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He ātete te maitai kore waikura e whakamahia whānuitia ana me ōna momo whakairo 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 e hono ana ki te whakangaromanga o ēnei paparanga, engari he onge i te taumata moroiti, i runga i te pūtake o te kore ōrite o te mata. I roto i tēnei mahi, ko te rerekētanga matū o te mata nano i kitea e te karu tirotiro me te tātari chemometric i tetahi taha. Ahakoa i whakaatuhia e te karu tirotiro whakaahua-X te hipoki ōrite o te paparanga Cr2O3 taiao, i whakaatuhia e te SDSS hurihuri matao he hua passivation ngoikore nā te tohatoha ā-rohe o ngā nanoislands whai rawa Fe3+ i runga i te paparanga oxide Fe/Cr. Mā tēnei mōhiotanga i te taumata ngota 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 te ātete waikura o ngā koranu ferrochromium he chromium, e hanga ana i te waikura/oxyhydroxide kaha e whakaatu ana i te whanonga passivating i roto i te nuinga o ngā taiao. Ki te whakatauritea ki ngā maitai kore waikura tikanga (austenitic me te ferritic), ko ngā maitai kore waikura super duplex (SDSS) me te ātete waikura pai ake he āhuatanga miihini pai ake1,2,3. Mā te kaha miihini kua piki ake ka taea te hanga hoahoa mama ake me te kiato ake. He rerekē, ko te SDSS ohanga he ātete teitei ki te waikura pitting me te kapiti, ka roa ake te ora ratonga me te whānui ake o ngā tono i roto i te whakahaere parahanga, 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 tana tono whānui. Nō reira, kua whakarerekētia te SDSS hei whakapai ake i ngā āhuatanga o runga ake nei. Hei tauira, ko te whakarerekētanga Ce me ngā tāpiringa teitei o te N 6, 7, 8 i whakaurua ki roto i te 2507 SDSS (Ce-2507). He pānga pai te kukū tika o te 0.08 wt.% o te huānga whenua onge (Ce) 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. Kua whakapai ake hoki 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 i ngā pāmahana rerekē (te pāmahana iti, te makariri me te wera) kia tutuki ai ngā āhuatanga miihini tino pai6,7,8. Heoi, ko te ātete waikura pai rawa atu o te SDSS nā te aroaro o tētahi kiriata waikura angiangi i runga i te mata, e pāngia ana e ngā āhuatanga maha, pērā i te aroaro o ngā wāhanga maha me ngā rohe kōpaka rerekē, ngā matūriki kāore e hiahiatia me ngā tauhohenga rerekē. kua whakapōturitia te hanganga moroiti kore-ōrite o roto o ngā wāhanga austenitic me ferritic rerekē 7. Nō reira, he mea tino nui te ako i ngā āhuatanga rohe moroiti o aua kiriata i te taumata o te hanganga hiko 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 pūnaha X-ray photoelectron photoelectron pakeke e wehewehe ana, engari he maha ngā wā kāore e taea te wehewehe, i ngā āhua matū o te huānga kotahi i ngā pūwāhi rerekē i te wāhi i runga i te nanoscale. 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 austenitic 17, ngā maitai kore waikura martensitic 18, me te SDSS 19, 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. Ka riro i ēnei pūhui he rahi iti kua tukatukahia e te werawera e tata ana ki a rātou anō, engari he rerekē te hanganga me te āhua waikura16,21. Nō reira, ko te whakaatu i te whakangaromanga o ngā kiriata waikura me te tango i te rua me mārama ki te kore ōrite o te mata i te taumata moroiti. Ahakoa ēnei whakaritenga, kei te ngaro tonu ngā aromatawai tauanga pērā i te rerekētanga waikura taha, inā koa o te rino i runga i te tauine nano/atomic, ā, kāore anō kia tūhuratia tōna hiranga mō te ātete waikura. Tae noa ki ēnei wā tata nei, i whakaahuahia te āhua matū o ngā momo huānga, pērā i te Fe me te Ca, i runga i ngā tauira maitai mā te whakamahi i te karuārai whakaahua hihi-X ngohengohe (X-PEEM) i roto i ngā whare irahiko synchrotron nanoscale. Mā te whakakotahitanga me ngā tikanga karuārai mimiti hihi-X (XAS) tairongo matū, 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 huānga me tōna āhua matū me te taumira ā-wāhi tae noa ki te tauine nanometer 23. Mā tēnei mātakitaki ā-tirohanga o te wāhi tīmatanga i raro i te karuārai ka āwhina i ngā whakamātautau matū ā-rohe, ā, ka taea te whakaatu ā-wāhi i ngā huringa matū kāore anō kia tūhuratia i roto i te paparanga Fe.
Ka whakawhānui ake tēnei rangahau i ngā painga o te PEEM ki te kite i ngā rerekētanga matū i te nanoscale, ā, ka whakaatu i tētahi tikanga tātari mata taumata-atomika hei mārama ki te whanonga waikura o Ce-2507. Ka whakamahia e ia ngā raraunga matū o te K-means cluster24 hei mahere i te hanganga matū ā-ao (he rerekētanga) o ngā huānga e whai wāhi ana, me ō rātou āhua matū e whakaatuhia ana i roto i tētahi whakaaturanga tatauranga. He rerekē ki te take tuku iho o te waikura i puta mai i te pakaru o te kiriata chromium oxide, ko te ngoikore o te passivation me te ngoikore o te ātete waikura e pā ana ki ngā nanoislands whai rawa Fe3+ e tata ana ki te paparanga waikura Fe/Cr, he hua pea tēnei o ngā waikura tiaki. I te wāhi i pakaru ai, ka hangaia he kiriata e puta ai 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 ngā 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 pāmahana rūma pumau, i whakaratohia e ēnei tātaritanga he māramatanga ki ngā kaupapa rahunga pea me ngā tukanga i muri i te waikura. I whakamahia te ara iahiko ōrite (Pikitia 1d) hei whakauru i ngā irahiko impedance spectroscopy hikohiko (EIS), ā, ko ngā hua whakauru e rite ana kei te whakaatuhia i roto i te Ripanga 1. I puta mai ngā haurua porowhita kāore i oti i te whakamātautau i ngā tauira otinga kua rongoatia me ngā tauira kua werahia, i te mea ko ngā haurua porowhita kua pēhia he mea huri matao (Pikitia 1b). I roto i te irahiko EIS, ka taea te whakaaro ko te radius haurua porowhita te ātete polarization (Rp)25,26. Ko te Rp o te SDSS i tukatukahia ki te otinga i roto i te Ripanga 1 e tata ana ki te 135 kΩ cm-2, heoi, mō te SDSS i mahi wera me te SDSS i hurihia matao ka kitea he iti ake ngā uara o te 34.7 me te 2.1 kΩ cm–2. Ko tēnei hekenga nui o te Rp e tohu ana i te pānga kino o te whakarerekētanga kirihou ki te ātete ki te kore e pāngia me te waikura, e whakaaturia ana i roto i ngā pūrongo o mua 27, 28, 29, 30.
a Nyquist, b, c Ngā hoahoa aukati me ngā āhuahanga Bode, me tētahi tauira ara iahiko ōrite mō d, ko RS te ātete irahiko, ko Rp te ātete whakapūmau, ā, ko QCPE te waikura huānga āhuahanga pumau i whakamahia hei whakatauira i te kaha kore-pai (n). I mahia ngā inenga EIS i te pūmanawa kore-kawenga.
Kei te whakaaturia ngā pūmau raupapa tuatahi i roto i te hoahoa Bode, ā, ko te papatahi 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 tōna uara mōrahi i roto i te whānuitanga auau whānui, kātahi ka heke iho (Pikitia 1c). Heoi, i roto i ngā take e toru, kei raro tonu tēnei uara 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 te tohatoha capacitance interfacial i ahu mai i te taratara o te mata, i te kore-ōrite rānei, inā koa i roto i te tauine atomika, te āhua fractal, te porosity electrode, te pūmanawa kore-ōrite, me te tohatoha iahiko e whakawhirinaki ana ki te mata. Āhua electrode31,32. Ātete 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 hohe o te electrolyte. Ko n he tau mana kore-ahu e whakaahua ana i te rerekētanga mai i te whanonga capacitive pai o te capacitor, arā, ko te tata atu o n ki te 1, ko te tata atu o CPE ki te capacitance parakore, ā, ki te tata a n ki te kore, he ātete. Ko te rerekētanga iti o n, tata ki te 1, e tohu ana i te whanonga capacitive kore-pai o te mata i muri i te whakamātautau polarization. Ko te QCPE o te SDSS hurihuri matao he teitei ake i ngā hua rite, 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 ake o te SDSS nā te mea he kiriata waikura tiaki kore i runga i te mata17. He nui ngā waikura Cr3+ me/ranei ngā hauwaiora i roto i tēnei kiriata whakakore, ko te nuinga kei roto ko ngā waikura Fe2+, Fe3+ me/ranei ngā (oxy)hydroxides 33. Ahakoa te ōrite o te mata, te paparanga waikura whakakore, me te kore he whati e kitea ana i runga i te mata, e whakatauhia ana e ngā whakaahua moroiti,6,7 he rerekē te whanonga waikura o te SDSS mahi-wera me te SDSS huri-matao, nō reira me ako hōhonu te hanganga moroiti whakarerekētanga me te āhuatanga hanganga o te maitai.
I tirotirohia 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 e rite ana tēnei ki te momo wāhanga matua, i kitea ngā rerekētanga i roto i ngā wāhanga rōrahi o ngā wāhanga, e whakarārangihia ana i roto i te Ripanga Tāpiri 1. Tērā pea nā te wāhanga wāhanga rerekē i te mata me te wāhanga rōrahi (XRD) i pāngia e te hohonu rerekē o te kitenga me te whakamahi i te X-ray diffraction me ngā pūtake pūngao rerekē o ngā photon taupatupatu te rerekētanga. Ko te ōwehenga teitei ake o te austenite 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 ōwehenga wāhanga. Hei tāpiri, ko te ātete waikura o te maitai e whakawhirinaki ana hoki ki te nui o te whakatikatika witi, te whakaiti rahi witi, te pikinga o ngā microdeformations me te kiato nekehanga e puta ana i te wā maimoatanga wera36,37,38. He ahua kirikiri ake ngā tauira i mahia-werahia, e tohu ana i ngā kirikiri rahi-micron, ko ngā mowhiti maeneene i kitea i roto i ngā tauira i hurihia-matao (Pikitia Tāpiri 3) e tohu ana i te whakatikatika nui o te kirikiri ki te nanoscale i roto i ngā mahi o mua6, e whai wāhi ana ki te hanganga kiriata passivation. me te pikinga o te ātete ki te waikura. Ko te nui ake o te kiato nekehanga e hono ana ki te iti ake o te ātete ki te pitting, e rite ana ki ngā inenga hiko.
Kua rangahaua ngā panonitanga o ngā āhua matū o ngā rohe iti o ngā huānga taketake mā te whakamahi i te X-PEEM. Ahakoa te nui o ngā huānga whakarewa, i whiriwhiria te Cr, Fe, Ni, me te Ce39 i konei nā te mea ko te Cr te huānga matua mō te hanganga o te kiriata passivation, ko te Fe te huānga matua i roto i te maitai, ā, ka whakarei ake te Ni i te passivation me te whakataurite i te hanganga wāhanga ferrite-austenitic me te kaupapa o te whakarerekē i te Ce. Mā te whakarerekē i te kaha o te irahiko synchrotron, i pania te RAS mai i te mata ki ngā āhuatanga matua o te Cr (taha L2.3), Fe (taha L2.3), Ni (taha L2.3) me te Ce (taha M4.5), te hanga wera me te hurihuri makariri Ce-2507 SDSS. I mahia te tātari raraunga tika mā te whakauru i te whakatikatika kaha me ngā raraunga kua whakaputaina (hei tauira, XAS 40, 41 i runga i te Fe L2, 3 ngā taha).
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 e rite ana o Cr me Fe L2,3 i ngā wāhi kua tohua takitahi. Ka tirotirohia e te taha L2,3 o te XAS ngā āhua 3d korekore i muri i te whakahihiko irahiko i ngā taumata wehewehe 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 XAS i te taha L2,3 i te pikitia 2b, e. Te whakataurite ki ngā kaiwhakawā. I whakaatuhia e te 42,43 e whā ngā tihi i kitea tata ki te taha L3, ko A (578.3 eV), B (579.5 eV), C (580.4 eV) me D (582.2 eV), e whakaata ana i te Cr3+ octahedral, e rite ana ki te katote Cr2O3. 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 maha o te mara tioata 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 X-PEEM o te SDSS kua whakarerekētia te āhua wera 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 kua hurihia matao e rite ana ki te taha e Cr L2.3 me te taha f Fe L2 .3 ( f ). Kua tuhia ngā hihi XAS ki ngā tūranga ā-wāhi rerekē kua tohua ki ngā whakaahua wera (a, d ), ko ngā rārangi iraira karaka i roto i (b) me (e) e tohu ana i ngā hihi XAS kua whakatauirahia o Cr3+ me te uara mara karaihe o te 2.0 eV. Mō ngā whakaahua X-PEEM, whakamahia he papatae wera hei whakapai ake i te mārama o te pānui whakaahua, kei reira 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, kāore i rerekē te āhua matū o ngā tāpiringa o ngā huānga whakarewa Ni me Ce mō ngā tauira e rua. He tuhi tāpiri. E whakaatu ana ngā Pikitia 5-9 i 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 ngā āhua waikura o Ni2+ i runga i te mata katoa i inehia o ngā tauira wera-mahi me ngā tauira matao-hurihuri (Kōrero Tāpiri). Me mōhio, i roto i te take o ngā tauira wera-mahi, kāore i kitea te tohu XAS o Ce, engari i roto i te take o ngā tauira matao-hurihuri, i kitea te hihi o Ce3+. Ko te kitenga o ngā ira Ce i roto i ngā tauira matao-hurihuri i whakaatu ko te Ce te nuinga o te wā ka puta i 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, ka huri te āhua matū o te matrix Fe i roto i te rohe iti i ngā pūwāhi e whitu kua tīpakohia matapōkeretia o te SDSS kua hurihia-matao, e whakaaturia ana i te Pikitia 2f. Hei tāpiri, kia tika ai te whakaaro mō ngā huringa o te āhua o te Fe i ngā wāhi kua tīpakohia 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 tioata maha mā te whakamahi i ngā mara tioata 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 mahi 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 tohuhia ana e 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 tuhinga o mua,45 ahakoa he rerekē te ōwehenga kaha o te rua, ko te ōwehenga kaha eg/t2g he ≈1, i tēnei wā ko te ōwehenga kaha eg/t2g he tata ki te 1. Mā tēnei ka whakakorea te tūponotanga ko te Fe3+ anake kei roto i te āhuatanga o nāianei. Ina whakaarohia te take o te Fe3O4 me te Fe2+ me te Fe3+, ko te āhuatanga tuatahi, e mōhiotia ana he ngoikore (kaha ake) te taha L3 mō te Fe, e tohu ana i te iti ake (nui ake) o ngā āhua t2g kore noho. E pā ana tēnei ki te Fe2+ (Fe3+), e whakaatu ana ko te āhuatanga tuatahi o te pikinga e tohu ana i te pikinga o te ihirangi o te Fe2+47. E whakaatu ana ēnei hua ko te noho tahi o te Fe2+ me te γ-Fe2O3, te α-Fe2O3 me/ranei te Fe3O4 te mea nui i runga i te mata hurihuri matao o ngā mea honohono.
Ngā whakaahua whakaahua wera irahiko whakaahua kua whakanuia o ngā hihi XAS (a, c) me (b, d) e whiti ana 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.
Ko ngā raraunga whakamātautau i whiwhi (Pikitia 4a me te Pikitia Tāpiri 11) kua tuhia ki te mata, ā, kua whakaritea ki ngā raraunga mō ngā pūhui parakore 40, 41, 48. 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). Ina koa, ko te ira 2-a (e tohuhia ana ko XAS-1) i roto i te Pikitia 3b, ā, i muri mai ko te ira 2-b (e tohuhia ana ko XAS-2) i kitea puta noa i te rohe kitenga katoa, ko ngā ira pērā i a E-3 i kitea i roto i te Pikitia 3d (e tohuhia ana ko XAS-3) i kitea i ngā wāhi motuhake. Hei tikanga, e whā ngā tawhā i whakamahia hei tautuhi i ngā āhua uara o nāianei i roto i te tauira e akohia ana: (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 SDSS e rangahauhia ana ngā wāhanga Fe e toru, arā, ko Fe0, Fe2+, me Fe3+. I tohu anō hoki te ōwehenga kaha kua tatauhia L2/L3 i te aroaro o ngā wāhanga e toru.
He whakaata XAS o Fe me ngā raraunga whakamātautau rerekē e toru i kitea (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 3) Whakataurite, ngā waru-ā-toru Fe2+, Fe3+ me ngā uara mara tioata o te 1.0 eV me te 1.5 eV, ia, ko ngā raraunga whakamātautau i inehia ki te bd (XAS-1, XAS-2, XAS-3) me ngā raraunga LCF kua arotauhia e rite ana (rārangi pango totoka), me te āhua o ngā whakaata XAS-3 me ngā paerewa Fe3O4 (āhua whakauru o Fe) me Fe2O3 (Fe3+ parakore).
I whakamahia he taunga whakakotahitanga rārangi (LCF) o ngā paerewa e toru 40, 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 mea i kitea he papa iti i roto i ngā raraunga katoa, ā, nā te mea hoki ko te rino whakarewa 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.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） 允记钝化层 下方 铁基体 （fe0） 的。 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 ( >сидного) что позволяет обнаруживать сигнал от железной матрицы (Fe0) ниже пассивирующего слоя. Ina hoki, ko te hohonutanga o te kitenga o te Fe (~6 nm) 49 mā te X-PEEM he nui ake i te matotoru e tumanakohia ana o te paparanga waikura (he paku neke atu i te 4 nm), e āhei ai te kitenga o te tohu mai i te whāriki rino (Fe0) i raro i te paparanga whakangāwari. .I whakahaerehia ngā huinga maha o Fe2+ me Fe3+ hei kimi i te otinga pai rawa atu mō ngā raraunga whakamātautau i tirohia. I te pikitia 4b e whakaatu ana i te whānuitanga XAS-1 mō te huinga o Fe2+ me Fe3+, i reira ko ngā ōwehenga o Fe2+ me Fe3+ he rite tonu mā te 45%, e tohu ana i ngā āhua waikura whakauru o Fe. Mō te whānuitanga XAS-2, ka huri te ōrau o Fe2+ me Fe3+ ki ~30% me te 60%, ia. He iti iho te Fe2+ i te Fe3+. Ko te ōwehenga o Fe2+ ki te Fe3, he ōrite ki te 1:2, ko te tikanga ka taea te hanga Fe3O4 i te ōwehenga kotahi i waenga i ngā iona Fe. Hei tāpiri, mō te whānuitanga XAS-3, ka huri te 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+, i tuhia te 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 ngā tihi pakihiwi (A: mai i Fe2+) me te ōwehenga kaha B/A e tohu ana he tata te whānuitanga o XAS-3, engari kāore e ōrite ki te whānuitanga o γ-Fe2O3. Ki te whakatauritea ki te papatipu γ-Fe2O3, he paku teitei ake te kaha o te tihi Fe 2p XAS o A SDSS (Pikitia 4e), e tohu ana i te kaha teitei ake o Fe2+. Ahakoa he rite te whānuitanga o XAS-3 ki te whānuitanga o γ-Fe2O3, kei reira a Fe3+ i ngā tūranga Oh me Td, ko te tautuhi i ngā āhua valence rerekē me te taunga anake i te taha L2,3, i te ōwehenga kaha L2/L3 rānei, he raruraru tonu. he kaupapa kōrero tonu nā te uaua o ngā āhuatanga rerekē e pā ana ki te whānuitanga whakamutunga41.
Haunga ngā rerekētanga āwhata i roto i te āhua matū o ngā rohe whai pānga kua tohua i whakaahuatia i runga ake nei, i aromatawaihia hoki te rerekētanga matū ā-ao o ngā huānga matua Cr me Fe mā te whakarōpū i ngā āwhata XAS katoa i whiwhihia i runga i te mata tauira mā te whakamahi i te tikanga whakarōpū K-means. . Kua whakatakotoria ngā kōtaha taha Cr L ki te hanga i ngā tautau tino pai e rua kua tohatohahia ki te wāhi i roto i ngā tauira wera-mahi me ngā tauira matao-hurihuri e whakaaturia ana i ngā Pikitia 5. E mārama ana kāore he huringa hanganga ā-rohe e kitea ana he rite, nā te mea he rite tonu ngā pokapū e rua o ngā āwhata XAS Cr. He tata rite tonu ēnei āhua āwhata o ngā tautau e rua ki ērā e rite ana ki a Cr2O342, ko te tikanga he ōrite te tawhiti o ngā paparanga Cr2O3 i runga i te SDSS.
Ko Cr L te tikanga o te K-ngā tautau rohe taha, ā, ko b ngā ​​pokapū XAS e rite ana. Ngā hua o te whakatairite K-ngā tikanga X-PEEM o te SDSS hurihuri-makariri: c Cr L2.3 rohe taha o ngā tautau K-ngā tautau me d ngā pokapū XAS e rite ana.
Hei whakaatu i ngā mahere taha FeL uaua ake, e whā me e rima ngā tautau kua arotauhia me ō rātou pokapū e pā ana (ngā kōtaha tirohanga) i whakamahia 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 whakauru i te LCF e whakaaturia ana i te Pikitia 4. Ko te pūmanawa pseudoelectrode Epsudo hei mahi a Fe0 i whakamahia hei whakaatu i te kore-ōrite matū moroiti o te kiriata waikura mata. Ka whakatauhia tata te Epsudo e te ture whakaranu,
ko \(\rm{E}_{\rm{Fe}/\rm{Fe}^{2 + (3 + )}}\) he rite ki te \(\rm{Fe} + 2e^ – \ ki te \rm { Fe}^{2 + (3 + )}\), 0.440 me te 0.036 V, ia. Ko ngā rohe he iti ake te pūmanawa he nui ake te ihirangi o te matū Fe3+. Ko te tohatoha pūmanawa i roto i ngā tauira kua whakarerekētia te wera 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 whakawhirinaki ana ki te tūranga i roto i te roto laminar o raro (Pikitia 6b). Engari, mō te hononga o ngā waikura rerekē me ngā ihirangi rerekē o Fe2+ me Fe3+ i roto i te SDSS hurihuri-makariri, ka taea te kite i te āhua kore-ōrite o te pseudopotential (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 uru ki te hāora me te wai50. I tēnei wā, ko ngā moutere whai rawa i te Fe3+ e kiia ana he horapa ā-rohe, ā, ka taea te whakaaro he wāhi waikura. I taua wā anō, ko te pikinga i roto i te mara pūmanawa, kaua ki te uara tino o te pūmanawa, ka taea te whakamahi hei tohu mō te kimi i ngā wāhi waikura hohe. Ka taea e tēnei tohatoha kore taurite o te Fe2+ me te Fe3+ i runga i te mata o te SDSS hurihuri matao te whakarerekē i te matū ā-rohe, me te whakarato i tētahi horahanga mata hohe whai hua ake i roto i te pakaru o te kiriata waikura me ngā tauhohenga waikura, kia taea ai te waikura tonu o te anga whakarewa o raro, ka hua ake te waikura o roto. te rerekētanga o ngā āhuatanga me te hekenga o ngā āhuatanga tiaki o te paparanga whakawhiti.
Ko ngā tautau K-means me ngā pokapū XAS e rite ana i roto i te rohe taha Fe L2.3 o te X-PEEM ac wera-whakarerekē me te df o te SDSS matao-hurihuri. a, d Ngā kauwhata tautau K-means kua whakakikoruatia ki ngā whakaahua X-PEEM. Ko te pūmanawa pseudoelectrode kua tatauhia (Epseudo) kua whakahuatia me te kauwhata tautau K-means. Ko te kanapa o te whakaahua X-PEEM, pērā i te tae i te Pikitia 2, he rite ki te kaha mimiti hihi-X.
Ko te Cr āhua ōrite engari he rerekē te āhua matū o te Fe ka hua ake he rerekētanga o te kino o te kiriata waikura me ngā tauira waikura i roto i te Ce-2507 i hurihia ki te wera me te Ce-2507 i hurihia ki te matao. Kua tino rangahauhia tēnei āhuatanga o te Ce-2507 i hurihia ki te matao. Mō te hanganga o ngā waikura me ngā hauwai o te Fe i roto i te hau taiao i roto i tēnei mahi tata koretake, ko ngā tauhohenga penei:
Ka puta ngā tauhohenga o runga ake nei i roto i ngā horopaki e whai ake nei i runga i te tātaritanga X-PEEM. 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 hua ake te hanganga o te paparanga Fe(OH)2 (whārite (5)), e whakarei ake ana i te tohu Fe2+ i roto i te Fe L-edge XAS. Mā te roa o te wā e pāngia ana e 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 pumau o te Fe, ko te Fe3O4 me te Fe2O3, ka taea hoki te hanga i roto i te paparanga tiaki whai rawa o te Cr3+, e pai ake ana te Fe3O4 ki tētahi hanganga ōrite me te piri. Ko te noho mai o ēnei e rua ka hua ake he āhua waikura whakauru (āwhiowhio XAS-1). Ko te āwhiowhio XAS-2 e rite ana ki te Fe3O4. Ahakoa ko te kitenga o ngā āwhiowhio XAS-3 i ētahi wāhi i tohu i te huringa katoa ki te γ-Fe2O3. Nā te mea ko te hohonutanga o te urunga o ngā hihi-X kua wherahia he tata ki te 50 nm, ko te tohu mai i te paparanga o raro ka hua ake he kaha ake o te tihi A.
E whakaatu ana te whānuitanga XPA he hanganga paparanga te wāhanga Fe i roto i te kiriata waikura me te paparanga waikura Cr. He rerekē ki ngā tohu o te korenga o te Cr2O3 i te wā o te waikura, ahakoa te paparanga ōrite o Cr2O3 i roto i tēnei mahi, he iti te ātete waikura e kitea ana i tēnei take, inā koa mō ngā tauira kua hurihia ki te matao. Ka taea te mārama ki te whanonga i kitea ko te rerekētanga o te āhua waikura matū i te paparanga o runga (Fe), e pā ana ki te mahi waikura. Nā te stoichiometry ōrite o te paparanga o runga (waikura rino) me te paparanga o raro (waikura chromium)52,53, he pai ake te taunekeneke (piripiri) i waenganui i a rāua ka arahi ki te kawe puhoi o ngā katote whakarewa, ngā katote hāora rānei i roto i te whatunga, ka arahi hoki ki te pikinga o te ātete waikura. Nō reira, he pai ake te ōwehenga stoichiometric tonu, arā, kotahi te āhua waikura o Fe, i ngā huringa stoichiometric ohorere. He mata ōrite ake te SDSS kua whakarerekētia ki te wera, he paparanga tiaki kiato ake, ā, he pai ake te ātete waikura. Mō te SDSS hurihuri-matao, ko te noho mai o ngā moutere whai rawa i te Fe3+ i raro i te paparanga tiaki ka takahi i te āhua o te mata, ā, ka puta te waikura karawaka me te papa tata, ka heke tere te Rp (Ripanga 1). Ka heke te whānuitanga EIS me tōna ātete waikura. Ka kitea ko te tohatoha ā-rohe o ngā moutere whai rawa i te Fe3+ nā te whakarerekētanga kirihou te nuinga e pā ana ki te ātete waikura, he mea hou tēnei i roto i tēnei mahi. Nō reira, ka whakaatuhia e tēnei rangahau ngā whakaahua moroiti tirotiro o te whakahekenga o te ātete waikura o ngā tauira SDSS i rangahauhia mā te tikanga whakarerekētanga kirihou.
Hei tāpiritanga, ahakoa he pai ake te mahi a te whakakotahitanga me ngā huānga whenua onge i roto i ngā maitai e rua-wāhanga, kāore tonu i te mārama te taunekeneke o tēnei huānga tāpiri me tētahi matrix maitai takitahi e pā ana ki te whanonga waikura e ai ki ngā raraunga karuārai tirohanga. Ko te putanga mai o ngā tohu Ce (mā ngā taha-M XAS) ka puta noa i ētahi wāhi i te wā e hurihuri matao ana, engari ka ngaro i te wā e whakarerekētia ana te SDSS, e tohu ana i te maturuturunga ā-rohe o Ce i roto i te matrix maitai, kaua ki te whakakotahitanga ōrite. Ahakoa kāore i te whakapai ake i ngā āhuatanga miihini o te SDSS6,7, ko te noho mai o ngā huānga whenua onge ka whakaiti i te rahi o ngā whakaurunga, ā, e whakaarohia ana ka aukati i te poka i te rohe tuatahi54.
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. Ka whakautua e mātou te pātai he aha te waikura o te maitai kore waikura ahakoa i raro i te paparanga waikura tiaki mā te ine i tōna hanganga moroiti, te matū o te 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 tō rātou taunga octahedral me te tetrahedral i te taha katoa o te Fe2+/Fe3+ whakauru, te pūtake o te kino me te waikura o te kiriata waikura matao-hurihuri SDSS. Ko ngā moutere nano 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 ki te whakatau i te pānga o te rerekētanga matū nanoscale ki te waikura, e tumanakohia ana ka whakaohohia e te mahi tonu ngā tukanga hangarau ki te whakapai ake i te ātete waikura o ngā maitai kore waikura i te wā hanga maitai.
Hei whakarite i te ingota Ce-2507 SDSS i whakamahia i roto i tēnei rangahau, i whakarewaina he ranunga whakauru kei roto ko te koranu matua Fe-Ce i hiritia ki te ngongo rino parakore i roto i te oumu whakaawe auau reo 150 kg hei whakaputa i te maitai rewa, ā, ka ringihia ki roto i te pokepoke. Ko ngā hanganga matū i inehia (wt%) kua whakarārangihia ki te Ripanga Tāpiri 2. Ka whakawerahia tuatahitia ngā ingota hei poraka. Kātahi ka whakamahanahia ki te 1050°C mō te 60 meneti kia puta ai te maitai i roto i te āhua o te wairewa totoka, kātahi ka tineia ki te wai ki te pāmahana rūma. I rangahauhia 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.
I tukatukahia ngā tauira porotaka (φ10 mm×15 mm) mō te pēhitanga wera kia rite te tuaka o te rango ki te ahunga whakarerekētanga o te poraka. I mahia te pēhitanga pāmahana-tiketike i ngā pāmahana rerekē i te awhe o te 1000-1150°C mā te whakamahi i te tauira wera Gleeble-3800 i te tere totoro pumau i te awhe o te 0.01-10 s-1. I mua i te whakarerekētanga, i whakamahanahia ngā tauira i te tere o te 10 °C s-1 mō te 2 meneti i te pāmahana kua tohua hei whakakore i te pikinga pāmahana. I muri i te whakatutukitanga o te ōritetanga pāmahana, i whakarerekētia te tauira ki te uara totoro pono o te 0.7. I muri i te whakarerekētanga, i tineia tonutia ngā tauira ki te wai hei tiaki i te hanganga whakarerekētanga. Kātahi ka tapahia te tauira kua whakapakeketia kia rite ki te ahunga pēhitanga. Mō tēnei rangahau, i whiriwhiria e mātou he tauira me te āhua totoro wera o te 1050°C, 10 s-1 nā te mea he teitei ake te pakeketanga moroiti i kitea i ētahi atu tauira7.
I whakamahia ngā tauira nunui (80 × 10 × 17 mm3) o te otinga totoka Ce-2507 i roto i tētahi mira hurihuri-rua ā-wāhanga-toru a LG-300 me ngā āhuatanga hangarau pai rawa atu i roto i ngā taumata whakarerekētanga katoa6. Ko te tere taumahatanga me te whakaiti matotoru mō ia ara he 0.2 m·s-1 me te 5%, ia.
I whakamahia he teihana mahi hikohiko Autolab PGSTAT128N mō ngā ine hikohiko SDSS i muri i te hurihuri makariri ki te 90% te whakaiti i te matotoru (1.0 te taumahatanga tūturu ōrite) me te pēhi wera i te 1050°C mō te 10 s-1 ki te taumahatanga tūturu o te 0.7. 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 whakapirihia ngā tauira ki te epoxy, ka waiho he wāhi tuwhera mahi o te 1 cm2 hei hikohiko mahi (te taha raro o te tauira porotaka). Kia tūpato i te wā e whakamaroke ana i te epoxy me te oro me te whakakanapa i muri mai kia kore ai e pakaru. I hurihia ngā mata mahi, ā, i whakakanapahia ki te whakatārewatanga whakakanapa taimana me te rahi matūriki o te 1 μm, i horoia ki te wai whakapūkara me te etanoru, ā, i whakamaroketia ki te hau makariri. I mua i ngā ine hikohiko, i tukuna ngā tauira kua whakakanapahia ki te hau mō ētahi rā hei hanga i tētahi kiriata waikura tūturu. Ka whakamahia he otinga wai o te FeCl3 (6.0 wt%), kua whakapūmautia ki te pH = 1.0 ± 0.01 me te HCl e ai ki ngā taunakitanga a ASTM, hei whakatere i te waikura o te maitai kore waikura55 nā te mea he waikura i te aroaro o ngā katote pūhaumāota me te kaha whakahāngai kaha me te pH iti. Ngā paerewa taiao G48 me A923. Rukuhia te tauira ki roto i te otinga whakamātautau mō te 1 hāora kia tata ki te āhua pumau i mua i te mahi i tētahi inenga. Mō ngā tauira otinga totoka, tauira wera-hanga, me tauira matao-hurihuri, i mahia ngā inenga ārai i ngā pūmanawa ara iahiko tuwhera (OPC) o te 0.39, 0.33, me te 0.25 V, ia, i roto i te awhe auau mai i te 1 105 ki te 0.1 Hz me te kaha o te 5 mV. I tuaruatia ngā whakamātautau matū katoa kia 3 ngā wā i raro i ngā āhuatanga ōrite hei whakarite i te taea te whakaputa anō i ngā raraunga.
Mō ngā inenga HE-SXRD, i inehia ngā poraka maitai tapawhā rua he 1 × 1 × 1.5 mm3 te rahi hei ine i te hanganga āhua hihi o tētahi mīhini wiriwiri pūngao-teitei Brockhouse i CLS, Kanata56. I kohia ngā raraunga i roto i te āhuahanga Debye-Scherrer, i te āhuahanga tuku rānei i te pāmahana rūma. Ko te roangaru hihi-X i whakatikatikaina ki te kaiwhakatikatika 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. I tū te tauira i 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 ngā raraunga katoa mā te whakamahi i tētahi pūoko rohe Perkin Elmer, pūoko hihi-X papatahi, pika 200 µm, 40 × 40 cm2 mā te whakamahi i te wā whakaaturanga o te 0.3 s me te 120 anga.
I whakahaerehia ngā inenga X-PEEM o ngā pūnaha tauira e rua kua tīpakohia i te teihana pito Beamline MAXPEEM PEEM 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 whakamātaotanga ki ngā photon synchrotron. I whiwhihia te taumira pūngao o te raina hihi mā te ine i te whānuitanga hua katote i roto i te rohe whakaoho mai i te N 1 s ki te 1\(\pi _g^ \ast\) tata ki te hv = 401 eV i roto i te N2 me te whakawhirinakitanga o te pūngao photon ki te E3/2, 57. I homai e ngā whānuitanga whakatata he ΔE (te whānui o te raina hihi) tata ki te 0.3 eV i roto 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，通过使画0-1mm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 边缘和边缘和边缘和边缘和边缘和Ce M4,5。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 ， 使禔1200 线 mm-1 光栅 改进 的 SX-700 单色器 于 于 于 用 用 用Fe 2p L2.3 边缘、Cr 2p L2.3 边缘、Cr 2p L2.3 边缘、Cr 2p L2.3、边缘和 Ce M4.5 边缘。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.Matawaihia te pūngao photon i roto i ngā taahiraa 0.2 eV. I ia pūngao, i tuhia ngā whakaahua PEEM mā te whakamahi i tētahi taputapu kite TVIPS F-216 CMOS kua honoa ki te muka me ngā ipu 2 x 2, e whakarato ana i te taumira o te 1024 x 1024 pika i roto i te tirohanga 20 µm. Ko te wā whakaaturanga o ngā whakaahua he 0.2 s, 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. I mahia ngā inenga katoa i te taunga noa mā te whakamahi i tētahi hihi photon kua whakarōpūtia. Ka kitea ētahi atu kōrero mō ngā inenga i roto i tētahi rangahau o mua. Whai muri i te ako i te aratau kite hua irahiko katoa (TEY) me tōna tono i roto i te X-PEEM49, e kiia ana ko te hohonutanga whakamātautau o tēnei tikanga he tata ki te 4-5 nm mō te tohu Cr me te tata ki te 6 nm mō te 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. Ko te XRD i kohia i te taha o te FeL he ranunga o te XRD o ngā waikura rino me te Fe0 mai i te matrix. I te take tuatahi, ko te kaha o ngā irahiko i tukuna mai i ahu mai i 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 te paparanga waikura ki te mata, ā, kia kohia e te tātari. I tēnei take, ko te tohu Fe0 nā ngā irahiko LVV Auger te nuinga, me ngā irahiko tuarua hoki i tukuna e rātou. Hei tāpiri, ka memeha te kaha TEY i tukuna e ēnei irahiko i te wā e mawhiti ana te irahiko, ka whakaiti ake i te urupare āwhata Fe0 i roto i te mahere rino XAS.
Ko te whakauru i te keri raraunga ki roto i tētahi 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 tētahi huarahi maha-ahu. He whānuitia te whakamahinga o te whakarōpū K-means i roto i ētahi mara, tae atu ki te tirohanga mīhini, te tukatuka whakaahua, te mōhiotanga tauira kore tirotiro, te mātauranga horihori, me te tātari whakarōpū. Hei tauira, he pai te mahi a te whakarōpū K-means i roto i te whakarōpū i ngā raraunga whakaahua hyperspectral. I roto i te kaupapa, mō ngā raraunga maha-āhuatanga, ka taea e te rauropi K-means te whakarōpū ngāwari i a rātou i runga i 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 rōpū), kei reira ia pika no tētahi rōpū i runga i te tohatoha ā-wāhi o te kore ōritetanga matū i roto i te hanganga hanganga moroiti o te maitai. E rua ngā wāhanga o te rauropi K-means: i te wāhanga tuatahi, ka tatauhia ngā pokapū K, ā, i te wāhanga tuarua, ka tohaina he rōpū ki ia pūwāhi me ngā pokapū tata. Ko te pokapū taumaha o tētahi tautau ka tautuhia ko te toharite tātaitanga o ngā pūwāhi raraunga (XAS spectrum) mō taua tautau. He maha ngā tawhiti hei tautuhi i ngā pokapū tata hei tawhiti Euclidean. Mō tētahi whakaahua whakauru o px,y (ko x me y te 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 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 kaha ngā hua kounga whakarōpū whakamutunga ki te kōwhiringa pai rawa atu o ngā pokapū tīmatanga. 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 tētahi pikitia hiato pūngao photon. Ka whakamahia te pūnaha K-means ki te 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 ngā pokapū pai rawa atu (ngā kōtaha hiato XAS) mō ia tātaritanga. tautau). Ka whakamahia hei ako i te tohatoha ā-wāhi, ngā huringa hiato ā-rohe, te whanonga waikura, me ngā āhua matū. Hei tauira, i whakamahia te pūnaha whakarōpū K-means mō ngā rohe Fe L-edge me Cr L-edge i roto i te X-PEEM mahi-wera me te X-PEEM hurihuri-matao. I whakamātauria ngā tau maha o ngā tautau K (ngā rohe o te hanganga moroiti) hei kimi i ngā tautau me ngā pokapū tino pai. Ina whakaaturia ēnei tau, ka tohaina ngā pika ki ngā pokapū o te tautau e rite ana. 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 ira parakore.
E wātea ana ngā raraunga e tautoko ana i ngā hua o tēnei rangahau mēnā he tono tika mai i te kaituhi o te WC.
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