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Simbi isingatsvinyike inoshandiswa zvakanyanya pamwe chete nesimbi dzayo dzakagadzirwa dzinoramba ngura mumamiriro ekunze nekuda kwepasivation layer ine chromium oxide. Kuora nekuora kwesimbi zvinowanzobatanidzwa nekuparadzwa kwezvikamu izvi, asi kashoma nekuonekwa kwekusawirirana kwepamusoro, zvichienderana nehukuru hwe microscopic. Mubasa iri, nanoscale chemical surface heterogeneity, yakaonekwa ne spectroscopic microscopy uye chemometric analysis, isingatarisirwi inotonga kuputsika nekuora kwe cold rolled cerium modified super duplex stainless steel 2507 (SDSS) panguva yekupisa kwayo. Kunyangwe X-ray photoelectron microscopy yakaratidza kufukidza kwakafanana kwe natural Cr2O3 layer, passivation performance ye cold rolled SDSS yaive isina kunaka nekuda kwekupararira kweFe3+ rich nanoislands paFe/Cr oxide layer. Ruzivo urwu rwe atomic scale runopa kunzwisisa kwakadzama kwepasiva simbi uye runotarisirwa kubatsira kurwisa ngura yesimbi dzakafanana dzine alloy.
Kubva pakagadzirwa simbi isina ngura, hunhu hwe ferrochrome hunodzivirira ngura hwave huchinzi hunokonzerwa ne chromium, iyo inoumba ma oxides/oxyhydroxides akasimba uye inoratidza hunhu hwepasi munzvimbo zhinji. Zvichienzaniswa nesimbi dzisina ngura dzechinyakare (austenitic ne ferritic) 1, 2, 3, super duplex stainless steels (SDSS) dzine hunhu huri nani hwekuora uye hunhu hwakanaka hwemakanika. Simba remakanika rakawedzerwa rinobvumira magadzirirwo akareruka uye akapfava. Kusiyana neizvi, SDSS inodhura ine hunhu hwakanyanya hwekuora kwegomba nekupwanyika, zvichikonzera hupenyu hwakareba hwebasa, nekudaro ichiwedzera kushandiswa kwayo mukudzora kusvibiswa, midziyo yemakemikari, uye indasitiri yemafuta negesi iri kunze kwenyika4. Zvisinei, huwandu hushoma hwekupisa kwekurapa kupisa uye kusagadzirwa zvakanaka zvinokanganisa kushandiswa kwavo kwakakura. Nokudaro, SDSS inogadziriswa kuti ivandudze mashandiro ari pamusoro apa. Semuenzaniso, shanduko yeCe yakaunzwa mu SDSS 2507 (Ce-2507) ine huwandu hwakawanda hwe nitrogen6,7,8. Chinhu chepasi chisingawanzoitiki (Ce) chine huwandu hwakakodzera hwe0.08 wt.% chine mhedzisiro yakanaka pahunhu hweDSS, sezvo ichivandudza kunatswa kwegorosi uye simba remuganhu wegorosi. Kusapera nekuora, simba rekudhonza uye simba rekupa, uye kushanda kwekupisa zvinovandudzikawo9. Nitrogen yakawanda inogona kutsiva nickel inodhura, zvichiita kuti SDSS ive nemutengo wakaderera10.
Munguva pfupi yapfuura, SDSS yakachinjwa nepurasitiki pakupisa kwakasiyana-siyana (cryogenic, cold uye hot) kuti iwane hunhu hwakanaka hwemakanika6,7,8. Zvisinei, kuramba kwakanaka kweSDSS nekuda kwekuvapo kwefirimu rakatetepa reoxide pamusoro kunokanganiswa nezvinhu zvakawanda zvakaita sekusawirirana kwemukati nekuda kwekuvapo kwezvikamu zvakasiyana-siyana zvine miganhu yakasiyana yegorosi, precipitates isingadiwe uye mhinduro dzakasiyana. 7. Nokudaro, kudzidza kwehunhu hwema microscopic domain yemafirimu akadaro kusvika padanho rechimiro chemagetsi kunova kwakakosha pakunzwisisa ngura yeSDSS uye kunoda matekiniki akaoma ekuyedza. Kusvika parizvino, nzira dzinonzwa pamusoro dzakadai seAuger electron spectroscopy11 uye X-ray photoelectron spectroscopy12,13,14,15 uye hard X-ray photoemission microscopy (HAX-PEEM)16 kazhinji dzakakundikana kuona kusiyana kwemakemikari muzvikamu zvepamusoro. mamiriro emakemikari echinhu chimwe chete munzvimbo dzakasiyana dzenzvimbo ye nanoscale. Zvidzidzo zvinoverengeka munguva pfupi yapfuura zvakabatanidza kuoxidation kwechromium munzvimbo nenzvimbo yakaonekwa yekuora kwesimbi dzisina kusimba dze austenitic17, simbi dze martensitic18 uye SDSS19,20. Zvisinei, zvidzidzo izvi zvakanyanya kutarisa pamhedzisiro yeCr heterogeneity (semuenzaniso, Cr3+ oxidation state) pakurasika kwengura. Kusiyana kwemativi mumamiriro ekuoxidation ezvinhu kunogona kukonzerwa nemakomponi akasiyana ane zvinhu zvakafanana, senge iron oxides. Makomponi aya, akagara nhaka saizi diki nekuda kwekurapwa kwethermomechanical, ari padyo nemumwe nemumwe, asi akasiyana mukugadzirwa uye mamiriro ekuoxidation16,21. Nokudaro, kuti uone kutsemuka kwemafirimu e oxide uye kupwanyika kwegomba kunotevera, zvakakosha kunzwisisa kusiyana kwepamusoro padanho re microscopic. Pasinei nezvinodiwa izvi, fungidziro dzehuwandu dzakadai sekusawirirana kwemativi mu oxidation, kunyanya yeFe pa nano- uye atomic scale, ichiri kushaikwa, uye hukama hwayo nekurasika kwengura huchiri kusaongororwa. Kusvika nguva pfupi yadarika, mamiriro emakemikari ezvinhu zvakasiyana-siyana, zvakaita seFe neCa22, pamasampuli esimbi aitsanangurwa nehuwandu uchishandisa soft X-ray photoelectron microscopy (X-PEEM) munzvimbo dze nanoscale synchrotron radiation. Pamwe chete ne chemically sensitive X-ray absorption spectroscopy (XAS), X-PEEM inogonesa kuyerwa kweXAS ne high spatial and spectral resolution, ichipa ruzivo rwemakemikari nezve kuumbwa kwezvinhu uye mamiriro azvo emakemikari ne spatial resolution kusvika pa 23 nanometer scale. . Kuongororwa uku kwe spectromicroscopic kwekutanga kunoita kuti zvikwanise kucherechedzwa kwemakemikari emunharaunda uye kunogona kuratidza shanduko dzemakemikari munzvimbo yesimbi isina kumboongororwa kare.
Chidzidzo ichi chinowedzera zvakanakira zvePEEM pakuona kusiyana kwemakemikari pa nanoscale uye chinopa nzira yekuongorora pamusoro peatomu yekunzwisisa maitiro ekuora kweCe-2507. Inoshandisa nzira yeK-means24 chemometric yakasanganiswa kuti iongorore hukama hwemakemikari epasi rose (hetero) ezvinhu zvinobatanidzwa, ayo mamiriro emakemikari anoratidzwa muchimiro chenhamba. Kusiyana nekuora kwakatangwa nekuparadzwa kwefirimu rechromium oxide muchiitiko chekare, kusaita zvakanaka uye kuramba kushoma kwekuora parizvino kunokonzerwa nezvitsuwa zveFe3+ zvakapfuma pedyo neFe/Cr oxide layer, izvo zvingave zvinhu zvinodzivirira. Iyo oxide inoparadza firimu rine madota uye inokonzera ngura.
Maitiro ekuparadza eSDSS 2507 akakanganisika akatanga kuongororwa achishandisa zviyero zve electrochemical. Pamufananidzo 1 inoratidza makomba eNyquist neBode esampuli dzakasarudzwa mu acidic (pH = 1) aqueous solution yeFeCl3 patembiricha yemumba. Electrolyte yakasarudzwa inoshanda se strong oxidizing agent, ichiratidza maitiro epassivation film yekuputsika. Kunyangwe zvinhu zvisina kugadzikana patembiricha yemumba, ongororo yakapa ruzivo rwezviitiko zvinogona kukundikana uye corrosion inotevera. Dunhu rakafanana (Mufananidzo 1d) rakashandiswa kukodzera electrochemical impedance spectroscopy (EIS) spectrum, uye mhedzisiro inoenderana inoratidzwa muTafura 1. Ma semicircles asina kukwana anoonekwa mu solution-treated uye hot-worked sampuli, nepo ma semicircles akamanikidzwa achionekwa mu cold-rolled counterparts (Mufananidzo .1b). MuEIS spectroscopy, radius ye semicircle inogona kutariswa se polarization resistance (Rp)25,26. Rp yenzira yekumhanyira yakagadziriswa mhinduro muTafura 1 inenge 135 kΩ cm–2, zvisinei, kukosha kwenzira yekumhanyira yakapiswa uye yakaputirwa inotonhora kwakaderera zvikuru, 34.7 uye 2.1 kΩ cm–2, zvichiteerana. Kudzikira kukuru kweRp kunoratidza mhedzisiro yakaipa yekuchinja kwepurasitiki pakusagadzikana uye kuramba ngura, sezvakaratidzwa mumishumo yapfuura 27, 28, 29, 30.
a Nyquist, b, c Bode impedance uye phase diagrams, uye d inoenderana ne equivalent circuit models, uko RS iri electrolyte resistance, Rp iri polarization resistance, uye QCPE ndiyo oxide ye constant phase element inoshandiswa ku model the non-ideal capacitance (n). EIS measurements inoitwa at open circuit potential.
Ma constanti akafanana anoratidzwa muBode plot, neplateau iri mu high frequency range inomiririra electrolyte resistance RS26. Sezvo frequency ichidzikira, impedance inowedzera uye negative phase angle inowanikwa, zvichiratidza capacitance dominance. Phase angle inowedzera, ichiramba iine maximum pamusoro pehuwandu hwakafara hwe frequency, uye yobva yadzikira (Mufananidzo 1c). Zvisinei, muzviitiko zvese zvitatu, iyi maximum ichiri pasi pe90°, zvichiratidza maitiro asina kunaka e capacitive nekuda kwekupararira kwe capacitive. Saka, QCPE constant phase element (CPE) inoshandiswa kumiririra interfacial capacitance distributions inobva mukuoma kwesurface kana inhomogeneity, kunyanya pa atomic scale, fractal geometry, electrode porosity, non-uniform potential, uye geometry ine chimiro che electrodes31,32. CPE impedance:
apo j iri nhamba yekufungidzira uye ω iri angular frequency. QCPE inguva isingachinjiki yefrequency inoenderana nenzvimbo yakavhurika inoshanda ye electrolyte. n inhamba yesimba isina dimension inotsanangura kutsauka kwe capacitor kubva pa capacitance yakanaka, kureva kuti n iri pedyo ne1, CPE iri pedyo ne capacitive chete, nepo n iri pedyo ne zero, inoita seyakasimba. Kutsauka kudiki kwe n, pedyo ne1, kunoratidza maitiro asina kunaka e capacitive epamusoro mushure mekuyedzwa kwe polarization. QCPE ye cold rolled SDSS yakakwira zvakanyanya kupfuura mamwe ayo, zvichireva kuti mhando yekumusoro haina kufanana zvakanyanya.
Zvichienderana nehukuru hwakawanda hwesimbi dzisina ngura dzinodzivirira ngura, huwandu hwakawanda hweSDSS hunowanzoita kuti SDSS isarambe ichidzivirira ngura nekuda kwekuvapo kwefirimu rekuchengetedza oxide rinofambisa pamusoro pechinhu 17. Mafirimu akadaro anowanzo kuve akapfuma muCr3+ oxides uye/kana hydroxides, kunyanya pamwe chete neFe2+, Fe3+ oxides uye/kana (oxy) hydroxides33. Pasinei nekufanana kwenzvimbo, pasi pechinhu oxide layer, uye pasina kupwanyika kwenzvimbo zvichienderana nemicroscope measurements6,7, maitiro ekuora kweSDSS yakapiswa uye yakaputirwa nechando akasiyana, saka kudzidza kwakadzama kwehunhu hwe microstructural kwakakosha kuti simbi ishanduke.
Maumbirwo esimbi isina tsvina yakakanganisika akadzidzwa nehuwandu uchishandisa maX-ray emukati uye e-synchrotron ane simba guru (Mifananidzo Yekuwedzera 1, 2). Ongororo yakadzama inopihwa muRuzivo Rwekuwedzera. Kunyangwe paine kubvumirana kwakawanda pamusoro perudzi rwechikamu chikuru, misiyano muzvikamu zvechikamu chehukuru yakawanikwa, iyo yakanyorwa muTafura Yekuwedzera 1. Misiyano iyi inogona kunge iri nekuda kwezvikamu zvechikamu zvisina homogeneous pamusoro uye muhuwandu, izvo zvinokanganiswa nekudzika kwakasiyana kwekuona kweX-ray diffraction (XRD). ) nemasosi akasiyana esimba e-incident photons34. Zvikamu zve austenite zvakakwirira muzvienzaniso zvakaputirwa zvinotonhora zvakatemwa neXRD kubva kunobva murabhoritari zvinoratidza kuti passivation iri nani uye resistance iri nani yengura35, nepo mhinduro dzakarurama uye dzehuwandu dzichiratidza maitiro akasiyana muzvikamu zvechikamu. Pamusoro pezvo, resistance yengura yesimbi inoenderanawo nehuwandu hwekugadziriswa kwezviyo, kuderedzwa kwehukuru hwezviyo, kuwedzera kwe microdeformations uye dislocation density inoitika panguva yekurapa kwethermomechanical36,37,38. Mienzaniso yakagadzirwa nekupisa yakaratidza hunhu hwemagiraini akawanda, zvichiratidza kuti ine magiraini makuru, nepo mhete dzakatsetseka dzakaonekwa mumienzaniso yakaputirwa nechando (Mufananidzo Wekuwedzera 3) dzairatidza kunatswa kwakakosha kwegiraini kusvika pahukuru hwe nanosize mubasa rekare. Izvi zvinofanirwa kubatsira kuumbwa kwefirimu risingapindi uye kuwedzera kwekudzivirira ngura. Kuwanda kwe dislocation density kunowanzobatanidzwa nekusadzivirira kudzika kwegomba, izvo zvinoenderana zvakanaka nekuyerwa kwemagetsi.
Kuchinja kwemamiriro emakemikari ema microdomains ezvinhu zvikuru kwakadzidzwa zvakarongeka uchishandisa X-PEEM. Kunyangwe paine zvimwe zvinhu zvinosanganisa, Cr, Fe, Ni naCe39 zvinosarudzwa pano, sezvo Cr iri chinhu chakakosha pakuumba firimu risingashande, Fe ndiyo chinhu chikuru chesimbi, uye Ni inowedzera kufambiswa kwesimba uye inoenzanisa chikamu cheferrite-austenitic. Maumbirwo uye kugadziriswa ndicho chinangwa cheCe. Nekugadzirisa simba re synchrotron beam, XAS yakabata hunhu hukuru hweCr (L2.3 edge), Fe (L2.3 edge), Ni (L2.3 edge), uye Ce (M4.5 edge) kubva pamusoro. -2507 SDSS. Kuongororwa kwedata kwakakodzera kwakaitwa nekubatanidza calibration yesimba nedata rakaburitswa (semuenzaniso XAS paFe L2, 3 ribs40,41).
Pamufananidzo 2 panoratidza mifananidzo yeX-PEEM yemagetsi anopisa (Mufananidzo 2a) uye akaputirwa nechando (Mufananidzo 2d) Ce-2507 SDSS uye mipendero yeXAS Cr neFe L2,3 inoenderana panzvimbo dzakanyorwa zvakasiyana. Mupendero weL2,3 XAS unoongorora mamiriro e3d asina kushandiswa emaerekitironi mushure me photoexcitation pamazinga ekupatsanurana kwe2p3/2 (L3 edge) uye 2p1/2 (L2 edge). Ruzivo nezvemamiriro eCr valence rwakawanikwa kubva mu X-ray diffraction analysis yemupendero weL2,3 muMufananidzo 2b,d. Kuenzanisa kwekubatanidza. 42, 43 yakaratidza kuti peaks ina A (578.3 eV), B (579.5 eV), C (580.4 eV), uye D (582.2 eV) dzakaonekwa pedyo nemupendero weL3, dzichiratidza maion eCr3+ octahedral, anoenderana neCr2O3. Ma spectra ekuyedza anowirirana nekuverenga kwedzidziso, sezvakaratidzwa mumapaneru b na e, akawanikwa kubva mukuverenga kwenzvimbo dzekristaro dzakawanda paCr L2.3 interface uchishandisa nzvimbo yekristaro ye2.0 eV44. Nzvimbo dzese dziri mbiri dzeSDSS dzakagadzirwa nekupisa nedzinotonhora dzakaputirwa nechikamu chakafanana cheCr2O3.
Mufananidzo wekupisa weX-PEEM SDSS yakagadzirwa nekupisa unoenderana nemucheto b Cr L2.3 uye mupendero c Fe L2.3, d Mufananidzo wekupisa X-PEEM yeSDSS yakaputirwa nechando inoenderana nemucheto e Cr L2.3 uye f Fe L2.3 yerutivi (e). MaXAS spectra akarongwa panzvimbo dzakasiyana-siyana dzakanyorwa pamifananidzo yekupisa (a, d) nemitsetse yeorenji ine madotsi muna (b) na (e) inomiririra XAS spectra yakaenzaniswa yeCr3+ ine kukosha kwekristaro ye2.0 eV. Pamifananidzo yeX-PEEM, palette yekupisa inoshandiswa kuvandudza kuverenga kwemufananidzo, uko mavara kubva pabhuruu kusvika kutsvuku anoenderana nekusimba kweX-ray absorption (kubva pasi kusvika kumusoro).
Pasinei nemamiriro ezvinhu emakemikari ezvinhu izvi zvesimbi, mamiriro emakemikari ekuwedzera kwezvinhu zveNi neCe alloying kune ese ari maviri akaramba akafanana. Mufananidzo wekuwedzera. Pamufananidzo 5-9 ratidza mifananidzo yeX-PEEM uye maXAS spectra anoenderana eNi neCe panzvimbo dzakasiyana pamusoro pezvinhu zvakapiswa uye zvakaputirwa nechando. Ni XAS inoratidza mamiriro eoxidation eNi2+ pamusoro pese pakaenzana pezvinhu zvakapiswa uye zvakaputirwa nechando (Kukurukurirana Kwekuwedzera). Zvakakosha kuziva kuti kana iri mienzaniso yakapiswa, chiratidzo cheXAS cheCe hachionekwi, nepo spectrum yeCe3+ yezvigadzirwa zvakapiswa ichionekwa pane imwe nguva. Kuonekwa kwemavara eCe muzvikamu zvakaputika zvakatonhora kwakaratidza kuti Ce inonyanya kuwanikwa muchimiro che precipitates.
MuSDSS yakakanganisika nekupisa, hapana shanduko yemuumbi weXAS yakaonekwa pamucheto weFe L2.3 (Mufananidzo 2c). Zvisinei, sezvakaratidzwa pamufananidzo 2f, Fe matrix inochinja chimiro chayo chemakemikari nemicroscope panzvimbo nomwe dzakasarudzwa zvisina kurongeka muSDSS inotonhora. Pamusoro pezvo, kuti tiwane pfungwa chaiyo yekuchinja kwemamiriro eFe panzvimbo dzakasarudzwa muMufananidzo 2f, zvidzidzo zvemunzvimbo zvakaitwa (Mufananidzo 3 neMufananidzo Wekuwedzera 10) umo nzvimbo diki dzakatenderera dzakasarudzwa. XAS spectra yeFe L2,3 edge yeα-Fe2O3 systems uye Fe2+ octahedral oxides dzakagadzirwa uchishandisa multiplet crystal field calculations uchishandisa crystal fields ye1.0 (Fe2+) uye 1.0 (Fe3+)44. Tinoona kuti α-Fe2O3 uye γ-Fe2O3 dzine symmetries dzakasiyana dzemuno45,46, Fe3O4 ine musanganiswa weFe2+ & Fe3+,47, uye FeO45 seFe2+ oxide yakaparadzaniswa (3d6). Tinoona kuti α-Fe2O3 uye γ-Fe2O3 dzine symmetries dzakasiyana dzemuno45,46, Fe3O4 ine musanganiswa weFe2+ & Fe3+,47, uye FeO45 seFe2+ oxide yakaparadzaniswa (3d6).Cherechedza kuti α-Fe2O3 uye γ-Fe2O3 dzine symmetries dzakasiyana dzemuno45,46, Fe3O4 inosanganisa Fe2+ neFe3+,47 neFeO45 muchimiro che formally divalent oxide Fe2+ (3d6).Ziva kuti α-Fe2O3 uye γ-Fe2O3 dzine ma symmetries akasiyana emunharaunda45,46, Fe3O4 ine musanganiswa weFe2+ neFe3+,47 uye FeO45 inoshanda seye divalent yepamutemo Fe2+ oxide (3d6). Ma ions ese eFe3+ mu α-Fe2O3 ane nzvimbo dzeOh chete, nepo γ-Fe2O3 inowanzo ratidzwa seFe3+ t2g [Fe3+5/3V1/3]eg O4 spinel ine nzvimbo dzisina chinhu munzvimbo dzemuenzaniso. Saka, ma ions eFe3+ muγ-Fe2O3 ane nzvimbo dzeTd neOh. Sezvambotaurwa mubasa rapfuura, kunyangwe huwandu hwesimba hwevaviri hwakasiyana, huwandu hwavo hwesimba eg/t2g i ≈1, nepo muchiitiko ichi chiyero chesimba chakacherechedzwa eg/t2g chingangoita 1. Izvi zvinobvisa mukana wekuti Fe3+ chete ivepo munyaya iyi. Tichifunga nezvenyaya yeFe3O4 nemusanganiswa weFe2+ neFe3+, zvinozivikanwa kuti chiratidzo chekutanga chisina kusimba (chakasimba) mumucheto weL3 weFe chinoratidza kusavapo kudiki (kwakakura) muchimiro chet2g. Izvi zvinoshanda kuFe2+ (Fe3+), izvo zvinoratidza kuwedzera kwechiratidzo chekutanga chinoratidza kuwedzera kwehuwandu hweFe2+47. Mhedzisiro iyi inoratidza kuti Fe2+ neγ-Fe2O3, α-Fe2O3 uye/kana Fe3O4 zvinonyanya kuoneka pamusoro pezvinhu zvinotonhora zvakaputirwa.
Mifananidzo yakakura ye photoemission electron thermal ye (a, c) uye (b, d) XAS spectra pamusoro peFe L2,3 edge panzvimbo dzakasiyana-siyana dzenzvimbo mukati menzvimbo dzakasarudzwa 2 neE muMifananidzo 2d.
Data rekuyedza rakawanikwa (Mufananidzo 4a neMufananidzo Wekuwedzera 11) rakarongwa uye rakaenzaniswa neremakemikari akachena 40, 41, 48. Chaizvoizvo, mhando nhatu dzakasiyana dzeFe L-edge XAS spectra dzakaonekwa nekuyedza (XAS-1, XAS-2 uye XAS-3: Mufananidzo 4a) dzakaonekwa munzvimbo dzakasiyana. Kunyanya, spectrum yakafanana ne2-a (inoratidzwa seXAS-1) muMufananidzo 3b yakaonekwa munzvimbo yese yekuda, ichiteverwa ne2-b spectrum (yakanyorwa seXAS-2), nepo spectrum yakafanana neE-3 yakaonekwa mumufananidzo 3d (inozivikanwa seXAS-3) yakaonekwa munzvimbo dzakati wandei. Kazhinji, maparameter mana anoshandiswa kuziva mamiriro evalence aripo mumuenzaniso weprobe: (1) maficha eL3 neL2 spectral, (2) nzvimbo dzesimba dzemaficha eL3 neL2, (3) musiyano wesimba reL3-L2, (4) L2 intensity ratio /L3. Zvichienderana nezvakaonekwa (Mufananidzo 4a), zvikamu zvitatu zveFe, zvinoti Fe0, Fe2+, uye Fe3+, zviripo pamusoro peSDSS yakadzidzwa. Chiyero chesimba chakaverengerwa L2/L3 chakaratidzawo kuvapo kwezvikamu zvitatu izvi.
a Ndakaona data rekuyedza rakasiyana-siyana (mitsara yakasimba XAS-1, XAS-2 uye XAS-3 inoenderana ne2-a, 2-b uye E-3 muMufananidzo 2 neMufananidzo 3) zvichienzaniswa neXAS Comparison spectra, octahedrons Fe2+, Fe3+, crystal field values ​​​​ye1.0 eV uye 1.5 eV, zvichiteerana, b–d Yakayerwa data rekuyedza (XAS-1, XAS-2, XAS-3) uye data reLCF rakagadziriswa rinoenderana (mutsara mutema wakasimba), uye kuenzanisa XAS-3 spectra neFe3O4 (mamiriro akasanganiswa eFe) uye Fe2O3 (pure Fe3+) standards.
Kubatanidzwa kwemutsetse (LCF) kwezviyero zvitatu40,41,48 kwakashandiswa kuyera kuumbwa kwesimbi oxide. LCF yakashandiswa kune matatu akasarudzwa Fe L-edge XAS spectra inoratidza musiyano wepamusoro, kureva XAS-1, XAS-2 uye XAS-3, sezvakaratidzwa muMufananidzo 4b–d. Kune LCF fittings, 10% Fe0 yakatariswa mune zvese zviitiko nekuda kwechikamu chidiki chatakaona mudata rese uye chokwadi chekuti simbi yesimbi ndiyo chikamu chikuru chesimbi. Zvechokwadi, kudzika kweprobation kweX-PEEM yeFe (~6 nm)49 kwakakura kupfuura ukobvu hweoxidation layer hunofungidzirwa (zvishoma > 4 nm), zvichibvumira kuonekwa kwechiratidzo kubva ku iron matrix (Fe0) pasi pe passivation layer. Zvechokwadi, kudzika kweprobation kweX-PEEM yeFe (~6 nm)49 kwakakura kupfuura ukobvu hweoxidation layer hunofungidzirwa (zvishoma > 4 nm), zvichibvumira kuonekwa kwechiratidzo kubva ku iron matrix (Fe0) pasi pe 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, kudzika kweprobe X-PEEM yeFe (~6 nm)49 kwakakura kupfuura ukobvu hunofungidzirwa hweoxidation layer (zvishoma >4 nm), izvo zvinoita kuti zvikwanisike kuona chiratidzo kubva ku iron matrix (Fe0) pasi pe passivation layer.Kutaura zvazviri, X-PEEM inoona Fe (~6 nm)49 yakadzika kupfuura ukobvu hunotarisirwa hwe oxide layer (inopfuura 4 nm), zvichibvumira kuonekwa kwezviratidzo kubva ku iron matrix (Fe0) pasi pe passivation layer. Kusanganiswa kwakasiyana-siyana kweFe2+ neFe3+ kwakaitwa kuti pave nemhinduro yakanakisisa yedata rekuyedza rakaonekwa. Pamufananidzo. Mufananidzo 4b unoratidza kusanganiswa kweFe2+ neFe3+ muXAS-1 spectrum, uko huwandu hweFe2+ neFe3+ huri pedyo, hunenge 45%, izvo zvinoratidza mamiriro e oxidation akasanganiswa eFe. Asi kune XAS-2 spectrum, chikamu cheFe2+ neFe3+ chinova ~30% uye 60%, zvichiteerana. Zviri mukati meFe2+ zvakaderera pane zveFe3+. Chiyero cheFe2+ neFe3 che1:2 chinoreva kuti Fe3O4 inogona kuumbwa pachiyero chimwe chete cheFe ions. Pamusoro pezvo, paXAS-3 spectrum, huwandu hweFe2+ neFe3+ hwakachinja huchienda ku ~10% ne80%, zvichiratidza kushanduka kwakanyanya kweFe2+ kuenda kuFe3+. Sezvambotaurwa pamusoro apa, Fe3+ inogona kubva kuα-Fe2O3, γ-Fe2O3 kana Fe3O4. Kuti unzwisise kuti Fe3+ inobva kupi, XAS-3 spectra dzakanyorwa pamwe chete neFe3+ standards dzakasiyana muFig. 4e dzichiratidza kufanana nematanho ese maviri kana Peak B yaonekwa. Zvisinei, simba repafudzi (A: kubva kuFe2+) uye chiyero chesimba B/A zvinoratidza kuti spectrum yeXAS-3 iri pedyo asi haina kufanana neiyo yeγ-Fe2O3. Zvichienzaniswa nebulk γ-Fe2O3, simba reFe2p XAS reA SDSS peak rakakwira zvishoma (Fig. 4e), izvo zvinoratidza simba reFe2+ rakakwirira. Kunyangwe spectrum yeXAS-3 yakafanana neyeγ-Fe2O3, uko Fe3+ iripo munzvimbo dzese dzeOh neTd, kuzivikanwa kwemamiriro akasiyana evalence uye kubatana chete nemucheto weL2,3 kana chiyero cheL2/L3 intensity ichiri dambudziko. Inyaya inodzokororwa yekukurukurirana nekuda kwekuoma kwezvinhu zvakasiyana-siyana zvinobatanidzwa muspectrum yekupedzisira41.
Pamusoro pekusarurana kwema spectral emamiriro emakemikari enzvimbo dzakasarudzwa dzatsanangurwa pamusoro apa, kusiyana kwemakemikari epasi rose kwezvinhu zvakakosha Cr naFe kwakaongororwa nekuisa muzvikamu zvese zveXAS spectra zvakawanikwa pamusoro pemuenzaniso uchishandisa nzira yeK-means clustering. Ma edge profiles Cr L akaiswa nenzira yekuti agadzire mapoka maviri akakodzera akapararira munzvimbo dzakasiyana muzvienzaniso zvinopisa uye zvinotonhora zvakaputirwa zvinoratidzwa muMifananidzo 5. Zviri pachena kuti hapana shanduko dzemunzvimbo dzakaonekwa, sezvo ma centroid maviri eXAS Cr spectra akafanana zvikuru. Maumbirwo aya espectral ema clusters maviri akafanana neaya anoenderana neCr2O342, zvinoreva kuti ma layers eCr2O3 akapararira zvakaenzana pamusoro peSDSS.
boka renzvimbo dzeK-means L-edge Cr, b inoenderana neXAS centroids. Mhedzisiro yekuenzanisa K-means X-PEEM yeSDSS yakaputirwa nechando: c mapoka enzvimbo dzeK-means edge dzeCr L2,3 uye d inoenderana neXAS centroids.
Kuti tiratidze mepu yeFeL edge yakaoma, mapoka mana nemashanu akagadziridzwa uye macentroid akabatana nawo (spectral distributions) anoshandiswa kune sampuli dzakagadzirwa nekupisa uye dzakaputirwa nechando, zvichiteerana. Nokudaro, chikamu (%) cheFe2+ neFe3+ chinogona kuwanikwa nekugadzirisa LCF inoratidzwa muMufananidzo 4. Pseudo potential sebasa reFe0 yakashandiswa kuratidza kusawirirana kwemakemikari emufirimu wepamusoro weoxide. 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 hwakakwira hweFe3+ compounds. Kugoverwa kwemukana mumuenzaniso wakakanganiswa nekupisa kune hunhu hwakaiswa layered hune shanduko huru inosvika 0.119 V (Mufananidzo 6a,b). Kugoverwa uku kwemukana kwakabatana zvakanyanya nepamusoro penzvimbo (Mufananidzo 6a). Hapana dzimwe shanduko dzine chekuita nenzvimbo dzakaonekwa mukati me lamellar (Mufananidzo 6b). Kusiyana neizvi, pakusanganiswa kwema oxide akasiyana ane zvirimo zvakasiyana zveFe2+ neFe3+ mu SDSS yakaputirwa nechando, hunhu husina kufanana hwe pseudopotential hunogona kuonekwa (Mufananidzo 6c, d). MaFe3+ oxides uye/kana (oxy) hydroxides ndizvo zvikamu zvikuru zvengura musimbi uye zvinopinda muokisijeni nemvura50. Muchiitiko ichi, zvinogona kuonekwa kuti zvitsuwa zvakapfuma muFe3+ zvakapararira munharaunda uye zvinogona kuonekwa senzvimbo dzengura. Muchiitiko ichi, gradient mumunda we potential, pane kukosha kwakakwana kwe potential, inogona kuonekwa sechiratidzo chekuwanikwa kwenzvimbo dze corrosion dzinoshanda51. Kupararira uku kweFe2+ neFe3+ pamusoro peSDSS inotonhora kunogona kushandura hunhu hwemakemikari emuno uye kupa nzvimbo inoshanda zvakanyanya mukupwanyika kwe oxide film uye corrosion reactions, nokudaro zvichibvumira matrix yesimbi iri pasi kuti irambe ichiora, zvichikonzera kusagadzikana kwemukati. uye kuderedza hunhu hwekudzivirira hwe passivating layer.
Mapoka eK-mean eFe L2,3 emucheto uye macentroid anoenderana eXAS e a–c anoshandiswa nekupisa X-PEEM uye d–f cold-rolled SDSS. a, d K-means cluster plot yakafukidzwa pamufananidzo weX-PEEM. Zvinofungidzirwa kuti pseudoelectrode potentials (epseudo) zvakataurwa pamwe chete nemadhayagiramu eK-means cluster. Kupenya kwemufananidzo weX-PEEM senge ruvara rwuri muMufananidzo 2 kunoenderana zvakananga nekusimba kweX-ray absorption.
Kuenzana kweCr asi mamiriro akasiyana emakemikari eFe anotungamira kune mavambo akasiyana ekupwanyika kwefirimu reoxide uye mapatani ekuora muCe-2507 yakaputirwa nekupisa uye yakaputirwa nechando. Hunhu uhwu hweCe-2507 yakaputirwa nechando hunozivikanwa. Nezvekuumbwa kwemaoxide nemahydroxide eFe mumhepo yemuchadenga, maitiro anotevera akavharwa mubasa iri semaitiro asina kwaakarerekera:
Zvichibva pakuyerwa kweX-PEEM, maitiro ari pamusoro apa akaitika mune zvinotevera. Bandauko diki rinoenderana neFe0 rinobatanidzwa nesimbi iri pasi. Maitiro esimbi Fe nenharaunda anotungamira pakuumbwa kweFe(OH)2 layer (equation (5)), iyo inowedzera chiratidzo cheFe2+ muXAS yemucheto weL weFe. Kuratidzwa kwenguva refu mumhepo kuchaguma nekuumbwa kweFe3O4 uye/kana Fe2O3 oxides mushure meFe(OH)252,53. Mhando mbiri dzeFe dzakagadzikana, Fe3O4 neFe2O3, dzinogonawo kuumbwa muCr3+ rich protective layer, uko Fe3O4 inofarira chimiro chakafanana uye chakabatana. Kuvapo kwezvose izvi kunoguma nemamiriro akasiyana e oxidation (XAS-1 spectrum). XAS-2 spectrum inonyanya kuenderana neFe3O4. Nepo XAS-3 spectra yakaonekwa panzvimbo dzakasiyana yakaratidza kushanduka kwakazara kuita γ-Fe2O3. Sezvo maX-ray asina kuputirwa aine kudzika kwekupinda kweinenge 50 nm, chiratidzo chinobva pasi pechikamu chinoguma nekusimba kwakanyanya kweA peak.
XRD spectrum inoratidza kuti chikamu cheFe mufirimu re oxide chine chimiro chakaiswa, icho chakabatanidzwa neCr oxide layer. Kusiyana ne passivation hunhu hwekuora nekuda kwekusawirirana kweCr2O317, pasinei ne sample yakaenzana yeCr2O3 muchidzidzo ichi, kusawirirana kwakaderera kwekuora kwakaonekwa munyaya iyi, kunyanya kune masampuli akaputirwa nechando. Maitiro akaonekwa anogona kunzwisiswa se heterogeneity ye chemical oxidation state ye top layer (Fe) ichikanganisa mashandiro ekuora. Kutamiswa zvishoma nezvishoma kwema ions esimbi kana oxygen mu lattice nekuda kwe stoichiometry imwechete yepamusoro (Fe oxide) ne layer dzakaderera (Cr oxide) 52,53 kunotungamira pakubatana kuri nani (kunamatira) pakati pawo. Izvi, zvinovandudza kusawirirana kwekuora. Naizvozvo, continuous stoichiometry, kureva imwe oxidation state yeFe, inonyanya kunaka pane kuchinja kwe stoichiometric kamwe kamwe. Thermally deformed SDSS ine nzvimbo yakafanana uye dense protective layer, iyo inopa kusawirirana kuri nani kwekuora. Zvisinei, kune SDSS inoputirwa nechando, kuvapo kwezvitsuwa zveFe3+ zvakapfuma pasi pechikamu chekudzivirira kunoparadza kusimba kwenzvimbo uye kunokonzera ngura ye galvanic ye substrate iri pedyo, izvo zvinotungamira kukudzikira kweRp (Tafura 1) muEIS spectra uye kuramba kwayo ngura. Nokudaro, zvitsuwa zvakapararira munharaunda zvakapfuma muFe3+ nekuda kwekuchinja kwepurasitiki zvinonyanya kukanganisa mashandiro ekudzivirira ngura, inova budiriro mubasa iri. Nokudaro, chidzidzo ichi chinoratidza ma spectromicrographs ekudzikira kwekudzivirira ngura nekuda kwekuchinja kwepurasitiki kwemasampuli eSDSS akadzidzwa.
Uyezve, kunyange hazvo kusanganiswa kwevhu rare earth musimbi dzemhando mbiri kuchiita zvirinani, kudyidzana kwechinhu ichi chakawedzerwa nesimbi yega yega maererano nemaitiro ekuora kunoramba kuri nyore kunzwisisa zvichibva pakuongorora kwe spectroscopic microscopy. Chiratidzo cheCe (pamwe neXAS M-edge) chinoonekwa panzvimbo shoma chete panguva yekutenderera kunotonhora, asi chinonyangarika panguva yekushanduka kweSDSS, zvichiratidza kuiswa kweCe musimbi panzvimbo pekubatanidza homogeneous. Kunyangwe hunhu hwemakanika hweSDSS husina kuvandudzwa6,7, kuvapo kweREE kunoderedza saizi yezvinosanganisirwa uye kunofungidzirwa kuti kunoderedza kudonha kwegomba panzvimbo yekutanga54.
Mukupedzisa, basa iri rinoburitsa pachena mhedzisiro yekusiyana kwenzvimbo pamusoro pengura ye2507 SDSS yakagadziriswa necerium nekuyera huwandu hwemakemikari ari muzvikamu zve nanoscale. Takapindura mubvunzo wekuti sei simbi isingatsvi ichiora kunyangwe yakafukidzwa ne protective oxide layer nekudzidza huwandu hwe microstructure, mamiriro emakemikari enzvimbo uye kugadzirisa masaini uchishandisa K-means clustering. Zvakaonekwa kuti zvitsuwa zveFe3+-rich, kusanganisira octahedral ne tetrahedral coordination yavo muchimiro che mixed Fe2+/Fe3+, itsime rekuparadzwa kwe oxide film uye itsime re corrosion ye cold-rolled SDSS. Nanoislands inotongwa neFe3+ inotungamira mukusagadzikana kwe corrosion kunyangwe paine stoichiometric Cr2O3 passivating layer yakakwana. Kuwedzera kune kufambira mberi kwemaitiro kwakaitwa mukuona mhedzisiro yekusiyana kwemakemikari e nanoscale pakuora, basa iri rinotarisirwa kukurudzira maitiro einjiniya ekuvandudza kuramba kwe corrosion kwesimbi dzisingatsvi panguva yekugadzira simbi.
Kugadzira ma ingots eCe-2507 SDSS akashandiswa muchidzidzo ichi, zvinhu zvakasanganiswa, kusanganisira Fe-Ce master alloy yakavharwa nemachubhu esimbi yakachena, zvakanyungudutswa muchoto che 150 kg che medium frequency induction kuti zvigadzire simbi yakanyungudutswa uye zvakadururwa muma molds ekukanda. Makemikari akayerwa (wt %) akanyorwa muSupplementary Table 2. Ingot inotanga yagadzirwa kuita mabhuroko. Zvadaro simbi yakanyungudutswa pa1050°C kwemaminitsi makumi matanhatu kusvika yaoma, yozodzimwa mumvura kusvika patembiricha yemukamuri. Sampuli dzakadzidzwa dzakadzidzwa zvakadzama uchishandisa TEM neDOE kudzidza zvikamu, saizi yetsanga uye chimiro. Ruzivo rwakadzama nezve sampuro uye maitiro ekugadzira runogona kuwanikwa mune mamwe masosi6,7.
Gadzirai sampuli dze cylindrical (φ10 mm × 15 mm) kuti mupinze nekupisa ne axis ye cylindrical yakatarisana nekwakagadziriswa kwe block. Kudzvanywa kwekupisa kwakanyanya kwakaitwa ne strain rate inogara iri pakati pe 0.01-10 s-1 patembiricha dzakasiyana dziri pakati pe 1000-1150°C uchishandisa Gleeble-3800 thermal simulator. Musati machinja, sampuli dzaipiswa patembiricha yakasarudzwa pa 10 °C s-1 kwemaminitsi maviri kuti dzibvise temperature gradient. Mushure mekusvika pakufanana kwetembiricha, sampuli dzakachinja kusvika pa true strain value ye 0.7. Mushure mekuchinja, inodzimwa nemvura nekukurumidza kuti ichengetedze chimiro chakakanganisika. Zvadaro sampuli dzakaoma dzakachekwa dzakaenzana nekwakamanikidzwa. Pachidzidzo ichi, takasarudza sampuli yakachinja pa 1050°C, 10 s-1 nekuda kwekuoma kwakanyanya kwakaonekwa kupfuura dzimwe sampuli7.
Sampuro dzakawanda (80 × 10 × 17 mm3) dzeCe-2507 solid solution dzakaedzwa pamuchina wemhando nhatu we LG-300 une mapoinzi maviri, uyo wakapa hunhu hwakanaka hwemakanika pakati pemamwe makirasi ese ekuchinja6. Kuderedzwa kwekusvuta uye ukobvu hwaive 0.2 m·s-1 uye 5% panzira yega yega, zvichiteerana.
Nzvimbo yekushandira yemagetsi yeAutolab PGSTAT128N yakashandiswa kuyera SDSS nemagetsi mushure mekukanda nechando kusvika pa90% ukobvu (1.0 yakaenzana ne true strain) uye kudzvanya nekupisa kusvika pa0.7 true strain pa1050 oC uye 10 s-1. Nzvimbo yekushandira ine cell ine maelectrode matatu ine calomel electrode yakaguta se electrode yekutarisa, graphite counter electrode, uye SDSS sample se electrode yekushanda. Masamples akachekwa kuita masilinda ane dhayamita ye11.3 mm, kumativi ayo waya dzemhangura dzakasungirirwa. Zvadaro sample yakadururwa ne epoxy resin, ichisiya nzvimbo yakashama ye1 cm2 se electrode yekushanda (nzvimbo yepasi ye sample ye cylindrical). Chenjerera panguva yekupisa epoxy uye panguva yekusandwa nekuporishwa kwakatevera kuti isatsemuke. Nzvimbo yekushandira inonamirwa nekuporishwa ne diamond polishing suspension ine saizi ye particle ye 1 micron, yakacheneswa nemvura yakasanganiswa ne ethanol uye yakaomeswa mumhepo inotonhora. Pamberi pekuyerwa kwe electrochemical, masamples akaporishwa aiiswa mumhepo kwemazuva akati wandei kuti agadzire natural oxide film. Mhinduro yemvura yeFeCl3 (6.0 wt.%), yakagadzikaniswa neHCl kusvika pH = 1.0 ± 0.01, yakashandiswa kukurumidzisa ngura yesimbi isingatsvedzi55, sezvo inowanikwa munzvimbo dzine hukasha uko ma chloride ions aripo ane simba rakasimba re oxidizing uye pH yakaderera sezvakatsanangurwa neASTM. Mitemo yakakurudzirwa ndeye G48 naA923. Samples dzakanyudzwa mu test solution kweawa imwe chete zvisati zvatorwa zviyero kuti zvisvike padanho repedyo ne stationary. Kune solid solution, hot-worked uye cold-rolled sampuli, impedance measurement frequency range yaive 1 × 105 ~ 0.1 Hz, uye open-circuit potential (OPS) yaive 5 mV, yaive 0.39, 0.33, uye 0.25 VSCE, zvichiteerana. Kuedza kwega kwega kwe electrochemical kwesampuli chero ipi zvayo kwakadzokororwa kanenge katatu pasi pemamiriro akafanana kuti kuve nechokwadi chekuti data rinodzokororwazve.
Pakuyerwa kweHE-SXRD, mabhuroko esimbi erectangular duplex 1 × 1 × 1.5 mm3 akayerwa pamutsetse weBrockhouse wiggler une simba guru paCLS, Canada kuti averenge huwandu hwechikamu 56. Kuunganidzwa kwedata kwakaitwa patembiricha yemukamuri muDebye-Scherrer geometry kana transport geometry. Kureba kwemaX-rays akaenzaniswa neLaB6 calibrant i0.212561 Å, iyo inoenderana ne58 keV, iyo yakanyanya kupfuura iyo yeCu Kα (8 keV) inowanzoshandiswa senzvimbo yeX-ray yerabhoritari. Sampuro inoiswa padaro re740 mm kubva pa detector. Vhoriyamu yekuona yesampuro yega yega i0.2 × 0.3 × 1.5 mm3, iyo inotsanangurwa nehukuru hwebeam uye ukobvu hwesampuro. Ruzivo rumwe nerumwe rwakaunganidzwa pachishandiswa Perkin Elmer area detector, flat panel X-ray detector, 200 µm pixels, 40 × 40 cm2, pachishandiswa nguva yekuratidzwa kwe 0.3 seconds uye 120 frames.
Kuyerwa kweX-PEEM kwemamodheru maviri akasarudzwa kwakaitwa paPEEM end station yeBeamline MAXPEEM line muMAX IV laboratory (Lund, Sweden). Masampuru akagadzirwa nenzira imwecheteyo yekuyerwa kwemagetsi. Masampuru akagadzirwa akachengetwa mumhepo kwemazuva akati wandei uye akabviswa mweya mukamuri revacuum rakakwirira kwazvo asati apiswa nemwaranzi ne synchrotron photons. Simba rekugadzirisa kwedanda rinowanikwa nekuyera ion output spectrum kubva kuN 1 s kusvika 1\(\pi _g^ \ast\) yenzvimbo ye excitation ine hv = 401 eV muN2 uye kuvimba kwesimba re photon paE3/2.57. Kukwana kweSpectral kwakapa ΔE (spectral linewidth) ~0.3 eV pamusoro pesimba rakayerwa. Saka, resolution yesimba re beamline yakafungidzirwa kuva E/∆E = 700 eV/0.3 eV > 2000 uye flux ≈1012 ph/s nekushandisa modified SX-700 monochromator ine Si 1200-line mm−1 grating yeFe 2p L2,3 edge, Cr 2p L2,3 edge, Ni 2p L2,3 edge, uye Ce M4,5 edge. Saka, resolution yesimba re beamline yakafungidzirwa kuva E/∆E = 700 eV/0.3 eV > 2000 uye flux ≈1012 ph/s nekushandisa modified SX-700 monochromator ine Si 1200-line mm−1 grating yeFe 2p L2.3 edge, Cr 2p L2.3 edge, Ni 2p L2.3 edge, uye Ce M4.5 edge. 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 Saka, simba rekugadzirisa remugero we beam rakafungidzirwa seE/∆E = 700 eV/0.3 eV > 2000 uye flux ≈1012 f/s uchishandisa modified SX-700 monochromator ine Si grating ye1200 lines/mm yeFe edge 2p L2 ,3, Cr edge 2p L2.3, Ni edge 2p L2.3, 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 modified SX-700 monochromator uye 1200 line Si grating. 3, Cr edge 2p L2.3, Ni edge 2p L2.3 uye Ce edge M4.5.Wedzera simba re photon mumatanho e 0.2 eV. Pasimba rega rega, mifananidzo yePEEM yakarekodhwa uchishandisa TVIPS F-216 CMOS detector ine 2 x 2 binning fiber optic connection inopa 1024 × 1024 pixels munzvimbo yekuona ye 20 µm. Nguva yekuratidzwa kwemifananidzo i 0.2 masekondi, avhareji yemafuremu gumi nematanhatu. Simba remufananidzo we photoelectron rinosarudzwa nenzira yekupa chiratidzo chepamusoro che secondary electron. Kuyerwa kwese kunoitwa pachiitiko chenguva dzose che dayamondi re linearly polarized. Kuti uwane rumwe ruzivo nezvekuyerwa, ona chidzidzo chekare58. Mushure mekudzidza iyo total electron yield (TEY)59 detection mode uye mashandisirwo ayo mu X-PEEM, kudzika kwekuona kwenzira iyi kunofungidzirwa pa ~4–5 nm yechiratidzo che Cr uye ~6 nm yechiratidzo che Fe. Kudzika kwe Cr kuri pedyo zvikuru ne oxide film thickness (~4 nm)60,61 nepo kudzika kwe Fe kuri kukuru kupfuura oxide film thickness. XAS yakaunganidzwa pedyo neFe L edge musanganiswa we iron oxide XAS neFeO kubva mu matrix. Muchiitiko chekutanga, simba remaerekitironi anoburitswa rinokonzerwa nemhando dzese dzemaerekitironi dzinobatsira kuTEY. Zvisinei, chiratidzo chesimbi chakachena chinoda simba re kinetic rakawanda kuti maerekitironi apfuure nepakati pe oxide layer, asvike pamusoro, uye aunganidzwe ne analyzer. Muchiitiko ichi, chiratidzo cheFe0 chinonyanya kukonzerwa nemaerekitironi eLVV Auger nemaerekitironi echipiri anoburitswa nawo. Pamusoro pezvo, simba reTEY rinopihwa nemaerekitironi aya rinoora panguva yekubuda kweerekitironi49 richideredza zvakanyanya siginecha yespectral yeFe0 mumepu yesimbi XAS.
Kubatanidza data mu data cubes (data reX-PEEM) idanho guru mukutsvaga ruzivo rwakakodzera (makemikari kana physical properties) nenzira ine mativi akawanda. K-means clustering inoshandiswa zvakanyanya munzvimbo dzakasiyana siyana, kusanganisira machine vision, image processing, unsupervised pattern recognition, artificial intelligence, uye classificatory analysis24. Semuenzaniso, K-means clustering inoshandiswa zvakanaka pa clustering hyperspectral image data62. Panyaya iyi, kune multi-object data, K-means algorithm inogona kuvabatanidza zviri nyore zvichienderana neruzivo nezvehunhu hwavo (photon energy characteristics). K-means clustering i iterative algorithm yekuparadzanisa data mu K non-overlapping groups (clusters), uko pixel yega yega iri ye specific cluster zvichienderana nekugoverwa kwe spatial kwe chemical inhomogeneity mu steel microstructural composition. K-means algorithm ine matanho maviri: danho rekutanga rinoverenga K centroids, uye danho rechipiri rinopa poindi yega yega ku cluster ine centroids dziri pedyo. Pakati pegiravhiti yeboka (centre of gravity) panotsanangurwa se meanthmetic mean yedata points (XAS spectra) yeboka iroro. Kune madaro akasiyana ekutsanangura macentroid ari pedyo seEuclidean distances. Pamufananidzo wekuisa px, y (x na y ari resolution muma pixels), CK ndiyo pakati pegiravhiti yeboka; mufananidzo uyu unogona kupatsanurwa (kuiswa cluster) muzvikamu zveK uchishandisa K-means63. Matanho ekupedzisira eK-means clustering algorithm ndeaya:
Danho rechipiri. Verenga huwandu hwemapikiseli ese zvichienderana ne centroid iripo. Semuenzaniso, inoverengerwa kubva padhara reEuclidean d pakati pepakati ne pixel yega yega:
Danho rechitatu: Isa pixel yega yega ku centroid iri pedyo. Wobva waverengazve nzvimbo dzeK centroid seizvi:
Danho rechina. Dzokorora maitiro aya (equations (7) uye (8)) kusvika macentroid asangana. Mhedzisiro yekupedzisira yemhando ye cluster inoenderana zvakanyanya nesarudzo yakanaka ye macentroid ekutanga63. Kune chimiro che data chePEEM chemifananidzo yesimbi, kazhinji X (x × y × λ) icube ye3D array data, nepo x ne y axes zvichimiririra ruzivo rwenzvimbo (pixel resolution) uye λ axis inoenderana ne energy spectral mode ye photons . K-means algorithm yakashandiswa kuongorora nzvimbo dzinofarira mu data re X-PEEM nekuparadzanisa ma pixel (ma clusters kana ma sub-blocks) zvichienderana nehunhu hwavo hwe spectral uye kubvisa centroid yakanakisa (XAS spectral curve) ye analyte yega yega (cluster). Inoshandiswa kudzidza spatial distribution, local spectral changes, oxidation behavior uye chemical state. Semuenzaniso, K-means clustering algorithm yakashandiswa kuFe L-edge neCr L-edge regions mu hot-worked ne cold-rolled X-PEEM. Nhamba dzakasiyana-siyana dzeK-clusters (nzvimbo dze microstructural) dzakaedzwa kuti dziwane mapoka nemacentroid akanakisa. Kana girafu yaratidzwa, mapixel anoiswazve kumacentroid akakodzera ecluster. Kugoverwa kwemavara ega ega kunoenderana nepakati pecluster, zvichiratidza kurongeka kwenzvimbo kwezvinhu zvemakemikari kana zvepanyama. Macentroid akabviswa isanganiswa yakatsetseka yemaspectra akachena.
Ruzivo runotsigira mhedzisiro yechidzidzo ichi runowanikwa kubva kumunyori weWC kana zvikakumbirwa zvine musoro.
Sieurin, H. & Sandström, R. Kusimba kwekutyoka kwesimbi isina tsvina ine duplex yakasungirirwa. Sieurin, H. & Sandström, R. Kusimba kwekutyoka kwesimbi isina tsvina ine duplex yakasungirirwa. Sieurin, H. & Sandström, R. Вязкость разрушения сварной дуплексной нержавеющей стали. Sieurin, H. & Sandström, R. Kusimba kwekutyoka kwesimbi isina tsvina yeduplex yakasungirirwa. 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. Kusimba kwekutyoka kwesimbi dzisina ngura dzakasungirirwa mbiri dzakasungirirwa.purojekiti. fractal. fur. 73, 377–390 (2006).
Adams, FV, Olubambi, PA, Potgieter, JH & Van Der Merwe, J. Kusagona ngura kwesimbi dzisina ngura mbiri muzvinhu zvakasarudzwa zve organic acids uye organic acid/chloride. Adams, FV, Olubambi, PA, Potgieter, JH & Van Der Merwe, J. Kusagona ngura kwesimbi dzisina ngura mbiri muzvinhu zvakasarudzwa zve organic acids uye organic acid/chloride.Adams, FW, Olubambi, PA, Potgieter, J. Kh. naVan Der Merwe, J. Kusagona ngura kwesimbi dzisina ngura mbiri munzvimbo dzine mamwe ma organic acids nema organic acids/chloride. 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. naVan Der Merwe, J. Kusagona ngura kwesimbi dzisina ngura mbiri munzvimbo dzine mamwe ma organic acids nema organic acids/chloride.inodzivirira ngura. Method Mater 57, 107–117 (2010).
Barella S. nevamwe. Hunhu hwekuoxidation kweFe-Al-Mn-C duplex alloys. Zvinhu 12, 2572 (2019).
Levkov, L., Shurygin, D., Dub, V., Kosyrev, K. & Balikoev, A. Chizvarwa chitsva chesimbi dzemhando yepamusoro-soro dzekugadzira michina yegesi nemafuta. Levkov, L., Shurygin, D., Dub, V., Kosyrev, K. & Balikoev, A. Chizvarwa chitsva chesimbi dzemhando yepamusoro-soro dzekugadzira michina yegesi nemafuta.Levkov L., Shurygin D., Dub V., Kosyrev K., Balikoev A. Chizvarwa chitsva chesimbi dzemhando yepamusoro dzeduplex dzemidziyo yekugadzira mafuta negasi.Levkov L., Shurygin D., Dub V., Kosyrev K., Balikoev A. Chizvarwa chitsva chesimbi dzemhando yepamusoro dzeduplex dzemidziyo yekugadzira gasi nemafuta. E3S webinar. 121, 04007 (2019).
Kingklang, S. & Uthaisangsuk, V. Kuongorora maitiro ekupisa kwesimbi isina tsvina yemhando mbiri 2507. Metall. Kingklang, S. & Uthaisangsuk, V. Kuongorora maitiro ekupisa kwesimbi isina tsvina yemhando mbiri 2507. Metall. Kingklang, S. & Uthaisangsuk, V. Исследование поведения горячей деформации дуплексной нержавеющей стали марки 2507. Metall. Kingklang, S. & Uthaisangsuk, V. Chidzidzo cheMaitiro eKuchinja Kunopisa kweSimbi Isina Kugadzirwa yeType 2507 Duplex. Metal. 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. naUtaisansuk, V. Kuferefeta Maitiro Ekupisa Ekuchinja Kwesimbi Isina Kugadzirwa yeType 2507 Duplex. Simbi.alma mater. trance. A 48, 95–108 (2017).
Zhou, T. nevamwe. Mhedzisiro yekutenderera kunotonhora kwakadzorwa pachimiro chidiki uye hunhu hwemakanika hwesimbi isina tsvina yecerium-modified super-duplex SAF 2507. alma mater. the science. project. A 766, 138352 (2019).
Zhou, T. nevamwe. Chimiro chinokonzerwa nekuchinja kwechimiro uye hunhu hwesimbi isingatsvinda yeSAF 2507 yakagadziriswa nesimbi isina tsvina. J. Alma mater. tangi rekuchengetera zvinhu. tekinoroji. 9, 8379–8390 (2020).
Zheng, Z., Wang, S., Long, J., Wang, J. & Zheng, K. Mhedzisiro yezvinhu zvisingawanzoitiki zvepasi pamaitiro ekupisa kwakanyanya kwesimbi ye austenitic. Zheng, Z., Wang, S., Long, J., Wang, J. & Zheng, K. Mhedzisiro yezvinhu zvisingawanzoitiki zvepasi pamaitiro ekupisa kwakanyanya kwesimbi ye austenitic.Zheng Z., Wang S., Long J., Wang J. naZheng K. Simba rezvinhu zvepasi zvisingawanzoitiki pamaitiro esimbi ye austenitic pasi pekupisa kwakanyanya. 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. Simba rezvinhu zvisingawanzoitiki zvepasi pamaitiro esimbi dzinoshandiswa pakupisa kwakanyanya.ngura. sainzi. 164, 108359 (2020).