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Ko te maitai kore waikura e whakamahia whānuitia ana me ōna momo whakairo he ātete ki te waikura i roto i ngā āhuatanga taiao nā te paparanga passivation kei roto ko te chromium oxide. Ko te waikura me te memeha o te maitai he mea hono ki te whakangaromanga o ēnei paparanga, engari he onge ki te putanga mai o ngā kore ōrite o te mata, i runga i te taumata moroiti. I roto i tēnei mahi, ko te rerekētanga matū o te mata nanoscale, i kitea e te karuārai tirotiro me te tātari chemometric, te mea ohorere e whakahaere ana i te pakaru me te waikura o te maitai kore waikura super duplex cerium whakarerekētia matao 2507 (SDSS) i te wā e rerekē ana te āhua. Ahakoa i whakaatuhia e te karuārai whakaahua-X he hipoki ōrite o te paparanga Cr2O3 tūturu, he ngoikore te mahi passivation o te SDSS matao nā te tohatoha ā-rohe o ngā nanoislands whai rawa Fe3+ i runga i te paparanga oxide Fe/Cr. Mā tēnei mōhiotanga tauine atomika ka whakaratohia he māramatanga hohonu mō te waikura maitai kore waikura, ā, e tumanakohia ana ka āwhina i te whawhai ki te waikura o ngā konganuku teitei-konumohe rite.
Mai i te hanganga o te maitai kore waikura, kua kīia ko ngā āhuatanga ārai-waikura o te ferrochrome nā te chromium, e hanga ana i ngā waikura/oxyhydroxides kaha, ā, e whakaatu ana i te whanonga whakangāwari i roto i te nuinga o ngā taiao. Ki te whakatauritea ki ngā maitai kore waikura tuku iho (austenitic me te ferritic) 1, 2, 3, he pai ake te ātete ki te waikura me ngā āhuatanga miihini pai rawa atu o ngā maitai kore waikura super duplex (SDSS). Mā te kaha miihini kua piki ake ka taea te hanga i ngā hoahoa māmā ake, kiato ake hoki. He rerekē, he nui te ātete o te SDSS ohanga ki te waikura pitting me te kapiti, ka roa ake te ora ratonga, ā, ka whānui ake tana tono ki te whakahaere parahanga, ki ngā ipu matū, me te umanga hinu me te hau moana4. Heoi, ko te whānuitanga whaiti o ngā pāmahana maimoatanga wera me te ngoikore o te hanganga e aukati ana i tā rātou tono whānui. Nō reira, ka whakarerekētia te SDSS hei whakapai ake i te mahi i runga ake nei. Hei tauira, i whakaurua te whakarerekētanga Ce ki te SDSS 2507 (Ce-2507) me te ihirangi hauota teitei6,7,8. He pānga pai tō te huānga whenua onge (Ce) i te kukū tika o te 0.08 wt.% ki ngā āhuatanga ā-pūkaha o te DSS, nā te mea ka whakapai ake i te whakatikatika o te witi me te kaha o te rohe witi. Ka whakapai ake hoki i te ātete ki te kakahu me te waikura, te kaha kume me te kaha hua, me te kaha mahi wera. Ka taea e te nui o te hauota te whakakapi i te nui o te nikara utu nui, ka nui ake te whai hua o te SDSS10.
Nō nā tata nei, kua whakapōturitia te SDSS kia rite ki te kirihou i ngā pāmahana rerekē (cryogenic, makariri me te wera) kia tutuki ai ngā āhuatanga miihini tino pai6,7,8. Heoi, ko te ātete waikura pai o te SDSS nā te aroaro o te kiriata waikura angiangi i runga i te mata e pāngia ana e ngā āhuatanga maha pērā i te rerekētanga ā-roto nā te aroaro o ngā āhua rerekē me ngā rohe kōpaka rerekē, ngā matū kore e hiahiatia me ngā tauhohenga rerekē.7. Nō reira, ko te ako i ngā āhuatanga rohe moroiti o aua kiriata tae noa ki te taumata o te hanganga hiko he mea nui hei mārama ki te waikura SDSS, ā, me whai tikanga whakamātautau uaua. Tae noa ki tēnei wā, ko ngā tikanga tairongo-mata pērā i te Auger electron spectroscopy11 me te X-ray photoelectron spectroscopy12,13,14,15 me te mārō X-ray photoemission microscopy (HAX-PEEM)16 kua kore e kitea ngā rerekētanga matū i roto i ngā paparanga mata. He maha ngā rangahau hou kua hono i te waikura ā-rohe o te chromium ki te whanonga waikura kua kitea o ngā maitai kore waikura austenitic17, ngā maitai martensitic18 me te SDSS19,20. Heoi, ko te arotahi matua o ēnei rangahau ko te pānga o te rerekētanga o te Cr (hei tauira, te āhua waikura Cr3+) ki te ātete waikura. Ka taea te whakaputa i te rerekētanga taha i roto i ngā āhua waikura o ngā huānga e ngā pūhui rerekē me ngā huānga ōrite, pērā i ngā waikura rino. Ko ēnei pūhui, kua riro mai i a rātou te rahi iti hei hua o te maimoatanga wera, kei te tata tetahi ki tetahi, engari he rerekē te hanganga me te āhua waikura16,21. Nō reira, kia kitea ai te pakaru o ngā kiriata waikura me te poka i muri mai, me mārama ki te rerekētanga o te mata i te taumata moroiti. Ahakoa ēnei whakaritenga, kei te ngaro tonu ngā whakatau tatauranga pērā i te rerekētanga taha i roto i te waikura, inā koa mō te Fe i te tauine nano me te atomika, ā, kāore anō kia tūhuratia tōna hononga ki te ātete waikura. Tae noa ki ēnei wā tata nei, i āta tautuhia te āhua matū o ngā momo huānga, pērā i te Fe me te Ca22, i runga i ngā tauira maitai mā te whakamahi i te karuārai whakaahua-X ngohengohe (X-PEEM) i roto i ngā whare irahiko synchrotron nanoscale. I te whakakotahitanga me te karuārai mimiti hihi-X tairongo matū (XAS), ka taea e te X-PEEM te ine i te XAS me te taumira ā-wāhi me te ā-tirohanga teitei, e whakarato ana i ngā mōhiohio matū mō te hanganga o ngā huānga me tō rātou āhua matū me te taumira ā-wāhi tae noa ki te rua tekau mā toru nanometer. . Mā tēnei tirohanga karuārai o te tīmatanga ka āwhina i ngā tirohanga matū ā-rohe, ā, ka taea te whakaatu i ngā huringa matū i roto i te wāhi o te paparanga rino kāore anō kia rangahaua i mua.
Ka whakawhānui ake tēnei rangahau i ngā painga o te PEEM ki te kite i ngā rerekētanga matū i te tauine nano, ā, ka whakaatuhia he tikanga tātari mata taumata-atomika hei mārama ki te whanonga waikura o Ce-2507. Ka whakamahia he huarahi kemometric K-means24 kua whakarōpūtia hei mahere i te ōritetanga matū (hetero) o te ao o ngā huānga e whai wāhi ana, ā, ko ō rātou āhua matū ka whakaatuhia i roto i tētahi whakaaturanga tatauranga. He rerekē ki te waikura i tīmatahia e te whakangaromanga o te kiriata waikura chromium i roto i te take tuku iho, ko te iti o te passivation me te iti o te ātete waikura e pā ana ki ngā moutere nano whai rawa Fe3+ e tata ana ki te paparanga waikura Fe/Cr, e taea ana te waiho hei āhuatanga tiaki. Ka whakangaromia e te waikura te kiriata iraira, ā, ka puta te waikura.
I arotakehia tuatahitia te whanonga waikura o te SDSS 2507 kua whakapōturitia mā te whakamahi i ngā inenga hikohiko. I te pikitia 1 e whakaatu ana i ngā kōpiko Nyquist me Bode mō ngā tauira kua tīpakohia i roto i te otinga wai waikawa (pH = 1) o FeCl3 i te pāmahana rūma. Ko te electrolyte kua tīpakohia he kaihohe waikura kaha, e whakaatu ana i te āhua o te kiriata passivation ki te pakaru. Ahakoa kāore te rauemi i pāngia e te poka pumau i te pāmahana rūma, i whakaratohia e te tātaritanga he māramatanga ki ngā takahanga rahunga pea me te waikura i muri mai. I whakamahia te ara iahiko ōrite (Pikitia 1d) hei whakauru i te whānuitanga o te inenga aukati hikohiko (EIS), ā, ko ngā hua whakauru e rite ana kei te whakaatuhia i roto i te Ripanga 1. Ka puta ngā haurua porowhita kāore i oti i roto i ngā tauira kua tukatukahia ki te otinga me te mahi wera, ko ngā haurua porowhita kua kōpekehia ka puta i roto i ngā tauira kua hurihia matao (Pikitia .1b). I roto i te inenga EIS, ka taea te whakaaro ko te radius o te haurua porowhita ko te ātete polarization (Rp)25,26. Ko te Rp o te ara rere i tukatukahia ki te otinga i roto i te Ripanga 1 e tata ana ki te 135 kΩ cm–2, heoi, he iti iho ngā uara o te ara rere i mahi-wera me te ara rere i hurihia-matao, 34.7 me te 2.1 kΩ cm–2, ia. Ko tēnei whakahekenga nui i roto i te Rp e whakaatu ana i te pānga kino o te whakarerekētanga kirihou ki te ātete ki te kore e pāngia me te waikura, e ai ki ngā pūrongo o mua27,28,29,30.
a Nyquist, b, c Ngā hoahoa aukati me ngā āhuahanga o Bode, me d ngā tauira ara iahiko ōrite e rite ana, ko RS te ātete irahiko, ko Rp te ātete whakapūmau, ā, ko QCPE te waikura o te huānga āhuahanga pumau e whakamahia ana hei whakatauira i te kaha kore-pai (n). Ka mahia ngā inenga EIS i te pūmanawa ara iahiko tuwhera.
Kei te whakaaturia ngā pūmau wā kotahi i roto i te kauwhata Bode, me te papatahi i roto i te awhe auau teitei e tohu ana i te ātete electrolyte RS26. I te hekenga o te auau, ka piki ake te aukati, ā, ka kitea he koki āhua kino, e tohu ana i te mana o te capacitance. Ka piki ake te koki āhua, ka mau tonu te mōrahi i runga i te awhe auau whānui, kātahi ka heke iho (Pikitia 1c). Heoi, i roto i ngā take e toru, kei raro tonu tēnei mōrahi i te 90°, e tohu ana i te whanonga capacitive kore-tino pai nā te marara capacitive. Nō reira, ka whakamahia te huānga āhua pūmau QCPE (CPE) hei tohu i ngā tohatoha capacitance atanga e puta mai ana i te taratara o te mata, i te kore-ōrite rānei, inā koa i te tauine atomika, te āhua fractal, te porosity electrode, te pūmanawa kore-ōrite, me te āhua me te āhua o ngā electrodes31,32. Āraitanga CPE:
ko j te tau pohewa, ā, ko ω te auau koki. Ko te QCPE he pūmau auau motuhake e rite ana ki te horahanga tuwhera whai hua o te electrolyte. Ko n he tau mana kore-ahu e whakaahua ana i te rerekētanga o te capacitor mai i te capacitance tino pai, arā, ko te tata atu o n ki te 1, ko te tata atu o te CPE ki te capacitive tino pai, engari ki te tata a n ki te kore, ka puta he ātete. Ko ngā rerekētanga iti o n, e tata ana ki te 1, e tohu ana i te whanonga capacitive kore-tino pai o te mata i muri i ngā whakamātautau polarization. Ko te QCPE o te SDSS hurihuri matao he teitei ake i ōna hoa, ko te tikanga he iti ake te ōrite o te kounga o te mata.
E rite ana ki te nuinga o ngā āhuatanga ātete waikura o ngā maitai kore waikura, ko te nui o te ihirangi Cr o te SDSS ka hua ake he ātete waikura pai rawa atu o te SDSS nā te mea he kiriata waikura tiaki pāhekoheko kei runga i te mata17. He nui ngā waikura Cr3+ me/ranei ngā hauwaiora i roto i aua kiriata pāhekoheko, ko te nuinga he mea hono atu ki ngā waikura Fe2+, Fe3+ me/ranei ngā (oxy)hauwaiora33. Ahakoa te ōrite o te mata, te paparanga waikura pāhekoheko, me te kore e kitea he pakaru o te mata e ai ki ngā inenga moroiti6,7, he rerekē te whanonga waikura o te SDSS mahi-wera me te SDSS huri-matao, nō reira me rangahau hōhonu ngā āhuatanga hanganga moroiti mō te whakarerekētanga o te maitai.
I rangahauhia te hanganga moroiti o te maitai kore waikura kua whakapōturitia mā te whakamahi i ngā hihi-X kaha-teitei o roto me te synchrotron (Ngā Pikitia Tāpiri 1, 2). Kei roto i ngā Mōhiohio Tāpiri he tātaritanga taipitopito. Ahakoa he whakaae whānui mō te momo wāhanga matua, i kitea ngā rerekētanga o ngā wāhanga wāhanga papatipu, e whakarārangihia ana i roto i te Ripanga Tāpiri 1. Tērā pea nā ngā wāhanga wāhanga kore-ōrite i te mata me te rōrahi ēnei rerekētanga, e pāngia ana e ngā hohonutanga kitenga hihi-X (XRD) rerekē. ) me ngā pūtake pūngao rerekē o ngā photon taupatupatu34. Ko ngā wāhanga austenite teitei i roto i ngā tauira hurihuri matao i whakatauhia e te XRD mai i tētahi pūtake taiwhanga e tohu ana i te pai ake o te passivation me te ātete waikura pai ake35, ko ngā hua tika ake me ngā hua tatauranga e tohu ana i ngā au rerekē i roto i ngā wāhanga wāhanga. Hei tāpiri, ko te ātete waikura o te maitai e whakawhirinaki ana hoki ki te nui o te whakamahine o te witi, te whakaiti i te rahi o te witi, te pikinga o ngā microdeformations me te kiato nekehanga e puta ana i te wā maimoatanga wera36,37,38. Ko ngā tauira i mahi werahia he āhua kirikiri ake, e tohu ana i ngā kirikiri he rahi-micron, ko ngā mowhiti maeneene i kitea i roto i ngā tauira i hurihia matao (Pikitia Tāpiri 3) he tohu mō te whakatikatika nui o te kirikiri ki te rahi-nano i ngā mahi o mua. Me āwhina tēnei i te hanganga kiriata kore mahi me te pikinga ake o te ātete ki te waikura. Ko te nui ake o te kiato nekehanga he mea hono ki te iti ake o te ātete ki te poka, e rite ana ki ngā inenga hikohiko.
I tirotirohia ngā panonitanga o te āhua matū o ngā rohe moroiti o ngā huānga matua mā te whakamahi i te X-PEEM. Ahakoa he nui ake ngā huānga whakarewa, ko Cr, Fe, Ni me Ce39 ngā mea i whiriwhiria i konei, nā te mea ko Cr te huānga matua mō te hanga i te kiriata kore mahi, ko Fe te huānga matua mō te maitai, ā, ka whakarei ake a Ni i te kore mahi, ā, ka taurite i te wāhanga ferrite-austenitic. Ko te hanganga me te whakarerekētanga te kaupapa o Ce. Mā te whakatikatika i te kaha hihi synchrotron, i hopukina e XAS ngā āhuatanga matua o Cr (taha L2.3), Fe (taha L2.3), Ni (taha L2.3), me Ce (taha M4.5) mai i te mata. -2507 SDSS. I mahia te tātari raraunga tika mā te whakauru i te whakatikatika pūngao me ngā raraunga kua whakaputaina (hei tauira, XAS i runga i te Fe L2, 3 rara40,41).
Kei te pikitia. E whakaatu ana te Pikitia 2 i ngā whakaahua X-PEEM o te Ce-2507 SDSS kua wera-mahi (Pikitia 2a) me te Ce-2507 SDSS kua hurihia-matao (Pikitia 2d) me ngā taha XAS Cr me Fe L2,3 e rite ana i ngā tūranga kua tohua takitahi. Ka tūhuratia e te taha L2,3 XAS ngā āhua 3d korekore o ngā irahiko i muri i te whakahihiko whakaahua i ngā taumata wehewehenga porowhita-hurihuri 2p3/2 (taha L3) me 2p1/2 (taha L2). I riro mai ngā mōhiohio mō te āhua valence o Cr mai i te tātaritanga diffraction hihi-X o te taha L2,3 i te Pikitia 2b,d. Whakatairite hononga. I whakaatuhia e te 42, 43 e whā ngā tihi A (578.3 eV), B (579.5 eV), C (580.4 eV), me D (582.2 eV) i kitea tata ki te taha L3, e whakaata ana i ngā iona Cr3+ octahedral, Cr2O3 e rite ana. E rite ana ngā irahiko whakamātautau ki ngā tātaitanga ariā, e whakaaturia ana i ngā panera b me e, i riro mai i ngā tātaitanga mara tioata maha i te atanga Cr L2.3 mā te whakamahi i te mara tioata o te 2.0 eV44. E pania ana ngā mata e rua o te SDSS wera-mahi me te matao-hurihuri ki tētahi paparanga Cr2O3 ōrite.
he Whakaahua wera o te SDSS wera-hanga X-PEEM e rite ana ki te taha b Cr L2.3 me te taha c Fe L2.3, d Whakaahua wera X-PEEM o te SDSS matao-hurihia e rite ana ki te taha e Cr L2.3 me te taha f Fe L2.3 o te taha (e). Ko ngā hihi XAS kua tuhia ki ngā tūranga ā-wāhi rerekē kua tohua ki ngā whakaahua wera (a, d) e ngā rārangi ira karaka i roto i te (b) me te (e) e tohu ana i ngā hihi XAS kua whakatauirahia o Cr3+ me te uara mara tioata o te 2.0 eV. Mō ngā whakaahua X-PEEM, ka whakamahia he papatae wera hei whakapai ake i te ngāwari o te pānui whakaahua, ko ngā tae mai i te kikorangi ki te whero he rite ki te kaha o te mimiti hihi-X (mai i te iti ki te teitei).
Ahakoa te taiao matū o ēnei huānga whakarewa, i noho tonu te āhua matū o ngā tāpiringa o ngā huānga whakarewa Ni me Ce mō ngā tauira e rua. He tuhi tāpiri. I te pikitia 5-9, whakaaturia ngā whakaahua X-PEEM me ngā hihi XAS e rite ana mō Ni me Ce i ngā tūranga rerekē i runga i te mata o ngā tauira wera-mahi me ngā tauira matao-hurihuri. E whakaatu ana a Ni XAS i te āhua waikura o Ni2+ i runga i te mata katoa i inehia o ngā tauira wera-mahi me ngā tauira matao-hurihuri (Kōrero Tāpiri). He mea nui kia mōhiotia, i roto i te take o ngā tauira wera-mahi, kāore te tohu XAS o Ce e kitea, engari ko te hihi o Ce3+ o ngā tauira matao-hurihuri e kitea ana i tētahi wāhi. Ko te kitenga o ngā ira Ce i roto i ngā tauira matao-hurihuri i whakaatu ko te Ce te nuinga kei roto i te āhua o ngā matūriki.
I roto i te SDSS kua whakarerekētia te āhua wera, kāore i kitea he huringa hanganga ā-rohe i roto i te XAS i te taha Fe L2.3 (Pikitia 2c). Heoi, e ai ki te pikitia 2f, ka huri te āhua matū o te matrix Fe i roto i te moroiti i ngā pūwāhi e whitu kua tīpakohia matapōkeretia i roto i te SDSS kua hurihia matao. Hei tāpiri, kia tika ai te whakaaro mō ngā huringa o te āhua o te Fe i ngā wāhi kua tīpakohia i roto i te Pikitia 2f, i whakahaerehia ngā rangahau mata ā-rohe (Pikitia 3 me te Pikitia Tāpiri 10) i reira i tīpakohia ai ngā rohe porowhita iti ake. I whakatauirahia ngā hihi XAS o te taha Fe L2,3 o ngā pūnaha α-Fe2O3 me ngā waikura octahedral Fe2+ mā te whakamahi i ngā tātaitanga mara karaihe maha mā te whakamahi i ngā mara karaihe o te 1.0 (Fe2+) me te 1.0 (Fe3+)44. E kite ana mātou he rerekē ngā ōrite ā-rohe o α-Fe2O3 me γ-Fe2O345,46, kei te Fe3O4 te huinga o te Fe2+ me te Fe3+,47, ā, ko te FeO45 he waikura Fe2+ takirua ā-ahua (3d6). E kite ana mātou he rerekē ngā ōritetanga ā-rohe o α-Fe2O3 me γ-Fe2O345,46, he huinga o Fe2+ me Fe3+ a Fe3O4,47, ā, ko FeO45 he waikura Fe2+ takirua ā-ahua (3d6).Kia mōhio koe he rerekē ngā ōrite ā-rohe o α-Fe2O3 me γ-Fe2O345,46, ka whakakotahi a Fe3O4 i te Fe2+ me te Fe3+,47 me te FeO45 i roto i te āhua o te waikura Fe2+ (3d6) he rite te rahi ki te rua.Kia mōhio koe he rerekē ngā ōrite ā-rohe o α-Fe2O3 me γ-Fe2O345,46, he huinga Fe2+ me Fe3+ a Fe3O4,47 ā, ko te FeO45 te mea e mahi ana hei waikura Fe2+ takirua ōkawa (3d6). Ko ngā iona Fe3+ katoa i roto i te α-Fe2O3 he tūranga Oh anake, ko te γ-Fe2O3 ia e whakaatuhia ana ko te Fe3+ t2g [Fe3+5/3V1/3]eg O4 spinel me ngā wāhi takoto kau i roto i ngā tūranga eg. Nō reira, ko ngā iona Fe3+ i roto i te γ-Fe2O3 he tūranga Td me Oh. E ai ki te kōrero i roto i te mahi o mua, ahakoa he rerekē ngā ōwehenga kaha o te rua, ko te ōwehenga kaha eg/t2g he ≈1, ko te ōwehenga kaha eg/t2g i kitea i tēnei wā he tata ki te 1. Mā tēnei ka whakakorea te tūponotanga ko te Fe3+ anake kei roto i tēnei wā. Ina whakaarohia te take o te Fe3O4 me ngā huinga o te Fe2+ me te Fe3+, e mōhiotia ana ko te āhuatanga tuatahi ngoikore (kaha) i te taha L3 o te Fe e tohu ana i te iti (nui) o te kore noho i roto i te āhua t2g. E pā ana tēnei ki te Fe2+ (Fe3+), e tohu ana i te pikinga o te tohu tuatahi e tohu ana i te pikinga o te ihirangi o te Fe2+47. E whakaatu ana ēnei hua ko te Fe2+ me te γ-Fe2O3, α-Fe2O3 me/ranei te Fe3O4 te mea nui i runga i ngā mata hurihuri matao o ngā mea honohono.
Ngā whakaahua wera irahiko tukunga whakaahua kua whakanuia o ngā irahiko XAS (a, c) me (b, d) puta noa i te taha Fe L2,3 i ngā tūranga ā-wāhi rerekē i roto i ngā rohe kua tohua 2 me E i roto i ngā Pikitia 2d.
I tuhia ngā raraunga whakamātautau i whiwhihia (Pikitia 4a me te Pikitia Tāpiri 11) ā, i whakaritea ki ngā raraunga o ngā pūhui parakore 40, 41, 48. Ko te tikanga, e toru ngā momo ira XAS taha-L Fe i tirohia i roto i te whakamātautau (XAS-1, XAS-2 me XAS-3: Pikitia 4a) i kitea i ngā wāhi rerekē o te wāhi. Ina koa, i kitea he ira rite ki te 2-a (e tohuhia ana ko XAS-1) i roto i te Pikitia 3b puta noa i te rohe katoa e hiahiatia ana, ā, i muri mai ko te ira 2-b (e tohuhia ana ko XAS-2), i te mea i kitea he ira rite ki te E-3 i roto i te Pikitia 3d (e kiia ana ko XAS-3) i kitea i roto i ētahi wāhi ā-rohe. I te nuinga o te wā, e whā ngā tawhā e whakamahia ana hei tautuhi i ngā āhua uara kei roto i te tauira tirotiro: (1) ngā āhuatanga ira L3 me L2, (2) ngā tūranga pūngao o ngā āhuatanga L3 me L2, (3) te rerekētanga pūngao L3-L2, (4) te ōwehenga kaha L2 /L3. E ai ki ngā tirohanga ā-kanohi (Pikitia 4a), kei runga i te mata o te SDSS i rangahauhia ngā wāhanga Fe e toru, arā, ko te Fe0, ko te Fe2+, me te Fe3+. I tohu anō hoki te ōwehenga kaha L2/L3 i te aroaro o ngā wāhanga e toru.
a I kitea ngā raraunga whakamātautau rerekē e toru (ko ngā rārangi totoka XAS-1, XAS-2 me XAS-3 e rite ana ki te 2-a, 2-b me E-3 i te Pikitia 2 me te Pikitia 3) i whakaritea ki ngā XAS whakaata. Whakataurite i ngā ira, ngā uara octahedron Fe2+, Fe3+, ngā uara mara tioata o te 1.0 eV me te 1.5 eV, ia, b–d I ine i ngā raraunga whakamātautau (XAS-1, XAS-2, XAS-3) me ngā raraunga LCF arotau e rite ana (rārangi pango totoka), me te whakataurite i ngā ira XAS-3 me ngā paerewa Fe3O4 (āhua whakauru o Fe) me Fe2O3 (Fe3+ parakore).
I whakamahia he huinga raina (LCF) o ngā paerewa e toru40,41,48 hei ine i te hanganga o te waikura rino. I whakatinanahia te LCF mō ngā ira XAS taha-L e toru kua tīpakohia e whakaatu ana i te rerekētanga teitei rawa atu, arā, ko XAS-1, XAS-2 me XAS-3, e whakaaturia ana i te Pikitia 4b–d. Mō ngā hononga LCF, i whakaarohia te 10% Fe0 i ngā wā katoa nā te iti o te papa i kitea e mātou i roto i ngā raraunga katoa me te meka ko te konganuku ferrous te wāhanga matua o te maitai. Ina hoki, ko te hohonutanga whakamātautau o X-PEEM mō te Fe (~6 nm)49 he nui ake i te matotoru o te paparanga waikura i whakatauhia (he paku neke atu i te 4 nm), e āhei ai te kite i te tohu mai i te whāriki rino (Fe0) i raro i te paparanga whakakorekore. Ina hoki, ko te hohonutanga whakamātautau o X-PEEM mō te Fe (~6 nm)49 he nui ake i te matotoru o te paparanga waikura i whakatauhia (he paku neke atu i te 4 nm), e āhei ai te kite i te tohu mai i te whāriki rino (Fe0) i raro i te paparanga whakakorekore. Действительно, пробная глубина X-PEEM для Fe (~ 6 нм)49 больше, чем предполагаемая толщина слоя окисления (> 4 ночпольного) обнаружить сигнал от железной матрицы (Fe0) под пассивирующим слоем. Ina hoki, ko te hohonutanga o te X-PEEM probe mō te Fe (~6 nm)49 he nui ake i te matotoru e whakaarohia ana o te paparanga waikura (he paku >4 nm), e taea ai te kite i te tohu mai i te matrix rino (Fe0) i raro i te paparanga passivation.Ina hoki, ka kitea e X-PEEM te Fe (~6 nm)49 i te hohonu atu i te matotoru e tumanakohia ana o te paparanga waikura (neke atu i te 4 nm), ka taea ai te kite i ngā tohu mai i te whāriki rino (Fe0) i raro i te paparanga whakawātea. I mahia ngā huinga maha o Fe2+ me Fe3+ hei kimi i te otinga pai rawa atu mō ngā raraunga whakamātautau i kitea. I runga i te pikitia. E whakaatu ana te Pikitia 4b i te huinga o Fe2+ me Fe3+ i roto i te whānuitanga XAS-1, kei reira ngā ōwehenga o Fe2+ me Fe3+ e tata ana, tata ki te 45%, e tohu ana i te āhua waikura whakauru o Fe. Engari mō te whānuitanga XAS-2, ka ~30% me te 60% te ōrau o Fe2+ me Fe3+, ia. He iti ake te ihirangi o Fe2+ i tērā o Fe3+. Ko te ōwehenga Fe2+ ki Fe3 o te 1:2 e tohu ana ka taea te hanga Fe3O4 i te ōwehenga kotahi o ngā katote Fe. Hei tāpiritanga, mō te whānuitanga XAS-3, i huri ngā ōrau o Fe2+ me Fe3+ ki ~10% me te 80%, e tohu ana i te huringa teitei ake o Fe2+ ki Fe3+. E ai ki te kōrero i runga ake nei, ka taea e Fe3+ te ahu mai i te α-Fe2O3, γ-Fe2O3, Fe3O4 rānei. Hei mārama ki te pūtake tino pea o Fe3+, ka tuhia ngā whānuitanga XAS-3 me ngā paerewa Fe3+ rerekē i te Pikitia 4e e whakaatu ana i te ōritetanga ki ngā paerewa e rua ina whakaarohia te Tihi B. Heoi, ko te kaha o te pakihiwi (A: mai i Fe2+) me te ōwehenga kaha B/A e tohu ana ko te whānuitanga o XAS-3 he tata ki te whānuitanga o γ-Fe2O3 engari kāore i te rite. Ki te whakatauritea ki te papatipu γ-Fe2O3, he paku teitei ake te kaha o te Fe 2p XAS o te tihi A SDSS (Pikitia 4e), e tohu ana i te kaha ake o te Fe2+. Ahakoa he rite te whānuitanga o XAS-3 ki tērā o γ-Fe2O3, kei reira a Fe3+ i ngā tūranga Oh me Td, he raruraru tonu te tautuhi i ngā āhua valence rerekē me te taunga mā te taha L2,3, mā te ōwehenga kaha L2/L3 rānei. He kaupapa kōrero e puta tonu ana nā te uaua o ngā āhuatanga rerekē e whai wāhi ana ki te whānuitanga whakamutunga41.
Haunga te wehewehe i ngā āhua matū o ngā rohe whai pānga kua tohua i runga ake nei, i aromatawaihia te rerekētanga matū ā-ao o ngā huānga matua Cr me Fe mā te whakarōpū i ngā ira XAS katoa i whiwhihia i runga i te mata tauira mā te whakamahi i te tikanga whakarōpū K-means. I whakatakotoria ngā kōtaha taha Cr L kia puta ai he rua ngā tautau tino pai kua tohatohahia ā-wāhi i roto i ngā tauira wera-mahi me ngā tauira matao-hurihuri e whakaaturia ana i ngā Pikitia 5. E mārama ana kāore i kitea he huringa hanganga ā-rohe, nā te mea he tino ōrite ngā pokapū e rua o ngā ira XAS Cr. He tata rite tonu ēnei āhua ira o ngā tautau e rua ki ērā e rite ana ki a Cr2O342, ko te tikanga he ōrite te tohatoha o ngā paparanga Cr2O3 puta noa i te SDSS.
he rōpū o ngā rohe taha-L Cr e tohu ana i te K, b ngā ​​pokapū XAS e rite ana. Ngā hua o te whakatairite X-PEEM K-tikanga o te SDSS hurihuri-makariri: c ngā rōpū o ngā rohe taha-K o te Cr L2,3 me d ngā pokapū XAS e rite ana.
Hei whakaatu i tētahi mahere taha FeL matatini ake, e whā me e rima ngā tautau kua arotauhia me ō rātou pokapū e pā ana (ngā tohatoha āwhata) e whakamahia ana mō ngā tauira mahi-wera me ngā tauira huri-matao. Nō reira, ka taea te whiwhi i te ōrau (%) o Fe2+ me Fe3+ mā te whakarerekē i te LCF e whakaaturia ana i te Pikitia 4. Ko te pūmanawa pseudoelectrode Epseudo hei mahi a Fe0 i whakamahia hei whakaatu i te kore-ōrite matū moroiti o te kiriata waikura mata. Ka whakatauhia tata te Epseudo e te ture whakaranu,
ko \(\rm{E}_{\rm{Fe}/\rm{Fe}^{2 + (3 + )}}\) he rite ki te \(\rm{Fe} + 2e^ – \to\rm { Fe}^{2 + (3 + )}\), arā, ko te 0.440 me te 0.036 V. Ko ngā wāhi he iti ake te pūmanawa he nui ake te ihirangi o ngā matū Fe3+. Ko te tohatoha pūmanawa i roto i tētahi tauira kua whakarerekētia te pāmahana he āhua paparanga me te huringa mōrahi o te 0.119 V (Pikitia 6a,b). He hononga tata tēnei tohatoha pūmanawa ki te āhua o te mata (Pikitia 6a). Kāore i kitea ētahi atu huringa e pā ana ki te tūranga i roto i te roto lamellar o raro (Pikitia 6b). Engari, mō te whakakotahitanga o ngā waikura rerekē me ngā ihirangi rerekē o Fe2+ me Fe3+ i roto i te SDSS hurihuri-makariri, ka kitea he āhua kore-ōrite o te pūmanawa rūpahu (Pikitia 6c, d). Ko ngā waikura Fe3+ me/ranei ngā waikura (oxy) ngā wāhanga matua o te waikura i roto i te maitai, ā, ka taea te uru ki te hāora me te wai50. I tēnei take, ka kitea ko ngā moutere whai rawa i te Fe3+ kua horapa ā-rohe, ā, ka taea te whakaaro he wāhi waikura. I tēnei take, ko te pikinga i roto i te mara pūmanawa, kaua ki te uara tino o te pūmanawa, ka taea te whakaaro hei tohu mō te wāhi o ngā rohe waikura hohe51. Ka taea e tēnei tohatoha kore-ōrite o te Fe2+ me te Fe3+ i runga i te mata o te SDSS hurihuri makariri te whakarerekē i ngā āhuatanga matū ā-rohe, me te whakarato i tētahi horahanga mata whai hua ake i roto i te pakaru kiriata waikura me ngā tauhohenga waikura, kia taea ai e te anga whakarewa o raro te waikura tonu, ka hua ake he kore-ōrite o roto. me te whakaiti i ngā āhuatanga tiaki o te paparanga whakawhiti.
Ngā tautau K-toharite o ngā rohe taha Fe L2,3 me ngā pokapū XAS e rite ana mō te a–c X-PEEM wera-mahi me te d–f SDSS matao-hurihuri. Kauwhata tautau a, d K-means kua whakakikoruatia ki te ahua X-PEEM. Kua whakahuatia ngā pūmanawa pseudoelectrode kua whakatauhia (epseudo) me ngā hoahoa tautau K-means. He rite tonu te kanapa o te ahua X-PEEM pēnei i te tae i te Pikitia 2 ki te kaha mimiti hihi-X.
Ko te Cr ōrite engari he rerekē te āhua matū o te Fe ka rerekē te pūtake o te pakaru o te kiriata waikura me ngā tauira waikura i roto i te Ce-2507 hurihuri-wera me te Ce-2507 hurihuri-matao. E mōhiotia whānuitia ana tēnei āhuatanga o te Ce-2507 hurihuri-matao. Mō te hanganga o ngā waikura me ngā hauwai o te Fe i roto i te hau o te āhuarangi, ko ngā tauhohenga e whai ake nei ka katihia i roto i tēnei mahi hei tauhohenga kūpapa:
I runga i te inenga o te X-PEEM, i puta te tauhohenga i runga ake nei i ngā take e whai ake nei. He pakihiwi iti e rite ana ki te Fe0 e hono ana ki te rino whakarewa kei raro. Ko te tauhohenga o te Fe whakarewa ki te taiao ka arahi ki te hanganga o te paparanga Fe(OH)2 (whārite (5)), e whakanui ana i te tohu Fe2+ i roto i te XAS o te taha L o te Fe. Ko te roa o te noho ki te hau ka hua ake te hanganga o ngā waikura Fe3O4 me/ranei Fe2O3 i muri i te Fe(OH)252,53. E rua ngā momo Fe pumau, ko te Fe3O4 me te Fe2O3, ka taea hoki te hanga i roto i te paparanga tiaki whai rawa i te Cr3+, kei reira te Fe3O4 e pai ake ai ki te hanganga ōrite me te piri. Ko te noho o ngā mea e rua ka hua ake he āhua waikura whakauru (āwhiowhio XAS-1). Ko te āwhiowhio XAS-2 e rite ana ki te Fe3O4. Ko ngā āwhiowhio XAS-3 i kitea i ētahi tūranga i tohu i te huringa katoa ki te γ-Fe2O3. Nā te mea he tata ki te 50 nm te hohonutanga o te werohanga o ngā hihi-X kāore i takaihia, ka hua ake te kaha ake o te tihi A i te tohu mai i te paparanga o raro.
E whakaatu ana te whānuitanga XRD he hanganga paparanga tō te wāhanga Fe i roto i te kiriata waikura, e honoa ana ki te paparanga waikura Cr. He rerekē ki te āhuatanga whakangāwari o te waikura nā te kore ōrite o te rohe o Cr2O317, ahakoa te paparanga ōrite o Cr2O3 i roto i tēnei rangahau, i kitea he iti te ātete waikura i tēnei take, inā koa mō ngā tauira hurihuri-matao. Ka taea te mārama ki te whanonga i kitea ko te rerekētanga o te āhua waikura matū o te paparanga o runga (Fe) e pā ana ki te mahi waikura. Ko te whakawhiti puhoi o ngā katote whakarewa, hāora rānei i roto i te whatunga nā te stoichiometry ōrite o ngā paparanga o runga (waikura Fe) me raro (waikura Cr)52,53 ka arahi ki te taunekeneke pai ake (piripiri) i waenganui i a rātou. Mā tēnei ka whakapai ake i te ātete waikura. Nō reira, he pai ake te stoichiometry tonu, arā, kotahi te āhua waikura o Fe, i ngā huringa stoichiometric ohorere. He mata ōrite ake te SDSS kua whakarerekētia te wera me te paparanga tiaki kiato ake, e whakarato ana i te ātete waikura pai ake. Heoi, mō te SDSS hurihuri-matao, ko te noho mai o ngā moutere whai rawa i te Fe3+ i raro i te paparanga tiaki ka whakangaro i te āhua o te mata, ā, ka puta te waikura karawaka o te papa tata, ka heke te Rp (Ripanga 1) i roto i ngā hihi EIS me tōna ātete waikura. Nō reira, ko ngā moutere kua horapa ā-rohe whai rawa i te Fe3+ nā te whakarerekētanga kirihou te mea nui hei awe i te mahi ātete waikura, he mea hou tēnei i roto i tēnei mahi. Nō reira, ka whakaatuhia e tēnei rangahau ngā whakaahua hikohiko o te whakahekenga o te ātete waikura nā te whakarerekētanga kirihou o ngā tauira SDSS i akohia.
I tua atu, ahakoa he pai ake te mahi a te whakarewa whenua onge i roto i ngā maitai takirua-wāhanga, kāore tonu i te kitea te taunekeneke o tēnei huānga tāpiri me te mata maitai takitahi e pā ana ki te whanonga waikura i runga i ngā tirohanga karuārai. Ka puta noa te tohu Ce (i te taha-M o te XAS) i ētahi tūranga i te wā e hurihuri makariri ana, engari ka ngaro i te wā e whakarerekētia ana te SDSS i te wera, e tohu ana i te whakatakotoranga ā-rohe o te Ce i roto i te mata maitai hei utu mō te whakarewa ōrite. Ahakoa kāore i te pai ake ngā āhuatanga hangarau o te SDSS6,7, ka whakaitihia e te aroaro o te REE te rahi o ngā whakaurunga, ā, e whakaarohia ana ka pehi i te poka i te pūtake54.
Hei whakamutunga, e whakaatu ana tēnei mahi i te pānga o te rerekētanga o te mata ki te waikura o te 2507 SDSS i whakarerekētia ki te cerium mā te ine i te ihirangi matū o ngā wāhanga nanoscale. I whakautua e mātou te pātai he aha te take e waikura ai te maitai kore waikura ahakoa kua pania ki te paparanga waikura tiaki mā te ako i te hanganga moroiti, te āhua matū o ngā āhuatanga mata me te tukatuka tohu mā te whakamahi i te whakarōpū K-means. Kua whakapumautia ko ngā moutere whai rawa i te Fe3+, tae atu ki ō rātou taunga octahedral me te tetrahedral puta noa i te hanganga o te Fe2+/Fe3+ whakauru, he pūtake o te whakangaromanga kiriata waikura me te pūtake o te waikura o te SDSS hurihuri-makariri. Ko ngā moutere nanoscale e whakahaerehia ana e te Fe3+ ka arahi ki te ātete waikura ngoikore ahakoa kei te aroaro o te paparanga Cr2O3 stoichiometric. Haunga ngā whanaketanga tikanga i mahia ki te whakatau i te pānga o te rerekētanga matū nanoscale ki te waikura, e tumanakohia ana ka whakaohohia e tēnei mahi ngā tukanga hangarau ki te whakapai ake i te ātete waikura o ngā maitai kore waikura i te wā hanga maitai.
Hei whakarite i ngā poro Ce-2507 SDSS i whakamahia i roto i tēnei rangahau, ko ngā wāhanga whakauru, tae atu ki te koranu matua Fe-Ce kua hiritia ki ngā ngongo rino parakore, i rewahia ki roto i te oumu whakapūngao auau reo 150 kg hei whakaputa i te maitai rewa, ā, i ringihia ki roto i ngā pokepoke whakarewa. Ko ngā hanganga matū i inehia (wt %) kua whakarārangihia ki te Ripanga Tāpiri 2. Ka hangaia te poro ki te wera tuatahi hei poraka. Kātahi ka whakamahanahia te maitai i te 1050°C mō te 60 meneti kia puta he wai totoka, kātahi ka tineia ki te wai kia tae ki te pāmahana rūma. I akohia ngā tauira i akohia mā te whakamahi i te TEM me te DOE hei ako i ngā āhua, te rahi o te witi me te āhua. Ka kitea ētahi atu kōrero taipitopito mō ngā tauira me te tukanga whakaputa i roto i ētahi atu puna6,7.
Tukatukahia ngā tauira porotaka (φ10 mm × 15 mm) mō te pēhi wera me te tuaka o te rango e whakarara ana ki te ahunga whakarerekētanga o te poraka. I mahia te pēhi pāmahana teitei i te tere taumahatanga pumau i te awhe o te 0.01-10 s-1 i ngā pāmahana rerekē i te awhe o te 1000-1150°C mā te whakamahi i te tauira wera Gleeble-3800. I mua i te whakarerekētanga, i whakamahanahia ngā tauira i te pāmahana i tīpakohia i te tere o te 10 °C s-1 mō te 2 meneti hei whakakore i te pikinga pāmahana. I muri i te whakatutukitanga o te ōritetanga pāmahana, i whakarerekētia ngā tauira ki te uara taumahatanga pono o te 0.7. I muri i te whakarerekētanga, ka tineia tonutia ki te wai hei pupuri i te hanganga whakarerekētanga. Kātahi ka tapahia ngā tauira kua whakapakeketia kia whakarara ki te ahunga pēhitanga. Mō tēnei rangahau, i whiriwhiria e mātou he tauira i whakarerekētia i te pāmahana i te 1050°C, 10 s-1 nā te mea he nui ake te pakeke o te moroiti i kitea i ētahi atu tauira7.
I whakamātauria ngā tauira papatipu (80 × 10 × 17 mm3) o te otinga totoka Ce-2507 i runga i tētahi mīhini whakarerekētanga huri-rua ā-wāhanga-toru LG-300, ā, koinei te mīhini i whakarato i ngā āhuatanga hangarau pai rawa atu i roto i ngā akomanga whakarerekētanga katoa6. Ko te tere taumahatanga me te whakaiti matotoru he 0.2 m·s-1 me te 5% mō ia ara, ia.
I whakamahia he teihana mahi hikohiko Autolab PGSTAT128N hei ine i te SDSS mā te hikohiko i muri i te hurihuri matao ki te 90% te whakaiti matotoru (1.0 te taumahatanga tūturu ōrite) me te pēhi wera ki te 0.7 te taumahatanga tūturu i te 1050 oC me te 10 s-1. He pūtau hiko-toru kei te teihana mahi me te hikohiko calomel kua kōtui hei hikohiko tohutoro, he hikohiko kaute karāhe, me te tauira SDSS hei hikohiko mahi. I tapahia ngā tauira ki roto i ngā rango me te diameter o te 11.3 mm, ā, ki ngā taha i whakapirihia ai ngā waea parahi. Kātahi ka ringihia te tauira ki te kapia epoxy, ka waiho he wāhi tuwhera mahi 1 cm2 hei hikohiko mahi (te mata o raro o te tauira porotaka). Kia tūpato i te wā e whakamaroke ana i te epoxy me te wā e whai ake nei te oro me te whakakanapa kia kore ai e pakaru. Ka pania te mata mahi ki te whakatārewatanga whakakanapa taimana me te rahi matūriki o te 1 micron, ka horoia ki te wai whakapūkara me te etanoru, ā, ka whakamarokehia ki te hau matao. I mua i ngā inenga hikohiko, i whakaatuhia ngā tauira kua whakakanapa ki te hau mō ētahi rā hei hanga i tētahi kiriata waikura tūturu. Kua whakamahia he otinga wai o te FeCl3 (6.0 wt.%), i whakapūmautia ki te HCl ki te pH = 1.0 ± 0.01, hei whakatere i te waikura o te kowiri tira 55, nā te mea ka kitea i roto i ngā taiao kaha kei reira ngā katote kōhaita me te kaha whakahāwea kaha me te pH iti e ai ki te ASTM. Ko ngā paerewa kua whakaarohia ko te G48 me te A923. I rumakina ngā tauira ki roto i te otinga whakamātautau mō te 1 hāora i mua i te tango i ngā inenga kia tae atu ki te āhua e tata ana ki te tūmau. Mō ngā tauira otinga totoka, ngā tauira mahi-wera me ngā tauira hurihuri-matao, ko te whānuitanga auau ine ātete he 1 × 105 ~ 0.1 Hz, ā, ko te pūmanawa ara iahiko tuwhera (OPS) he 5 mV, arā, 0.39, 0.33, me te 0.25 VSCE. I tuaruatia ia whakamātautau hikohiko o tētahi tauira i raro i ngā āhuatanga ōrite kia toru ngā wā kia taea ai te whakaputa anō i ngā raraunga.
Mō ngā inenga HE-SXRD, i inehia ngā poraka maitai tapawhā rua 1 × 1 × 1.5 mm3 i runga i te aho wiriwiri Brockhouse pūngao-teitei i CLS, Kanata hei ine i te hanganga ā-wāhanga56. I kohia ngā raraunga i te pāmahana rūma i roto i te āhuahanga Debye-Scherrer, i te āhuahanga kawe rānei. Ko te roanga ngaru o ngā hihi-X i whakatikatikaina ki te tauira LaB6 he 0.212561 Å, e rite ana ki te 58 keV, he nui ake i tērā o Cu Kα (8 keV) e whakamahia whānuitia ana hei pūtake hihi-X taiwhanga. Ka whakatakotoria te tauira ki te tawhiti o te 740 mm mai i te pūoko. Ko te rōrahi kitenga o ia tauira he 0.2 × 0.3 × 1.5 mm3, e whakatauhia ana e te rahi o te hihi me te matotoru o te tauira. I kohia ia o ēnei raraunga mā te whakamahi i tētahi taputapu kite rohe Perkin Elmer, he taputapu kite hihi-X papatahi, he pika 200 µm, 40 × 40 cm2, me te whakamahi i te wā whakaatu o te 0.3 hēkona me te 120 anga.
I whakahaerehia ngā inenga X-PEEM o ngā pūnaha tauira e rua kua tīpakohia i te teihana pito PEEM o te raina Beamline MAXPEEM i te taiwhanga MAX IV (Lund, Sweden). I whakaritea ngā tauira i te ara kotahi me ngā inenga hikohiko. I puritia ngā tauira kua whakaritea ki te hau mō ētahi rā, ā, i tangohia te hau i roto i te rūma korehau tino teitei i mua i te whakamātao ki ngā photon synchrotron. Ka whiwhihia te taumira pūngao o te hihi mā te ine i te whānuitanga putanga katote mai i te N 1 s ki te 1\(\pi _g^ \ast\) o te rohe whakaoho me te hv = 401 eV i roto i te N2 me te whakawhirinakitanga o te pūngao photon ki te E3/2.57. Nā te taunga spectral i homai te ΔE (whānui raina spectral) ~0.3 eV i runga i te whānuitanga pūngao i inehia. Nō reira, i whakatauhia te taumira pūngao raina hihi ko E/∆E = 700 eV/0.3 eV > 2000 me te rerenga ≈1012 ph/s mā te whakamahi i tētahi monochromator SX-700 kua whakarerekētia me tētahi whatanga Si 1200-raina mm−1 mō te taha Fe 2p L2,3, te taha Cr 2p L2,3, te taha Ni 2p L2,3, me te taha Ce M4,5. Nō reira, i whakatauhia te taumira pūngao o te raina hihi ko E/∆E = 700 eV/0.3 eV > 2000 me te rerenga ≈1012 ph/s mā te whakamahi i tētahi monochromator SX-700 kua whakarerekētia me tētahi whatanga Si 1200-raina mm−1 mō te taha Fe 2p L2.3, te taha Cr 2p L2.3, te taha Ni 2p L2.3, me te taha Ce M4.5. Таким образом, энергетическое разрешение канала пучка было оценено как E/∆E = 700 эВ/0,3 эВ > 2000 и/10ф ≤ использовании модифицированного монохроматора SX-700 с решеткой Si 1200 штрихов/мм для Fe кромка 2p L2,3, кромка 2,3, кромка Cr 2 кромка Ce M4,5. Nō reira, i whakatauhia te taumira pūngao o te hongere hihi ko E/∆E = 700 eV/0.3 eV > 2000 me te rerenga ≈1012 f/s mā te whakamahi i tētahi monochromator SX-700 kua whakarerekētia me te kupenga Si o te 1200 rārangi/mm mō te taha Fe 2p L2 ,3, te taha Cr 2p L2.3, te taha Ni 2p L2.3, me te taha Ce 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 通过使甿田单色器和Si 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C。因此 ， 光束线 能量 分辨率 为 为 为 为 δe = 700 EV/0.3 EV> 2000 和 ≈1012 PH/S 通过 700 EV/0.3 EV>单色器 和 SI 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 边缘缘、Cr 2p L2.3 边缘、Ni 2p L2.3 边羘缘。Nō reira, i te wā e whakamahia ana he monochromator SX-700 kua whakarerekētia me te whatanga Si raina 1200. 3, te taha Cr 2p L2.3, te taha Ni 2p L2.3 me te taha Ce M4.5.Whakawhanuihia te pūngao photon i roto i ngā taahiraa 0.2 eV. I ia pūngao, i tuhia ngā whakaahua PEEM mā te whakamahi i tētahi pūoko CMOS TVIPS F-216 me tētahi hononga muka whatu 2 x 2 e whakarato ana i te 1024 × 1024 pika i roto i te tirohanga 20 µm. Ko te wā whakaaturanga o ngā whakaahua he 0.2 hēkona, ko te toharite he 16 anga. Ka whiriwhiria te pūngao whakaahua irahiko i roto i tētahi huarahi hei whakarato i te tohu irahiko tuarua mōrahi. Ka mahia ngā inenga katoa i te taunga noa o tētahi hihi photon kua whakarōpūtia. Mō ētahi atu kōrero mō ngā inenga, tirohia tētahi rangahau o mua58. Whai muri i te ako i te aratau kitenga hua irahiko katoa (TEY)59 me tōna tono i roto i te X-PEEM, ka whakatauhia te hohonutanga kitenga o tēnei tikanga ki te ~4–5 nm mō te tohu Cr me te ~6 nm mō te tohu Fe. He tino tata te hohonutanga Cr ki te matotoru o te kiriata waikura (~4 nm)60,61 i te mea he nui ake te hohonutanga Fe i te matotoru o te kiriata waikura. Ko te XAS i kohia tata ki te taha FeL he ranunga o te waikura rino XAS me te FeO mai i te matihiko. I te take tuatahi, ko te kaha o ngā irahiko i tukuna mai nā ngā momo irahiko katoa e whai wāhi ana ki te TEY. Heoi, me nui ake te kaha nekeneke o te tohu rino parakore kia taea ai e ngā irahiko te haere mā roto i te paparanga waikura, te tae ki te mata, me te kohia e te kaitātari. I tēnei take, ko te tohu Fe0 te nuinga nā ngā irahiko LVV Auger me ngā irahiko tuarua i tukuna e rātou. Hei tāpiri, ko te kaha TEY i tukuna e ēnei irahiko ka memeha haere i te wā o te ara mawhiti irahiko49 ka whakaiti ake i te waitohu ā-ira o Fe0 i roto i te mahere rino XAS.
Ko te whakauru i te keri raraunga ki roto i ngā poraka raraunga (raraunga X-PEEM) he taahiraa matua ki te tango i ngā mōhiohio e tika ana (ngā āhuatanga matū, ā-tinana rānei) i roto i te huarahi maha-ahu. He whānuitia te whakamahinga o te whakarōpū K-means i roto i ētahi wāhanga, tae atu ki te tirohanga mīhini, te tukatuka whakaahua, te mōhio tauira kore tirotiro, te mātauranga horihori, me te tātari whakarōpū24. Hei tauira, he pai te whakamahinga o te whakarōpū K-means ki te whakarōpū i ngā raraunga whakaahua hyperspectral62. I roto i te kaupapa, mō ngā raraunga maha-mea, ka taea e te rauropi K-means te whakarōpū i a rātou kia rite ki ngā mōhiohio e pā ana ki ō rātou āhuatanga (ngā āhuatanga pūngao photon). Ko te whakarōpū K-means he rauropi auau mō te wehewehe raraunga ki ngā rōpū K kore-taupoki (ngā whakarōpū), kei reira ia pika no tētahi whakarōpū motuhake i runga i te tohatoha ā-wāhi o te kore ōritetanga matū i roto i te hanganga hanganga moroiti maitai. E rua ngā taahiraa o te rauropi K-means: ko te taahiraa tuatahi ka tatau i ngā pokapū K, ā, ko te taahiraa tuarua ka tohaina ia pūwāhi ki tētahi whakarōpū me ngā pokapū tata. Ko te pokapū taumaha o tētahi tautau ka tautuhia ko te toharite tātaitanga o ngā pūwāhi raraunga (ngā hihi XAS) o taua tautau. He rerekē ngā tawhiti hei tautuhi i ngā pokapū tata hei tawhiti Euclidean. Mō tētahi whakaahua whakauru o px,y (ko x me y ngā taumira i roto i ngā pika), ko CK te pokapū taumaha o te tautau; ka taea te wehewehe (te whakarōpū) i tēnei whakaahua ki ngā tautau K mā te whakamahi i te K-means63. Ko ngā mahi whakamutunga o te pūnaha whakarōpū K-means ko:
Hipanga 2. Tātaihia te taumata o te mema o ngā pika katoa e ai ki te pokapū o nāianei. Hei tauira, ka tātaihia mai i te tawhiti Euclidean d i waenganui i te pokapū me ia pika:
Hipanga 3 Tautapahia ia pika ki te pokapū tata. Kātahi ka tatau anō i ngā tūranga pokapū K penei:
Hipanga 4. Whakahokia te tukanga (ngā whārite (7) me (8)) kia tūtaki rā anō ngā pokapū. He hononga nui ngā hua kounga tautau whakamutunga ki te kōwhiringa pai rawa atu o ngā pokapū tīmatanga63. Mō te hanganga raraunga PEEM o ngā whakaahua maitai, ko te tikanga ko X (x × y × λ) he poraka o ngā raraunga rarangi 3D, ko ngā tuaka x me y e tohu ana i ngā mōhiohio ā-wāhi (taumira pika) ā, ko te tuaka λ e rite ana ki te aratau hiato pūngao o ngā photon. I whakamahia te pūnaha K-means hei tūhura i ngā rohe e hiahiatia ana i roto i ngā raraunga X-PEEM mā te wehewehe i ngā pika (ngā tautau, ngā poraka iti rānei) e ai ki ō rātou āhuatanga hiato me te tango i te pokapū pai rawa atu (te pihi hiato XAS) mō ia tātari (tautau). Ka whakamahia hei ako i te tohatoha ā-wāhi, ngā huringa hiato ā-rohe, te whanonga waikura me te āhua matū. Hei tauira, i whakamahia te pūnaha tautau K-means mō ngā rohe Fe L-edge me Cr L-edge i roto i te X-PEEM wera-mahi me te X-PEEM hurihuri-matao. I whakamātauria ngā tau maha o ngā tautau-K (ngā rohe hanganga-iti) hei kimi i ngā tautau me ngā pokapū pai rawa atu. Ina whakaaturia te kauwhata, ka tohaina ngā pika ki ngā pokapū tautau tika. Ka rite ia tohatoha tae ki te pokapū o te tautau, e whakaatu ana i te whakaritenga ā-wāhi o ngā mea matū, ā-tinana rānei. Ko ngā pokapū i tangohia he huinga rārangi o ngā iraira parakore.
Kei te wātea ngā raraunga e tautoko ana i ngā hua o tēnei rangahau mai i te kaituhi WC e pā ana ki tēnā, ki tēnā mēnā he tono tika.
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