibazo gisanzwe cya corruption iterwa no kwangirika kwa firime ya chromium oxide, imikorere mibi y’ubu n’ubudahangarwa bubi bwo kurwanya corruption biterwa n’ibirwa bya nanois bya Fe3+ biri hafi y’urwego rwa oxide rwa Fe/Cr, bishobora kuba biterwa na oxides zo kurinda. Mu mwanya w’ivunika, hakorwa firime itera corruption.
Imyitwarire ya SDSS 2507 yangiritse yabanje gusuzumwa hakoreshejwe ibipimo bya elegitoroniki. Ku ishusho ya 1 yerekana imiyoboro ya Nyquist na Bode ku bipimo byatoranijwe mu bisubizo by'amazi bya aside (pH = 1) bya FeCl3 ku bushyuhe bw'icyumba. Electrolyte yatoranijwe ikora nk'ikintu gikomeye gitera ogisijeni, kigaragaza imiterere ya firime yo kwangirika. Nubwo ibikoresho bitanyuze mu bushyuhe bw'icyumba buhamye, ubu bushakashatsi bwatanze ubumenyi ku bintu bishobora kwangirika n'imikorere ya nyuma ya ruswa. Urusobe rw'amashanyarazi (Ishusho ya 1d) rwakoreshejwe mu guhuza spectra ya electrochemical impedance spectroscopy (EIS), kandi ibisubizo bijyanye n'uburyo bwo kuyishyiramo bigaragara mu mbonerahamwe ya 1. Uduce tw'amazi tutuzuye twagaragaye mu gihe cyo gupima ingero zavuwe n'izishyushye, mu gihe uduce tw'amazi twakonjeshejwe twakonjeshejwe (Ishusho ya 1b). Muri spectra ya EIS, radius y'uruziga ishobora gufatwa nk'ubudahangarwa bwa polarization (Rp)25,26. Ingano ya Rp ya SDSS yavuwe muri Table ya 1 ni hafi 135 kΩ cm-2, ariko kuri SDSS ishyushye ikozwe mu buryo bukonje n'ikozwe mu buryo bukonje dushobora kubona agaciro kari hasi cyane ka 34.7 na 2.1 kΩ cm-2. Uku kugabanuka gukomeye kwa Rp bigaragaza ingaruka mbi zo kwangirika kwa pulasitiki ku kudakora no kudakora neza kw'ingufu, nk'uko bigaragara muri raporo zabanje 27, 28, 29, 30.
Imbonerahamwe ya Nyquist, b, c Bode impedance na phase diagrams, hamwe na circuit mode ingana na d, aho RS ari resistance ya electrolyte, Rp ari resistance ya polarization, na QCPE ni oxide ya phase element ihoraho ikoreshwa mu kwerekana capacitance idakwiye (n). Ibipimo bya EIS byakozwe ku bushobozi bwo kutagira umutwaro.
Ibipimo bya mbere by’umurongo bigaragazwa muri igishushanyo cya Bode kandi plateau y’umuvuduko mwinshi igaragaza electrolyte resistance RS26. Uko umuvuduko ugabanuka, impedance iriyongera kandi inguni y’icyiciro kibi iraboneka, bigaragaza ko capacitance ari yo iganza. Inguni y’icyiciro iriyongera, igumana agaciro kayo ntarengwa mu rugero rwagutse rw’umuvuduko, hanyuma ikagabanuka (Ishusho ya 1c). Ariko, muri ibyo bihe uko ari bitatu, iki gipimo ntarengwa kiracyari munsi ya 90°, bigaragaza imyitwarire idakwiye ya capacitive bitewe no gukwirakwira kwa capacitive. Bityo, QCPE constant phase element (CPE) ikoreshwa mu kwerekana ikwirakwira rya capacitance interfacial rikomoka ku guhindagurika k’ubuso cyangwa kutumvikana, cyane cyane mu bijyanye n’ubunini bwa atome, geometry ya fractal, porosity ya electrode, ubushobozi butari bumwe, n’ikwirakwira ry’umuvuduko ushingiye ku buso. Geometry ya electrode31,32. Impedance ya CPE:
aho j ari umubare wiyumvirwa naho ω ikaba ari umurongo w’inguni. QCPE ni umurongo uhoraho wigenga ujyanye n’agace gafunguye k’amashanyarazi. n ni umubare w’ingufu utagira ingano usobanura ihinduka ry’imyitwarire ikwiye ya capacitor, ni ukuvuga ko iyo n yegereye 1, CPE yegereye ubushobozi bwo gukora, kandi niba n iri hafi ya zeru, ni ukurwanya. Ihinduka rito rya n, hafi ya 1, rigaragaza imyitwarire idakwiriye ya capacitor y’ubuso nyuma yo gupima polarisation. QCPE ya SDSS ikora neza iri hejuru cyane ugereranyije n’ibicuruzwa bisa, bivuze ko ubwiza bw’ubuso budasa neza.
Bijyanye n'imiterere myinshi y'ibyuma bitagira umugese birwanya ingese, Cr nyinshi ya SDSS muri rusange ituma SDSS irwanya ingese cyane bitewe n'uko hari firime ya okiside irinda ikoresheje ikoranabuhanga 17. Iyi firime ikoresha ikoranabuhanga ubusanzwe ikungahaye kuri okiside za Cr3+ na/cyangwa hydroxides, ahanini ikubiyemo Fe2+, okiside za Fe3+ na/cyangwa hydroxides (okiside) 33. Nubwo ubuso bungana, urwego rwa okiside ikoresha ikoranabuhanga ridahindagurika, kandi nta gucikagurika kugaragara ku buso, nk'uko bigaragazwa n'amashusho ya mikorosikopi, 6,7 imyitwarire ya corruption ya SDSS ikoreshwa mu buryo bushyushye n'ubukonje iratandukanye bityo ikaba isaba inyigo yimbitse ku miterere ya microdeformity n'imiterere y'icyuma.
Imiterere y’icyuma kitagira umugese yasuzumwe mu buryo bw’ingano hakoreshejwe imirasire ya X-rays y’imbere n’iy’ingufu nyinshi (Ishusho y’inyongera 1, 2). Isesengura rirambuye riratangwa mu makuru y’inyongera. Nubwo ibi bihuye cyane n’ubwoko bw’igice cy’ingenzi, itandukaniro ryabonetse mu bice by’ingano by’ibice, byanditse mu mbonerahamwe y’inyongera 1. Itandukaniro rishobora guterwa n’igice cy’igice cy’ingano kidasa ku buso n’igice cy’ingano (XRD) bitewe n’ubujyakuzimu butandukanye bwo kubibona hakoreshejwe imirasire ya X hamwe n’ingufu zitandukanye za fotoni z’impanuka. Igipimo kinini cya austenite mu bipimo bikonje, bigenwa na XRD bivuye ku isoko rya laboratwari, bigaragaza ko ihindagurika ry’ikirere rirushaho kuba ryiza hanyuma ikanarwanya ingese neza 35, mu gihe ibisubizo by’ukuri kandi by’imibare bigaragaza imiterere itandukanye mu bipimo by’ibice. Byongeye kandi, kurwanya ingese kw’icyuma biterwa kandi n’urwego rwo kunoza ingese, kugabanuka kw’ingano y’ingano, kwiyongera kwa mikorobe n’ubucucike bw’ihindagurika ry’ibice bibaho mu gihe cyo kuvurwa n’ubushyuhe 36,37,38. Ingero zishyushye zigaragaza imiterere y’ibinyampeke, bigaragaza ko ari ibinyampeke bingana na mikoroni, mu gihe impeta zoroshye zagaragaye mu ngero zikonje (Ishusho y’inyongera ya 3) zigaragaza ko ibinyampeke byarushijeho kumera neza mu kazi kabanje6, ibyo bikaba byagombye gutuma habaho kudakora neza kw’ibinyampeke no kwiyongera k’ubudahangarwa bw’ingufu. Ubucucike bwinshi bwo gutandukana kw’ibinyampeke bukunze kujyana no kudakora neza kw’ibinyampeke, ibyo bikaba bihuye neza n’ibipimo by’amashanyarazi.
Impinduka mu miterere y’ibinyabutabire bya microdomains by’ibintu by’ibanze byigwaga neza hakoreshejwe X-PEEM. Nubwo hari ibintu byinshi bivanze, Cr, Fe, Ni, na Ce39 byatoranyijwe hano kubera ko Cr ari ingenzi mu ikorwa rya filime ya passivation, Fe ni ingenzi mu byuma, kandi Ni yongera passivation kandi ikaringaniza imiterere ya ferrite-austenitic phase hamwe n’intego yo guhindura Ce. Mu guhindura ingufu z’imirasire ya synchrotron, RAS yasizwe hejuru n’ibintu by’ingenzi bya Cr (edge ​​​​L2.3), Fe (edge ​​​​L2.3), Ni (edge ​​​​L2.3) na Ce (edge ​​​​M4.5). Guhindura ubushyuhe no gukonjesha Ce-2507 SDSS. Isesengura ry’amakuru ryakozwe hakoreshejwe uburyo bwo gupima ingufu hamwe n’amakuru yasohotse (urugero: XAS 40, 41 kuri Fe L2, edges 3).
Ku ishusho ya 2, ishusho ya X-PEEM igaragaza amashusho ya X-PEEM y’ibishyushye (Ishusho ya 2a) n’ibikonje (Ishusho ya 2d) Ce-2507 SDSS hamwe n’inkombe za XAS zijyanye na Cr na Fe L2,3 ahantu hashyizwe ikimenyetso ukwaho. Inkombe ya L2,3 ya XAS isuzuma imiterere ya 3d idafite abantu nyuma yo gusohora electron ku rwego rwo gutandukanya spin-orbit 2p3/2 (inkombe ya L3) na 2p1/2 (inkombe ya L2). Amakuru yerekeye imiterere ya valence ya Cr yabonetse kuri XAS ku nkombe ya L2,3 mu ishusho ya 2b, e. Igereranya n’abacamanza. 42,43 yagaragaje ko imisozi ine yagaragaye hafi y’inkombe ya L3, yitwa A (578.3 eV), B (579.5 eV), C (580.4 eV) na D (582.2 eV), igaragaza octahedral Cr3+, ijyanye na Cr2O3 ion. Ibipimo by'igerageza bihuye n'ibipimo by'imitekerereze byagaragajwe mu duce twa b na e, byabonetse mu mibare myinshi y'umurima wa kristu ku gice cya Cr L2.3 hakoreshejwe umurima wa kristu wa 2.0 eV44. Ubuso bwombi bwa SDSS ishyushye n'ubukonje buzungurutse butwikiriwe n'urwego rumwe rwa Cr2O3.
Ishusho y'ubushyuhe ya X-PEEM ya SDSS yahinduwe mu bushyuhe ijyanye na b Cr L2.3 impande na c Fe L2.3 impande, d Ishusho y'ubushyuhe ya X-PEEM ya SDSS ikonje izunguruka ijyanye na e Cr L2.3 impande na f Fe L2 .3 impande (f). Imiterere ya XAS ishushanyije ahantu hatandukanye hagaragara ku mashusho y'ubushyuhe (a, d), imirongo y'umuhondo irimo utudomo muri (b) na (e) igaragaza imiterere ya XAS ya Cr3+ ifite agaciro ka kristu ka 2.0 eV. Ku mashusho ya X-PEEM, koresha palette y'ubushyuhe kugira ngo wongere uburyo bwo gusoma ishusho, aho amabara kuva ku bururu kugeza ku mutuku ahwanye n'ubukana bw'imirasire ya X (kuva hasi kugeza hejuru).
Uko ibi bintu by'icyuma bihagaze kose, imiterere ya shimi yo kongeramo ibintu bya Ni na Ce kuri ibyo bice byombi ntiyahindutse. Ishusho y'inyongera. Ishusho ya 5-9 yerekana amashusho ya X-PEEM n'ibipimo bya XAS bihuye na Ni na Ce ku myanya itandukanye ku buso bw'ibipimo byakozwe bishyushye n'ibikonje. Ni XAS igaragaza imiterere ya oxidation ya Ni2+ ku buso bwose bwapimwe bw'ibipimo byakozwe bishyushye n'ibikonje (Ibiganiro by'inyongera). Ni ngombwa kumenya ko, ku ngero zakozwe bishyushye, ikimenyetso cya XAS cya Ce nticyagaragaye, mu gihe ku ngero zakozwe bikonje, imiterere ya Ce3+ yagaragaye. Kubona utudomo twa Ce mu ngero zakozwe bikonje byagaragaje ko Ce igaragara cyane mu buryo bw'imvura.
Muri SDSS yangiritse cyane mu bushyuhe, nta mpinduka mu miterere ya XAS ku nkengero za Fe L2,3 zagaragaye (Ishusho ya 2c). Ariko, matrix ya Fe ihindura imiterere yayo ya shimi ku ngingo zirindwi zatoranijwe mu buryo butunguranye za SDSS ikonje, nk'uko bigaragara ku Ishusho ya 2f. Byongeye kandi, kugira ngo haboneke igitekerezo nyacyo cy'impinduka mu miterere ya Fe ku hantu hatoranijwe ku Ishusho ya 2f, hakozwe inyigo ku buso bw'aho hantu (Ishusho ya 3 n'Ishusho y'inyongera ya 10) aho uturere duto tw'uruziga twatoranijwe. Imiterere ya XAS y'inkombe ya Fe L2,3 ya sisitemu za α-Fe2O3 na okiside za Fe2+ octahedral yashushanyijwe hakoreshejwe imibare myinshi ya kristu hakoreshejwe kristu ya 1.0 (Fe2+) na 1.0 (Fe3+)44. Tubona ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ifite uruvange rwa Fe2+ na Fe3+,47, na FeO45 nk'umusemburo wa Fe2+ uhuza (3d6). Tubona ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ifite uruvange rwa Fe2+ na Fe3+,47, na FeO45 nk'umusemburo wa Fe2+ uhuza (3d6) ku buryo bwemewe.Menya ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ihuza Fe2+ na Fe3+,47 na FeO45 mu buryo bwa okiside ivanze Fe2+ (3d6).Menya ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ifite uruvange rwa Fe2+ na Fe3+,47 na FeO45 ikora nk'umusemburo wa Fe2+ (3d6). Iyoni zose za Fe3+ muri α-Fe2O3 zifite imyanya ya Oh gusa, mu gihe γ-Fe2O3 ihagarariwe na Fe3+ t2g [Fe3+5/3V1/3]eg O4 spinel ifite imyanya idafite umwanya mu myanya isanzwe. Kubwibyo, iyoni za Fe3+ muri γ-Fe2O3 zifite imyanya ya Td na Oh. Nkuko byavuzwe mu nyandiko ibanza,45 nubwo igipimo cy'ubukana bw'ibi byombi gitandukanye, igipimo cy'ubukana bwabyo urugero/t2g ni ≈1, mu gihe muri iki gihe igipimo cy'ubukana cyagaragaye urugero/t2g kingana na 1. Ibi bikuraho ko muri iki gihe ari Fe3+ gusa ihari. Urebye urugero rwa Fe3O4 hamwe na Fe2+ na Fe3+, ikimenyetso cya mbere, kizwiho kugira umupaka wa L3 udafite imbaraga (ukomeye) kuri Fe, kigaragaza umubare muto (munini) w’imiterere ya t2g idafite abantu. Ibi bireba Fe2+ (Fe3+), bigaragaza ko ikimenyetso cya mbere cy’ubwiyongere kigaragaza ukwiyongera kw’ibikubiye muri Fe2+47. Ibi bisubizo bigaragaza ko kubaho kwa Fe2+ na γ-Fe2O3, α-Fe2O3 na/cyangwa Fe3O4 byiganje ku buso bukonje bw’ibivanze.
Amashusho yagutse y’ubushyuhe bwa photoelectron ya spectra ya XAS (a, c) na (b, d) yambukiranya inkombe ya Fe L2,3 mu myanya itandukanye y’ahantu mu turere twatoranijwe 2 na E mu ishusho ya 2d.
Amakuru yabonetse mu igerageza (Ishusho ya 4a n'Ishusho y'inyongera ya 11) ashushanywa kandi akagereranywa n'amakuru y'ibinyabutabire 40, 41, 48. Ubwoko butatu butandukanye bwa spectra ya Fe L-edge XAS yabonetse mu igerageza (XAS-1, XAS-2 na XAS-3: Ishusho ya 4a). By'umwihariko, spectra ya 2-a (yitiriwe XAS-1) mu Ishusho ya 3b ikurikiwe na spectra ya 2-b (yitiriwe XAS-2) yabonetse mu gace kose ko gupima, mu gihe spectra nka E-3 zabonetse mu ishusho ya 3d (yitiriwe XAS-3) zabonetse ahantu runaka. Nk'ubusanzwe, ibipimo bine byakoreshejwe mu kugaragaza imiterere ya valence iriho mu cyitegererezo kirimo kwigwa: (1) imiterere ya spectra L3 na L2, (2) imyanya y'ingufu y'imiterere ya L3 na L2, (3) itandukaniro ry'ingufu L3-L2., (4) igipimo cy'ubukana bwa L2/L3. Dukurikije uko byagaragaye mu buryo bw’amaso (Ishusho ya 4a), ibice bitatu bya Fe, ari byo Fe0, Fe2+, na Fe3+, biri ku buso bwa SDSS burimo kwigwa. Igipimo cy’ubukana cyabazwe L2/L3 cyanagaragaje ko ibice bitatu byose biriho.
Spectra ya XAS ya Fe yiganye hamwe n'amakuru atatu atandukanye yabonetse y'igerageza (imirongo ikomeye XAS-1, XAS-2 na XAS-3 ihuye na 2-a, 2-b na E-3 mu Ishusho ya 2 na 3) Igereranya, Octahedrons Fe2+, Fe3+ hamwe n'agaciro ka kristalo ka 1.0 eV na 1.5 eV, uko bikurikirana, amakuru y'igerageza yapimwe hakoreshejwe bd (XAS-1, XAS-2, XAS-3) hamwe n'amakuru ya LCF ahuye nayo (umurongo w'umukara ukomeye), ndetse no mu buryo bwa spectra ya XAS-3 hamwe na Fe3O4 (imiterere ivanze ya Fe) na Fe2O3 (Fe3+ y'umwimerere).
Uburyo bwo guhuza umurongo (LCF) bw’ibipimo bitatu 40, 41, 48 bwakoreshejwe mu gupima imiterere ya okiside y’icyuma. LCF yashyizwe mu bikorwa kuri spectra eshatu zatoranijwe za Fe L-edge XAS zigaragaza itandukaniro rikomeye, ari zo XAS-1, XAS-2 na XAS-3, nk'uko bigaragara ku Ishusho ya 4b–d. Ku bijyanye n’ibikoresho bya LCF, 10% Fe0 yitabwaho mu bihe byose bitewe n’uko twabonye agace gato mu makuru yose, ndetse no kubera ko icyuma cy’icyuma ari cyo gice cy’ingenzi cy’icyuma. Mu by’ukuri, ubujyakuzimu bw’igeragezwa bwa X-PEEM kuri Fe (~6 nm)49 buruta ubunini bw’urwego rwa oxidation bugereranyijwe (bugera kuri 4 nm gato), butuma hamenyekana ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation. Mu by’ukuri, ubujyakuzimu bw’igeragezwa bwa X-PEEM kuri Fe (~6 nm)49 buruta ubunini bw’urwego rwa oxidation bugereranyijwe (bugera kuri 4 nm gato), butuma hamenyekana ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation. Действительно, Кнаная глубина X-PEEM для Fe (~ 6 нм) 49 больше, чем предполагаемая толщина слоя окисления (немного> 4 нм), что позволяет обнаружить у от железной матрицы (Fe0) Mu by’ukuri, ubujyakuzimu bwa probe X-PEEM kuri Fe (~6 nm)49 buruta ubunini bw’urwego rwa oxidation (burenze gato 4 nm), bituma bishoboka kubona ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation.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 ），允许检测来自钝化层下方的铁基体（ 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） 允许 检测 来自 钝化层 下方 （0 fe0） 的。 信号 信号 信号 信号 信号 信号 信号 信号 信号 信号 信号 信号Фактически, глубина обнаружения Fe (~ 6 нм) 49 с помощью X-PEEM больше, чем предполагаемая толщина оксидного слоя (немного> 4 нм), что позваляет обнаруживать с слоя. Mu by’ukuri, ubujyakuzimu bwo kubona Fe (~6 nm) 49 na X-PEEM buruta ubunini bw’urwego rwa okiside (burenze gato 4 nm), ibyo bikaba bituma hamenyekana ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation. .Hakozwe uburyo butandukanye bwo guhuza Fe2+ na Fe3+ kugira ngo haboneke igisubizo cyiza gishoboka ku makuru yabonetse. Ku ishusho ya 4b hagaragazwa spectrum ya XAS-1 ku guhuza Fe2+ na Fe3+, aho ibipimo bya Fe2+ na Fe3+ byari bisa kuri 45%, bigaragaza imiterere ya oxidation ivanze ya Fe. Mu gihe kuri spectrum ya XAS-2, igipimo cya Fe2+ na Fe3+ kiba ~30% na 60%, uko bikurikirana. Fe2+ ​​ni munsi ya Fe3+. Igipimo cya Fe2+ na Fe3, kingana na 1:2, bivuze ko Fe3O4 ishobora kuboneka ku gipimo kimwe hagati ya iyoni za Fe. Byongeye kandi, kuri spectrum ya XAS-3, igipimo cya Fe2+ na Fe3+ kiba ~10% na 80%, bigaragaza ko Fe2+ ihinduka cyane muri Fe3+. Nkuko byavuzwe haruguru, Fe3+ ishobora kuva kuri α-Fe2O3, γ-Fe2O3 cyangwa Fe3O4. Kugira ngo dusobanukirwe aho bishoboka cyane ko haboneka Fe3+, spectrum ya XAS-3 yashushanyijwe hakoreshejwe ibipimo bitandukanye bya Fe3+ ku Ishusho ya 4e, bigaragaza ko ibipimo byombi bisa mu gihe cyo gusuzuma peak ya B. Ariko, ubukana bw'insongero z'urutugu (A: kuva kuri Fe2+) n'igipimo cy'ubukana bwa B/A bigaragaza ko spectrum ya XAS-3 iri hafi, ariko ntihuye n'igipimo cya γ-Fe2O3. Ugereranyije na γ-Fe2O3 nyinshi, peak ya Fe 2p XAS ya A SDSS ifite ubukana buri hejuru gato (Ishusho ya 4e), bigaragaza ubukana buri hejuru bwa Fe2+. Nubwo spectrum ya XAS-3 isa n'iya γ-Fe2O3, aho Fe3+ iboneka mu myanya ya Oh na Td, kumenya imiterere itandukanye ya valence no guhuza gusa ku nkengero za L2,3 cyangwa igipimo cy'ubukana bwa L2/L3 biracyari ikibazo. ni ingingo ikomeje kuganirwaho bitewe n'ubukana bw'ibintu bitandukanye bigira ingaruka ku gipimo cya nyuma41.
Uretse itandukaniro rya spectral mu miterere y’ibinyabutabire mu turere twatoranijwe twavuzwe haruguru, itandukaniro ry’ibinyabutabire ku isi hose ry’ibintu by’ingenzi Cr na Fe ryanasuzumwe hashyirwa mu byiciro spectra zose za XAS zabonetse ku buso bw’icyitegererezo hakoreshejwe uburyo bwa K-means clustering. . Impapuro za Cr L zishyirwaho kugira ngo zikore amatsinda abiri meza akwirakwijwe mu buryo bushyushye n’akonje agaragara ku ishusho ya 5. Biragaragara ko nta mpinduka z’imiterere y’aho hantu zibonwa nk’aho zisa, kubera ko centroid ebyiri za XAS Cr spectra zihwanye. Izi shusho za spectral z’amatsinda abiri zisa hafi n’izijyanye na Cr2O342, bivuze ko urwego rwa Cr2O3 ruri ku murongo ungana kuri SDSS.
Cr L K-means edge region clusters, na b ni XAS centroids bihuye. Ibisubizo by'igereranya rya K-means X-PEEM rya SDSS ikora: c Cr L2.3 edge region ya K-means clusters na d bihuye na XAS centroids.
Kugira ngo hagaragazwe amakarita y’inkombe za FeL agoye cyane, hakoreshejwe amatsinda ane na atanu yakozwe neza hamwe na centroids zijyanye nayo (imiterere ya spectral) ku bipimo byakozwe mu buryo bushyushye n’ibikonje, uko bikurikirana. Kubwibyo, ijanisha (%) rya Fe2+ na Fe3+ rishobora kuboneka hakoreshejwe LCF igaragara ku Ishusho ya 4. Pseudo pseudo potential nk'uko byakozwe na Fe0 yakoreshejwe kugira ngo hagaragazwe ubusumbane bwa microchemical bwa filime ya oxide yo hejuru. Epseudo igereranywa n'itegeko ryo kuvanga,
aho \(\rm{E}_{\rm{Fe}/\rm{Fe}^{2 + (3 + )}}\) bingana \(\rm{Fe} + 2e^ – \ kuri \rm {Fe}^{2 + (3 + )}\), 0.440 na 0.036 V, uko bikurikirana. Uduce dufite ubushobozi buke dufite ingano nini y'ibinyabutabire bya Fe3+. Ingano y'ubushobozi mu ngero zahinduwe mu bushyuhe ifite imiterere y'urwego ifite impinduka ntarengwa ya 0.119 V (Ishusho ya 6a, b). Uku gukwirakwiza ubushobozi bifitanye isano ya hafi n'imiterere y'ubuso (Ishusho ya 6a). Nta zindi mpinduka zishingiye ku mwanya mu gice cy'imbere cy'inyuma cyagaragaye (Ishusho ya 6b). Ibinyuranye n'ibyo, ku isano ya okiside zitandukanye n'ibirimo bitandukanye bya Fe2+ na Fe3+ muri SDSS ikonje, umuntu ashobora kubona imiterere idahuye y'ubushobozi buke (Ishusho ya 6c, d). Okiside ya Fe3+ na/cyangwa hydroxides (okside) ni byo bigize ingese mu cyuma kandi binyura muri ogisijeni n'amazi50. Muri iki gihe, ibirwa bikungahaye kuri Fe3+ bifatwa nk'ibikwirakwiriye mu gace runaka kandi bishobora gufatwa nk'ahantu hangiritse. Muri icyo gihe, imiterere y'ubutaka bushobora kwangirika, aho kuba agaciro ka burundu k'ubushobozi, ishobora gukoreshwa nk'ikimenyetso cy'aho ahantu hashobora kwangirika. Uku gukwirakwira gutandukanye kwa Fe2+ na Fe3+ ku buso bwa SDSS ikonje bishobora guhindura imiterere y'aho hantu no gutanga ubuso bukora neza mu kwangirika kwa oxide film no kwangirika, bityo bigatuma habaho kwangirika guhoraho kwa matrix y'icyuma kiri munsi, bigatera kwangirika imbere. Ubudasa bw'imiterere no kugabanuka kw'imiterere y'uburinzi bw'urwego rudakora.
Amatsinda ya K-means na centroids za XAS zijyanye nazo mu gace ka Fe L2.3 k'inkombe ya X-PEEM ac na df ya SDSS ikonje. a, d Amatsinda ya K-means ashyizwe ku mashusho ya X-PEEM. Ingano ya pseudoelectrode potential yabazwe (Epseudo) ivugwa hamwe n'amatsinda ya K-means. Umucyo w'ishusho ya X-PEEM, nk'ibara riri ku Ishusho ya 2 ujyanye n'ubukana bwa X-ray.
Kuba Cr ingana ariko imiterere itandukanye ya Fe itera kwangirika kwa firime ya okiside itandukanye no kwangirika mu miterere itandukanye ya Ce-2507 ishyushye n'ifite firime ikonje. Iyi miterere ya Ce-2507 ikozwe mu buryo bukonje yasuzumwe neza. Ku bijyanye no kurema okiside na hydroxide za Fe mu kirere kiri hafi kuba mu buryo butari bwo, ingaruka ni izi zikurikira:
Ibi byavuzwe haruguru bibaho mu bihe bikurikira bishingiye ku isesengura rya X-PEEM. Urutugu ruto rujyanye na Fe0 rufitanye isano n'icyuma kiri munsi yacyo. Uburyo Fe y'icyuma ikorana n'ibidukikije butuma habaho urwego rwa Fe (OH)2 (ikigereranyo (5)), byongerera ikimenyetso cya Fe2+ muri Fe L-edge XAS. Kwishyira mu kirere igihe kirekire bishobora gutuma habaho Fe3O4 na/cyangwa Fe2O3 oxydes nyuma ya Fe(OH)252,53. Ubwoko bubiri buhamye bwa Fe, Fe3O4 na Fe2O3, bushobora no kubaho mu urwego rurinda Cr3+ rwinshi, aho Fe3O4 ikunda imiterere imwe kandi ifatana. Kubaho kwabyo byombi bivamo imiterere ivanze ya oxidation (XAS-1 spectrum). XAS-2 spectrum ahanini ihuye na Fe3O4. Mu gihe kwitegereza XAS-3 spectra ahantu henshi byagaragaje ko yahindutse burundu muri γ-Fe2O3. Kubera ko ubujyakuzimu bw'imirasire ya X-rays ifunguye ari nka nanometero 50, ikimenyetso gituruka ku gice cyo hasi gitanga ubukana bwinshi bw'agasongero ka A.
Uburyo bwa XPA bugaragaza ko igice cya Fe muri filime ya oxide gifite imiterere y’icyiciro kimwe hamwe n’urwego rwa oxide rwa Cr. Bitandukanye n’ibimenyetso byo kudakora neza bitewe n’uko Cr2O3 itameze neza mu gihe cyo kwangirika, nubwo urwego rumwe rwa Cr2O3 muri iki gikorwa, ubudahangarwa buke bwa corrosion bugaragara muri iki kibazo, cyane cyane ku bipimo bikonje. Imyitwarire yagaragaye ishobora kumvikana nk’ubusumbane bw’imiterere ya chemical oxidation mu rwego rwo hejuru (Fe), bigira ingaruka ku mikorere ya corrosion. Bitewe na stoichiometry imwe y’urwego rwo hejuru (iron oxide) n’urwego rwo hasi (chromium oxide)52,53 imikoranire myiza (gufatana) hagati yabyo ituma ibyuma cyangwa ogisijeni bitwara buhoro mu buryo bworoshye mu nzira, ibyo bigatuma ubudahangarwa buke bwiyongera. Kubwibyo, ikigereranyo cya stoichiometric gihoraho, ni ukuvuga imiterere imwe ya oxidation ya Fe, ni byiza kuruta impinduka zitunguranye za stoichiometric. SDSS yahinduwe n’ubushyuhe ifite ubuso bumwe, urwego rurinda cyane, kandi irwanya corrosion neza. Mu gihe kuri SDSS ikonje, kuba hari ibirwa bikungahaye kuri Fe3+ munsi y’urwego rurinda bibangamira ubusugire bw’ubuso kandi bigatera ingese ya galvanic hamwe n’ubutaka buri hafi, bigatuma Rp igabanuka cyane (Imbonerahamwe ya 1). Ingano ya EIS n’ubudahangarwa bwayo bwo kwangirika biragabanuka. Bigaragara ko ikwirakwira ry’ibirwa bikungahaye kuri Fe3+ mu gace bitewe no kwangirika kwa pulasitiki bigira ingaruka cyane ku kurwanya ingese, ari na yo ntambwe ikomeye muri iki gikorwa. Bityo, ubu bushakashatsi bugaragaza amashusho ya mikorosikopi yerekana kugabanuka k’ubudahangarwa bwo kwangirika kw’ibipimo bya SDSS byizwe hakoreshejwe uburyo bwo kwangirika kwa pulasitiki.
Byongeye kandi, nubwo guhuza ibintu by’ubutaka budasanzwe mu byuma bifite ibice bibiri bigaragaza imikorere myiza, uburyo iki kintu cyongera imbaraga gikorana na matrix y’icyuma ku giti cyacyo mu bijyanye n’imyitwarire yo kwangirika hakurikijwe amakuru ya microscopy ya spectroscopic ntabwo ari ingenzi. Kugaragara kw’ibimenyetso bya Ce (binyuze kuri XAS M-edges) bigaragara ahantu hake gusa mu gihe cyo gukonja, ariko bishira mu gihe cyo guhinduka gushyuha kwa SDSS, bigaragaza imvura ya Ce mu gace k’icyuma, aho kuba alloying ihuye. Nubwo bidateza imbere cyane imiterere ya SDSS6,7, kuba hari ibintu by’ubutaka budasanzwe bigabanya ingano y’ibirimo kandi bikekwa ko bibuza ko ibintu bigwa mu gace k’ibanze54.
Mu gusoza, iki gikorwa kigaragaza ingaruka z'ubusumbane bw'ubuso ku kwangirika kwa 2507 SDSS yahinduwe na cerium binyuze mu gupima ingano y'ibinyabutabire mu bice bya nanoscale. Turasubiza ikibazo cy'impamvu icyuma kitagira umugese cyangirika ndetse no munsi y'urwego rwa oxide rurinda binyuze mu gupima imiterere yacyo, shimi y'ubuso, no gutunganya ibimenyetso hakoreshejwe uburyo bwa K-means clustering. Byaragaragaye ko ibirwa bikungahaye kuri Fe3+, harimo n'imikoranire yabyo ya octahedral na tetrahedral ku buryo bwose bwa Fe2+/Fe3+, ari byo bitera kwangirika no kwangirika kwa oxide film SDSS ikonje. Ibirwa bya nanois byiganjemo Fe3+ bituma habaho ubudahangarwa bubi bwo kwangirika ndetse no mu gihe hari urwego ruhagije rwa stoichiometric Cr2O3 passivating. Uretse iterambere ry'uburyo bwo kumenya ingaruka z'ubusumbane bw'ibinyabutabire bya nanoscale ku kwangirika, imirimo ikomeje yitezweho gutera imbaraga inzira z'ubuhanga mu kunoza ubudahangarwa bw'ibyuma bitagira umugese mu gihe cyo gukora ibyuma.
Mu gutegura ingot ya Ce-2507 SDSS yakoreshejwe muri ubu bushakashatsi, imvange irimo Fe-Ce master alloy ifunze umuyoboro w'icyuma cyuzuye yashongeshejwe mu itanura rya kilogarama 150 kugira ngo hakorwe icyuma gishongeshejwe hanyuma gisukwa mu ibumba. Ibigize imiti byapimwe (wt%) bigaragazwa mu mbonerahamwe y'inyongera ya 2. Ingot zibanza gushyuha zigakorwamo ibice. Hanyuma zigashyirwa ku bushyuhe bwa 1050°C mu gihe cy'iminota 60 kugira ngo icyuma kibe mu buryo bukomeye, hanyuma zigashyirwa mu mazi kugeza ku bushyuhe bw'icyumba. Ingero zakoreweho ubushakashatsi zasuzumwe birambuye hakoreshejwe TEM na DOE kugira ngo zige ibyiciro, ingano y'ingano n'imiterere. Amakuru arambuye ku ngero n'uburyo bwo kuzikora aboneka mu zindi nkomoko6,7.
Ingero za cylindrical (φ10 mm × 15 mm) zo gukandagira ubushyuhe zatunganyijwe ku buryo umurongo wa silindiri uhuye n'icyerekezo cyo gukandagira kw'ibyuma. Gukandagira ubushyuhe bwinshi byakozwe ku bushyuhe butandukanye buri hagati ya 1000-1150 °C hakoreshejwe simulator y'ubushyuhe ya Gleeble-3800 ku gipimo gihoraho cyo gukandagira kiri hagati ya 0.01-10 s-1. Mbere yo gukandagira, ingero zashyushywaga ku gipimo cya 10 °C s-1 mu gihe cy'iminota 2 ku bushyuhe bwatoranijwe kugira ngo hakurweho ubushyuhe. Nyuma yo kugera ku bushyuhe bumwe, ingero yahinduwe ku gipimo nyacyo cya 0.7. Nyuma yo gukandagira, ingero zahitaga zizimwa n'amazi kugira ngo imiterere yangiritse igumeho. Ingero ikomeye icibwa ijyanye n'icyerekezo cyo gukandagira. Muri ubu bushakashatsi bwihariye, twahisemo ingero ifite ubushyuhe bwa 1050 °C, 10 s-1 kuko ubukomere bwagaragaye bwari buri hejuru kurusha izindi ngero7.
Ingero nini (80 × 10 × 17 mm3) z'umuti ukomeye wa Ce-2507 zakoreshejwe mu ruganda rwa LG-300 rufite ibice bitatu rudahuza rufite imiterere myiza ya mekanike mu zindi nzego zose zo guhindura imiterere.6. Igipimo cyo gukurura no kugabanya ubunini kuri buri nzira ni 0.2 m·s-1 na 5%, uko bikurikirana.
Imashini ikoresha amashanyarazi ya Autolab PGSTAT128N yakoreshejwe mu gupima amashanyarazi ya SDSS nyuma yo kugabanya ubunini bwa 90% (ubunini bungana na 1.0) no nyuma yo gushyushya kuri 1050°C kuri 10 s-1 kugeza ku bunini bungana na 0.7. Iyi mashini ifite akazu ka electrode eshatu gafite electrode yuzuye ya calomel nk'imashini ikoreshwa, electrode ikoreshwa na grafiti, n'icyitegererezo cya SDSS nk'imashini ikoreshwa. Ingero zaciwemo silindari zifite umurambararo wa mm 11.3, ku mpande zayo insinga z'umuringa zashongeshejwe. Ingero zafashwe na epoxy, hasigara ahantu hafunguye ho gukora electrode ikora (uruhande rwo hasi rw'icyitegererezo cy'uruziga). Witondere mu gihe cyo gusya epoxy no kuyisiga no kuyisukura kugira ngo hirindwe ko yacikagurika. Ubuso bw'aho bakorera bwaraseswaga kandi bugasukurwa hakoreshejwe icyuma gisukura cya diyama gifite ingano ya 1 μm, bugasukurwa n'amazi ya distilled na ethanol, hanyuma bukamishwa mu mwuka ukonje. Mbere yo gupima amashanyarazi, ingero zasukuwe zashyirwaga mu mwuka iminsi myinshi kugira ngo zikore filime karemano ya okiside. Umuti w'amazi wa FeCl3 (6.0 wt%), uhamye kuri pH = 1.0 ± 0.01 hamwe na HCl nk'uko ASTM yabisabye, ukoreshwa mu kwihutisha ingese y'icyuma kitagira umugese55 kuko irangirika iyo hari iyoni za chloride zifite ubushobozi bukomeye bwo gukaraba hamwe na pH nkeya Ibipimo by'ibidukikije G48 na A923. Shyira icyitegererezo mu gisubizo cy'igerageza isaha 1 kugira ngo kigere ku rwego ruhamye mbere yo gukora ibipimo ibyo ari byo byose. Ku bipimo by'umuti ukomeye, ushyushye, n'ibikonje, ibipimo bya impedance byakozwe kuri potentials za open circuit (OPC) za 0.39, 0.33, na 0.25 V, uko bikurikirana, mu ntera kuva kuri 1 105 kugeza kuri 0.1 Hz hamwe n'ubunini bwa 5 mV. Ibizamini byose bya chimique byasubiwemo nibura inshuro 3 mu bihe bimwe kugira ngo amakuru ashobore kugaruka.
Ku bipimo bya HE-SXRD, ibyuma bya duplex bifite impande ebyiri bifite uburebure bwa 1 × 1 × 1.5 mm3 byapimwe kugira ngo harebwe imiterere y’urumuri rw’icyuma gikoresha ingufu nyinshi cya Brockhouse muri CLS, muri Kanada56. Gukusanya amakuru byakozwe muri geometry ya Debye-Scherrer cyangwa geometry yo kohereza amakuru ku bushyuhe bw’icyumba. Ubunini bw’urumuri rwa X-ray bwapimwe hakoreshejwe calibrator ya LaB6 ni 0.212561 Å, bungana na 58 keV, iri hejuru cyane y’iya Cu Kα (8 keV) ikunze gukoreshwa nk'isoko ya X-ray yo muri laboratwari. Icyitegererezo cyashyizwe ku ntera ya mm 740 uvuye ku gikoresho cyo gupima. Ingano yo gupima buri gipimo ni 0.2 × 0.3 × 1.5 mm3, bigenwa n'ingano y'urumuri n'ubugari bw'icyitegererezo. Amakuru yose yakusanyijwe hakoreshejwe icyuma gipima ahantu cya Perkin Elmer, icyuma gipima ahantu hagari cya X-ray, pixels 200 µm, 40×40 cm2 hakoreshejwe igihe cyo kureba cya 0.3 s na frame 120.
Ibipimo bya X-PEEM by’uburyo bubiri bwatoranijwe byakorewe kuri sitasiyo ya Beamline MAXPEEM PEEM muri laboratwari ya MAX IV (Lund, Suwede). Ibipimo byateguwe kimwe n’ibipimo bya elegitoroniki. Ibipimo byateguwe byabitswe mu kirere iminsi myinshi bikurwamo imyuka mu cyumba cy’ubushyuhe bwinshi mbere yo kubyazwa imirasire na fotoni za synchrotron. Ingufu z’umurongo w’umuraba zabonetse hapimwa spectrum y’umusaruro wa ion mu gace k’ubushyuhe kuva kuri N 1 s kugeza kuri 1\(\pi _g^ \ast\) hafi ya hv = 401 eV muri N2 hifashishijwe ingufu za fotoni kuri E3/2, 57. Spektara yo hafi yatanze ΔE (ubugari bw’umurongo wa spectra) hafi ya 0.3 eV mu rwego rw’ingufu zapimwe. Kubera iyo mpamvu, igisubizo cy’ingufu za beamline cyagereranyijwe kuba E/∆E = 700 eV/0.3 eV > 2000 na flux ≈1012 ph/s hakoreshejwe monochromator yahinduwe ya SX-700 ifite Si 1200-line mm−1 grating kuri Fe 2p L2,3 edge, Cr 2p L2,3 edge, Ni 2p L2,3 edge, na Ce M4,5 edge. Kubera iyo mpamvu, igisubizo cy'ingufu za beamline cyagereranyijwe kuba E/∆E = 700 eV/0.3 eV > 2000 na flux ≈1012 ph/s hakoreshejwe monochromator yahinduwe ya SX-700 ifite Si 1200-line mm−1 grating kuri Fe 2p L2.3 edge, Cr 2p L2.3 edge, Ni 2p L2.3 edge, na Ce M4.5 edge. Таким кромка Cr 2p L2,3, кромка Ni 2p L2,3 и кромка Ce M4,5. Bityo, ubushobozi bwo kugaragaza ingufu z'umuyoboro w'imirasire bwapimwe nka E/∆E = 700 eV/0.3 eV > 2000 na flux ≈1012 f/s hakoreshejwe monochromator yahinduwe ya SX-700 ifite Si grating y'imirongo 1200 / mm kuri Fe edge 2p L2 ,3, Cr edge 2p L2.3, Ni edge 2p L2.3, na Ce edge M4.5.因此，光束线能量分辨率估计为 E / ΔE = 700 eV / 0.3 eV> 2000 和通量≈1012 ph / s ，通过使用带有 Si 1200 线 mm-1 光栅的改进的 SX-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 为 为 为 δe = 700 EV / 0.3 EV> 2000 和 1210 PH / S ， 使用 带有 带有 1200 线 mm-1 光栅 改进 的 SX-700 单色器Bityo, iyo ukoresheje monochromator ya SX-700 yahinduwe ifite umurongo wa 1200 Si grating. 3, Cr edge 2p L2.3, Ni edge 2p L2.3 na Ce edge M4.5.Gupima ingufu za fotoni mu ntambwe za 0.2 eV. Kuri buri ngufu, amashusho ya PEEM yafashwe hakoreshejwe uburyo bwa TVIPS F-216 CMOS bufatanye na fibre hamwe n'udusanduku 2 x 2, butanga ubushobozi bwa pikseli 1024 x 1024 mu gice cyo kureba cya 20 µm. Igihe cyo kwerekana amashusho cyari 0.2 s, impuzandengo ya frame 16. Ingufu z'ishusho ya fotoelectron zitoranywa mu buryo bwo gutanga ikimenyetso ntarengwa cya electron. Ibipimo byose byakozwe mu buryo busanzwe hakoreshejwe fotoni ifite polarized linearly. Amakuru menshi ku bipimo aboneka mu bushakashatsi bwakozwe mbere. Nyuma yo kwiga uburyo bwo kubona electron yield (TEY) n'ikoreshwa ryayo muri X-PEEM49, ubujyakuzimu bw'igerageza ry'ubu buryo bubarirwa kuri 4-5 nm ku kimenyetso cya Cr na 6 nm kuri Fe. Ubujyakuzimu bwa Cr buri hafi cyane n'ubunini bwa oxide film (~4 nm)60,61 mu gihe ubujyakuzimu bwa Fe buruta ubunini. XRD ikusanyirijwe ku nkengero za Fe L ni uruvange rwa XRD ya okiside z'icyuma na Fe0 bivuye muri matrix. Mu rubanza rwa mbere, ubukana bwa elektroni zisohoka buturuka ku bwoko bwose bushoboka bwa elektroni zigira uruhare muri TEY. Ariko, ikimenyetso cy'icyuma gisanzwe gisaba ingufu nyinshi za kinetike kugira ngo elektroni zinyure mu gice cya okiside zigere hejuru hanyuma zikusanyirizwe n'umuhanga mu gusesengura. Muri iki gihe, ikimenyetso cya Fe0 giterwa ahanini na elektroni za LVV Auger, ndetse na elektroni za kabiri zisohoka nazo. Byongeye kandi, ubukana bwa TEY buterwa n'izi elektroni bubora mu nzira yo gutoroka elektroni, birushaho kugabanya igisubizo cya Fe0 spectral mu ikarita y'icyuma ya XAS.
Gushyira amakuru mu gice cy'amakuru (amakuru ya X-PEEM) ni intambwe y'ingenzi mu gukuramo amakuru ajyanye nayo (imiterere ya chimique cyangwa physique) mu buryo bunyuranye. K-means clustering ikoreshwa cyane mu nzego zitandukanye, harimo kureba imashini, gutunganya amashusho, kumenya imiterere idakurikiranywe, ubwenge bw'ubukorano, no gusesengura ibyiciro. Urugero, K-means clustering yakoze neza mu gukusanya amakuru y'amashusho ya hyperspectral. Muri rusange, ku makuru afite imiterere myinshi, K-means algorithm ishobora kuyashyira mu byiciro byoroshye hashingiwe ku makuru yerekeye imiterere yayo (imiterere y'ingufu za photon). K-means clustering ni algorithm isubiramo yo kugabanya amakuru mu matsinda ya K adahurirana (amatsinda), aho buri pixel iba mu itsinda runaka bitewe n'uburyo chemical inhomogeneity ikwirakwizwa mu miterere y'icyuma. K-means algorithm irimo ibyiciro bibiri: mu cyiciro cya mbere, K centroids zirabarirwa, naho mu cyiciro cya kabiri, buri ngingo ihabwa itsinda rifite centroids zegeranye. Hagati y'uburemere bw'itsinda ritowe nk'ikigereranyo cy'amakuru y'ingingo z'amakuru (XAS spectrum) kuri iryo tsinda. Hari intera zitandukanye zo gusobanura centroids zegeranye nk'intera ya Euclidean. Ku ishusho yinjiyemo ya px, y (aho x na y ari igisubizo muri pikseli), CK ni yo hagati y'uburemere bw'itsinda; iyi shusho ishobora gucibwamo ibice (clustered) mu matsinda ya K hakoreshejwe K-means63. Intambwe za nyuma za algorithme ya K-means clustering ni:
Intambwe ya 2. Kubara ubunyamuryango bwa pikseli zose ukurikije centroid iriho ubu. Urugero, bibarwa uhereye ku ntera ya Euclidean d iri hagati y'aho hagati na buri pikseli:
Intambwe ya 3 Shyira buri pixel kuri centroid iri hafi. Hanyuma ongera ubare imyanya ya centroid ya K ku buryo bukurikira:
Intambwe ya 4. Subiramo inzira (ibigereranyo (7) na (8)) kugeza igihe centroids zihurira. Ibisubizo bya nyuma by'ubwiza bw'amatsinda bifitanye isano rikomeye n'amahitamo meza ya centroids z'ibanze. Ku miterere y'amakuru ya PEEM y'amashusho y'icyuma, ubusanzwe X (x × y × λ) ni agace k'amakuru ya 3D, mu gihe axes za x na y zigaragaza amakuru y'ahantu (resolution ya pixel) naho axis ya λ ihuye n'ishusho ya spectral ya photon. Algorithm ya K-means ikoreshwa mu gushakisha uturere dushishikajwe n'amakuru ya X-PEEM binyuze mu gutandukanya pixels (amatsinda cyangwa sub-blocks) hakurikijwe imiterere ya spectral yazo no gukuramo centroids nziza (XAS spectral profiles) kuri buri cluster. Analyte ikoreshwa mu kwiga ikwirakwizwa ry'ahantu, impinduka za spectral zo mu gace, imyitwarire ya oxidation, n'imiterere ya chemical. Urugero, K-means clustering algorithm yakoreshejwe mu turere twa Fe L-edge na Cr L-edge mu bice bya X-PEEM ishyushye kandi ikonje. Imibare itandukanye ya K clusters (uturere tw’imiterere mito) yageragejwe kugira ngo haboneke clusters na centroids nziza. Iyo iyi mibare igaragajwe, pixels zishyirwa kuri cluster centroids zijyanye nayo. Buri tandukaniro ry'amabara rihuye n'aho hagati muri cluster, bigaragaza imiterere y'ahantu y'ibintu bya shimi cyangwa physical. Clusters zakuwemo ni uruvange rw'umurongo wa spectra nziza.
Amakuru ashyigikira ibyavuye muri ubu bushakashatsi araboneka iyo umwanditsi wa WC abisabye mu buryo bwumvikana.
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