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Yerekana karuseli ya sisitemu eshatu icyarimwe.Koresha Utubuto na Ibikurikira kugirango unyuze mumashusho atatu icyarimwe, cyangwa ukoreshe utubuto twa slide kumpera kugirango wimuke unyuze mubice bitatu icyarimwe.
Duplex 2205 ibyuma bidafite ingese (DSS) bifite imbaraga zo kurwanya ruswa bitewe nuburyo busanzwe bwa duplex, ariko ibidukikije bikabije bikomoka kuri CO2 birimo peteroli na gaze bivamo ingaruka zitandukanye za ruswa, cyane cyane ibyobo, bibangamira cyane umutekano n’ubwizerwe bwa peteroli na kamere gasi.iterambere rya gaze.Muri iki gikorwa, ikizamini cyo kwibiza hamwe nikizamini cya electrochemiki gikoreshwa hamwe na microscopi ya laser confocal na X-ray fotoelectron spectroscopy.Ibisubizo byerekanye ko impuzandengo yubushyuhe bwo gutera 2205 DSS yari 66.9 ° C.Iyo ubushyuhe buri hejuru ya 66.9 ℃, ubushobozi bwo gusenyuka, intera ya passivation hamwe nubushobozi bwo kwangirika buragabanuka, ubunini bwa passivation yubucucike buriyongera, kandi ibyiyumvo bya pitingi byiyongera.Hamwe no kwiyongera kwubushyuhe, radiyo ya capacitive arc 2205 DSS iragabanuka, kurwanya ubuso no kurwanya ihererekanyabubasha bigenda bigabanuka buhoro buhoro, kandi ubucucike bwabaterankunga nabatwara ibintu murwego rwa firime yibicuruzwa bifite n + p-bipolar biranga nabyo yiyongera, ibirimo Cr oxide murwego rwimbere rwa firime bigabanuka, byongera ibirimo Fe oxyde murwego rwo hanze, iseswa ryurwego rwa firime ryiyongera, ituze rigabanuka, umubare wibyobo nubunini bwa pore byiyongera.
Mu rwego rwo kwihutisha iterambere ry’ubukungu n’imibereho myiza y’abaturage n’iterambere ry’imibereho, icyifuzo cy’umutungo wa peteroli na gaze gikomeje kwiyongera, bigatuma iterambere rya peteroli na gazi rigenda ryerekeza buhoro buhoro mu majyepfo y’iburengerazuba no mu nyanja hamwe n’ibihe bikomeye ndetse n’ibidukikije, bityo imikorere y’imikorere kumanura tubing bigenda birushaho gukomera..Kwangirika 1,2,3.Mu rwego rwo gucukumbura peteroli na gaze, iyo kwiyongera kwa CO2 4 hamwe n’umunyu hamwe na chlorine 5, 6 mu mazi yakozwe, umuyoboro usanzwe wa karuboni 7 ushobora kwangirika cyane, kabone niyo ibuza ruswa byaterwa mu mugozi, ruswa ntishobora guhagarikwa neza ibyuma ntibishobora kuba byujuje ibisabwa byigihe kirekire mubikorwa byangiza CO28,9,10 ibidukikije.Abashakashatsi bahindukiriye ibyuma bitagira ibyuma (DSS) hamwe no kurwanya ruswa.2205 DSS, ibikubiye muri ferrite na austenite mubyuma bigera kuri 50%, bifite imiterere myiza yubukanishi no kurwanya ruswa, firime ya passivation yo hejuru irakomeye, ifite uburyo bwiza bwo kurwanya ruswa, igiciro kiri munsi yicy'amavuta ashingiye kuri nikel 11 . muri serivisi.
Kugeza ubu, ubushakashatsi bwinshi bwakozwe na CO2- na Cl-piting ruswa 2205 DSS bwakorewe mu gihugu no mu mahanga [16,17,18].Ebrahimi19 yasanze kongeramo umunyu wa potasiyumu dichromate kumuti wa NaCl bishobora kubuza 2205 DSS, kandi kongera ubukana bwa dichromate ya potasiyumu byongera ubushyuhe bukabije bwa 2205 DSS.Nyamara, ubushobozi bwo gushira 2205 DSS bwiyongera bitewe no kongeramo ubunini bwa NaCl kuri potasiyumu dichromate kandi bikagabanuka hamwe no kwiyongera kwa NaCl.Han20 yerekana ko kuri 30 kugeza 120 ° C, imiterere ya 2205 DSS yerekana pasiporo ni uruvange rwimbere rwa Cr2O3, imbere ya FeO, hamwe na Cr ikize;iyo ubushyuhe buzamutse bugera kuri 150 ° C, firime ya passivation irashonga., imiterere yimbere ihinduka kuri Cr2O3 na Cr (OH) 3, naho urwego rwo hanze ruhinduka kuri okiside ya Fe (II, III) na hydroxide ya Fe (III).Peguet21 yasanze gutobora ibyuma bya S2205 bidafite ibyuma mubisubizo bya NaCl mubisanzwe bibaho bitari munsi yubushyuhe bukabije (CPT) ahubwo mubipimo byubushyuhe (TTI).Thiadi22 yanzuye avuga ko uko ubukana bwa NaCl bwiyongera, kurwanya ruswa ya S2205 DSS bigabanuka cyane, kandi n’uburyo bubi bushobora gukoreshwa, niko kurwanya ruswa bishobora kwangirika.
Muri iyi ngingo, imbaraga zishobora gusikana, impedance spectroscopy, ubushobozi buhoraho, umurongo wa Mott-Schottky hamwe na microscopi ya optique ya elegitoronike yakoreshejwe kugirango bige ku ngaruka z’umunyu mwinshi, Cl- yibanze hamwe nubushyuhe ku myitwarire ya ruswa ya 2205 DSS.na fotoelectron spectroscopy, itanga ishingiro ryamahame yimikorere myiza ya 2205 DSS mubidukikije bya peteroli na gaze birimo CO2.
Ibikoresho byo kwipimisha byatoranijwe mubisubizo bivuwe nicyuma 2205 DSS (icyiciro cyicyuma 110ksi), kandi ibyingenzi byimiti bigaragara mumbonerahamwe 1.
Ingano yicyitegererezo cyamashanyarazi ni mm 10 × 10 mm × 5 mm, isukurwa na acetone kugirango ikureho amavuta na Ethanol yuzuye kandi yumye.Inyuma yikizamini cyagurishijwe kugirango uhuze uburebure bukwiye bwinsinga z'umuringa.Nyuma yo gusudira, koresha multimeter (VC9801A) kugirango urebe neza amashanyarazi yikizamini cyo gusudira, hanyuma ushireho ubuso budakora hamwe na epoxy.Koresha 400 #, 600 #, 800 #, 0000 .
Priston (P4000A) ikora amashanyarazi hamwe na sisitemu ya electrode eshatu yakoreshejwe.Electrode ya platine (Pt) ifite ubuso bwa cm 1 yakoraga nka electrode ifasha, DSS 2205 (ifite ubuso bwa cm2) yakoreshejwe nka electrode ikora, naho electrode yerekana (Ag / AgCl) yari Byakoreshejwe.Igisubizo cyicyitegererezo cyakoreshejwe mubizamini cyateguwe ukurikije (Imbonerahamwe 2).Mbere yikizamini, igisubizo cyiza cya N2 (99,99%) cyatsinzwe kuri 1 h, hanyuma CO2 itangwa muminota 30 kugirango yanduze igisubizo., na CO2 mubisubizo byahoraga muburyo bwuzuye.
Banza, shyira icyitegererezo muri tank kirimo igisubizo cyikizamini, hanyuma ubishyire mubwogero bwamazi buhoraho.Ubushyuhe bwambere bwo gushiraho ni 2 ° C, kandi izamuka ryubushyuhe rigenzurwa ku gipimo cya 1 ° C / min, kandi ubushyuhe buragenzurwa.kuri 2-80 ° C.Celsius.Ikizamini gitangirira kubushobozi buhoraho (-0.6142 Vs.Ag/AgCl) kandi ikizamini cyo kugorora ni Itongo.Ukurikije ibipimo byubushyuhe bwo gupima ibipimo, Itondekanya irashobora kumenyekana.Ubushuhe aho ubucucike buriho bugera kuri 100 μA / cm2 byitwa ubushyuhe bukomeye.Ikigereranyo cy'ubushyuhe bukomeye bwo gutobora ni 66.9 ° C.Ubushyuhe bwikizamini kumirongo ya polarisiyasi hamwe na spedance spécranité byatoranijwe kuba 30 ° C, 45 ° C, 60 ° C na 75 ° C, kandi ikizamini cyasubiwemo inshuro eshatu mubihe bimwe byintangarugero kugirango bigabanye gutandukana.
Icyitegererezo cyicyitegererezo cyerekanwe kubisubizo cyabanje gukubitwa polarite kuri cathode (-1.3 V) muminota 5 mbere yo kugerageza umurongo wa potentiodynamic polarisation kugirango ukureho firime ya oxyde yakozwe hejuru yicyitegererezo, hanyuma ikaboneka mumashanyarazi. 1 h kugeza igihe voltage ya ruswa itazashyirwaho.Igipimo cya scan ya dinamike ishobora guhinduka umurongo yashyizwe kuri 0.333mV / s, naho ubushobozi bwa scan intera yashyizwe kuri -0.3 ~ 1.2V na OCP.Kugirango tumenye neza ikizamini, ibihe bimwe byikizamini byasubiwemo inshuro 3.
Porogaramu yo gupima impedance - Sitidiyo ya Versa.Ikizamini cyakozwe bwa mbere ku bushobozi butajegajega bw’umuzunguruko, amplitione y’umuvuduko w’imihindagurikire y’imihindagurikire yashyizwe kuri mV 10, naho inshuro yo gupima yashyizwe kuri 10-22-105 Hz.Kugaragaza amakuru nyuma yo kugerageza.
Igihe cyogupima igihe cyo kugerageza: hitamo ubushobozi butandukanye bwa passivation ukurikije ibisubizo bya anodic polarisiyasi yumurongo, bapima It curve kumurongo uhoraho, kandi uhuze umurongo wa logarithm wikubye kabiri kugirango ubare umusozi wumurongo uteganijwe wo gusesengura film.uburyo bwo gushiraho firime passivating.
Nyuma yumuzunguruko wumuzunguruko uhagaze neza, kora ikizamini cya Mott-Schottky.Ikizamini gishobora gusuzumwa 1.0 ~ -1.0V (vS.Ag/AgCl), igipimo cya scan 20mV / s, inshuro yikizamini yashyizwe kuri 1000Hz, ikimenyetso cyo kwishima 5mV.
Koresha X-ray ifoto ya ecran ya ecran (XPS) (ESCALAB 250Xi, UK) kugirango ugerageze gusuzuma imiterere nuburyo bwa chimique ya firime passivation yo hejuru nyuma ya firime 2205 DSS hanyuma ukore ibipimo byo gupima impanuro ikwiye ukoresheje software nziza.ugereranije nububiko bwububiko bwa atome nibisobanuro bifitanye isano23 kandi bigahinduka ukoresheje C1s (284.8 eV).Imiterere ya ruswa hamwe nuburebure bwibyobo byintangarugero byaranzwe no gukoresha microscope ya ultra-deep optique (Zeiss Smart Zoom5, Ubudage).
Icyitegererezo cyageragejwe kubushobozi bumwe (-0.6142 V rel. Ag / AgCl) nuburyo buhoraho bushobora kubaho kandi umurongo wo kwangirika wanditswemo igihe.Ukurikije ibipimo ngenderwaho bya CPT, ubwinshi bwa polarisiyasi bwiyongera buhoro buhoro hamwe nubushyuhe bwiyongera.1 yerekana ubushyuhe bukomeye bwa 2205 DSS mugisubizo cyagereranijwe kirimo 100 g / L Cl– hamwe na CO2 yuzuye.Birashobora kugaragara ko ku bushyuhe buke bwigisubizo, ubwinshi bwubu ntabwo buhinduka hamwe no kongera igihe cyo kwipimisha.Kandi iyo ubushyuhe bwigisubizo bwiyongereye kugera ku gaciro runaka, ubucucike buriho bwiyongereye vuba, byerekana ko umuvuduko wo gusesa firime passivasi wiyongereye hamwe no kwiyongera kwubushyuhe bwigisubizo.Iyo ubushyuhe bwumuti ukomeye bwiyongereye kuva kuri 2 ° C kugeza kuri 67 ° C, ubucucike bwa polarisiyasi ya 2205DSS bwiyongera kugera kuri 100µA / cm2, naho impuzandengo yubushyuhe bukabije bwa 2205DSS ni 66.9 ° C, ni nka 16,6 ° C. hejuru ya 2205DSS.bisanzwe 3.5 wt.% NaCl (0.7 V) 26.Ubushyuhe bukomeye bwo gutobora buterwa nubushobozi bwakoreshejwe mugihe cyo gupimwa: uko ubushobozi bwakoreshejwe, niko ubushyuhe bwapimwe ubushyuhe bukabije.
Gushira ubushyuhe bukomeye bwa 2205 duplex idafite ibyuma mubisubizo byagereranijwe birimo 100 g / L Cl– hamwe na CO2 yuzuye.
Ku mutini.2 yerekana ibibanza bya ac impedance ya 2205 DSS mubisubizo byagereranijwe birimo 100 g / L Cl- hamwe na CO2 yuzuye mubushyuhe butandukanye.Birashobora kugaragara ko igishushanyo cya Nyquist cya 2205DSS mubushyuhe butandukanye kigizwe numurongo mwinshi, hagati-na-na-ya-ya-ya-ya-ya-ya-ya-ya-ya-ya-ya-ya,Iradiyo ya capacitive arc yerekana agaciro ko guhangana na firime passivating hamwe nagaciro kokwirinda kwishyurwa mugihe cya electrode.Muri rusange biremewe ko uko radiyo nini ya capacitive arc, ari nako irwanya ruswa yo kwangirika kwicyuma cya substrate mu gisubizo27.Ku bushyuhe bwubushyuhe bwa 30 ° C, radiyo ya capacitive arc ku gishushanyo cya Nyquist hamwe nu mpande ya fonction ku gishushanyo cya modulus ya impedance | Z |Bode nimwe murwego rwo hejuru kandi 2205 DSS ruswa niyo yo hasi.Nkuko ubushyuhe bwibisubizo bwiyongera, | Z |modedance modulus, arc radius hamwe nigisubizo cyo guhangana nigabanuka, hiyongereyeho, inguni yicyiciro nayo igabanuka kuva kuri 79 Ω ikagera kuri 58 Ω mukarere kegeranye hagati, byerekana impinga nini hamwe nigice cyimbere cyimbere hamwe nigice gito (porous) cyo hanze nicyo nyamukuru ibiranga firime idahwitse ya28.Kubwibyo, uko ubushyuhe buzamuka, firime ya pasivi yakozwe hejuru yubutaka bwicyuma irashonga kandi igacika, bigabanya intege nke zo kurinda insimburangingo kandi bikangiza kwangirika kwibintu 29.
Ukoresheje porogaramu ya ZSimDeme kugirango uhuze amakuru ya impedance ya spekiteri, umuzenguruko uhwanye nawo werekana ku gishushanyo cya 330, aho amafaranga ari yo buryo bwo gukemura ibibazo, Q1 ni ubushobozi bwa firime, Rf ni ukurwanya firime yakozwe na pasiporo, Q2 ni ebyiri ubushobozi bwa layer, na Rct nigikorwa cyo kwimura amafaranga.Uhereye kubisubizo byo guhuza kumeza.3 yerekana ko uko ubushyuhe bwumuti wigana bwiyongereye, agaciro ka n1 kagabanuka kuva 0.841 kagera kuri 0.769, ibyo bikaba byerekana ko hiyongereyeho icyuho kiri hagati yubushobozi bwibice bibiri no kugabanuka kwubucucike.Kurwanya kwishyurwa kwishyurwa Rct yagabanutse buhoro buhoro kuva kuri 2.958 × 1014 igera kuri 2.541 × 103 Ω cm2, ibyo bikaba byaragabanutse buhoro buhoro kugabanuka kwangirika kwibikoresho.Kurwanya igisubizo amafaranga yagabanutse kuva kuri 2.953 kugera kuri 2,469 Ω cm2, kandi ubushobozi bwa Q2 bwa firime passivasi bwaragabanutse buva kuri 5.430 10-4 bugera kuri 1.147 10-3 Ω cm2, ubwitonzi bwigisubizo bwiyongera, ituze rya firime pasiporo iragabanuka , nigisubizo Cl-, SO42-, nibindi) muburyo bwiyongera, byihutisha isenywa rya firime passiyo31.Ibi biganisha ku kugabanuka kwa firime Rf (kuva 4662 ikagera kuri 849 Ω cm2) no kugabanuka kwurwanya polarisiyasi Rp (Rct + Rf) yakozwe hejuru yicyuma cya duplex idafite ibyuma.
Kubwibyo, ubushyuhe bwigisubizo bugira ingaruka ku kurwanya ruswa ya DSS 2205. Ku bushyuhe buke bwigisubizo, inzira yogukora iba hagati ya cathode na anode imbere ya Fe2 +, igira uruhare mukwangirika vuba no kwangirika anode, kimwe na passivation ya firime yakozwe hejuru, yuzuye kandi yuzuye Ubucucike, ihererekanyabubasha ryinshi ryo gukemura hagati y ibisubizo, bidindiza isenyuka rya matrix yicyuma kandi ryerekana kurwanya ruswa.Mugihe ubushyuhe bwigisubizo bwiyongereye, kurwanya kwimura kwishyurwa Rct bigabanuka, umuvuduko wibisubizo hagati ya ion mubisubizo byihuta, kandi umuvuduko wo gukwirakwiza ion zikaze wihuta, kuburyo ibicuruzwa byambere byangirika byongeye kuboneka hejuru yubuso. substrate kuva hejuru yicyuma substrate.Filime yoroheje yoroheje igabanya intege nke zo kurinda substrate.
Ku mutini.Igicapo ca 4 kirerekana imbaraga zishobora kuba zingana na 2205 DSS mubisubizo bigereranijwe birimo 100 g / L Cl– hamwe na CO2 yuzuye mubushyuhe butandukanye.Birashobora kugaragara ku gishushanyo ko iyo ubushobozi buri mu ntera kuva kuri -0.4 kugeza 0.9 V, umurongo wa anode ku bushyuhe butandukanye ufite uturere twa passiwasi igaragara, kandi ubushobozi bwo kwangirika ni -0.7 kugeza -0.5 V. Nku ubucucike bwongera amashanyarazi agera kuri 100 μA / cm233 umurongo wa anode mubisanzwe witwa ubushobozi bwo gutera (Eb cyangwa Etra).Mugihe ubushyuhe buzamutse, intera ya passivation iragabanuka, ubushobozi bwo kwangirika buragabanuka, ubwinshi bwikigero cyangirika gikunda kwiyongera, kandi umurongo wa polarisiyasi uramanuka ujya iburyo, ibyo bikaba byerekana ko firime yakozwe na DSS 2205 mubisubizo byagereranijwe ikora. ibikorwa.ibirimo 100 g / l Cl– hamwe na CO2 byuzuye, byongera ibyiyumvo byo gutobora ruswa, byangizwa byoroshye na ion zikaze, biganisha ku kwangirika kwa matrix yicyuma no kugabanuka kwangirika kwangirika.
Birashobora kugaragara kuva ku mbonerahamwe ya 4 ko iyo ubushyuhe buzamutse buva kuri 30 ° C bukagera kuri 45 ° C, ubushobozi bwo kurenza urugero bugabanukaho gato, ariko ubucucike bwa passivisiyasi yubunini buringaniye bwiyongera cyane, byerekana ko kurinda firime ya pasiporo munsi yibi ibintu byiyongera hamwe n'ubushyuhe bwiyongera.Iyo ubushyuhe bugeze kuri 60 ° C, ubushobozi bwo guterana buragabanuka cyane, kandi iyi nzira igaragara cyane uko ubushyuhe buzamuka.Twabibutsa ko kuri 75 ° C impinga nini yinzibacyuho igaragara mumashusho, byerekana ko hariho ruswa ishobora kwangirika hejuru yicyitegererezo.
Kubwibyo, hamwe no kwiyongera kwubushyuhe bwigisubizo, ubwinshi bwa ogisijeni yashonze mugisubizo buragabanuka, agaciro ka pH hejuru yubuso bwa firime kagabanuka, kandi ituze rya firime ya pasiporo iragabanuka.Mubyongeyeho, uko ubushyuhe bwibisubizo buringaniye, niko ibikorwa bya ion bitera mubisubizo kandi niko umuvuduko wo kwangirika kurwego rwa firime ya substrate.Oxide ikozwe murwego rwa firime igwa byoroshye kandi igakora hamwe na cations murwego rwa firime kugirango ibe ibibyimba byoroshye, byongerera amahirwe yo gutobora.Kubera ko firime yongeye kuvugururwa irekuye, ingaruka zo kurinda substrate ni nkeya, ibyo bikaba byongera kwangirika kwicyuma.Ibisubizo bya dinamike polarisiyasi ishobora kugeragezwa bihuye nibisubizo bya impedance spectroscopy.
Ku mutini.Igicapo 5a cerekana Igoramye kuri 2205 DSS mugisubizo cyicyitegererezo kirimo 100 g / L Cl– hamwe na CO2 yuzuye.Ubucucike bwa passivation nkibikorwa byigihe byabonetse nyuma ya polarisiyasi kubushyuhe butandukanye kuri 1 h kuri mV -300 mV (ugereranije na Ag / AgCl).Birashobora kugaragara ko passivation yubucucike bwa 2205 DSS kubushobozi bumwe nubushyuhe butandukanye burasa, kandi inzira igenda igabanuka buhoro buhoro hamwe nigihe kandi ikunda kugenda neza.Ubwo ubushyuhe bwagendaga bwiyongera buhoro buhoro, ubucucike bwa passiyo ya 2205 DSS bwiyongereye, ibyo bikaba byari bihuye n’ibisubizo bya polarisiyasi, byanagaragaje ko ibimenyetso biranga urwego rwa firime kurwego rwicyuma byagabanutse hamwe nubushyuhe bwo gukemura.
Potentiostatike polarisiyasi ya 2205 DSS muburyo bumwe bwo gukora firime hamwe nubushyuhe butandukanye.(a) Ubucucike buriho nigihe, (b) Gukura firime pasiporo logarithm.
Gutohoza isano iri hagati yubucucike bwa passivation nigihe nubushyuhe butandukanye kubushobozi bumwe bwo gukora firime, nkuko bigaragara muri (1) 34:
Aho ndi ni passivation yubucucike bwubushobozi bwa firime, A / cm2.A ni agace ka electrode ikora, cm2.K ni ahantu hahanamye hajyanye.igihe, s
Ku mutini.5b yerekana logI na logt umurongo kuri 2205 DSS mubushyuhe butandukanye kubushobozi bwa firime imwe.Dukurikije amakuru yubuvanganzo, 35 iyo umurongo uhanamye K = -1, urwego rwa firime rwakozwe hejuru yubutaka ruba rwinshi kandi rufite imbaraga zo kurwanya ruswa neza.Iyo kandi umurongo ugororotse uhanamye K = -0.5, igipande cya firime cyakozwe hejuru kirekuye, kirimo ibyobo byinshi bito kandi bifite imbaraga zo kutangirika kwangirika kwicyuma.Birashobora kugaragara ko kuri 30 ° C, 45 ° C, 60 ° C, na 75 ° C, imiterere yurwego rwa firime ihinduka kuva kumyenge yuzuye ikajya mu myobo irekuye ukurikije umurongo watoranijwe.Ukurikije Model Defect Model (PDM) 36,37 birashobora kugaragara ko ubushobozi bwakoreshejwe mugihe cyikizamini butagira ingaruka kubucucike bwubu, byerekana ko ubushyuhe bugira ingaruka muburyo bwo gupima ubucucike bwa anode mugihe cyibizamini, bityo rero yiyongera hamwe n'ubushyuhe bwiyongera.igisubizo, n'ubucucike bwa 2205 DSS iriyongera, kandi kurwanya ruswa bigabanuka.
Imiterere ya semiconductor yimiterere ya firime yoroheje yakozwe kuri DSS igira ingaruka ku kurwanya kwangirika kwayo38, ubwoko bwa semiconductor hamwe nubucucike bwabatwara bwurwego ruto rwa firime bigira ingaruka kumeneka no gutobora ibice bito bya firime DSS39,40 aho ubushobozi bwa C na E bwa ibishobora kuba byoroshye firime yujuje isano MS, ikibanza cyumwanya wa semiconductor kibarwa muburyo bukurikira:
Muri formula, ε ni uruhushya rwa firime ya passivasi yubushyuhe bwicyumba, bingana na 1230, ε0 ni uruhushya rwa vacuum, bingana na 8,85 × 10–14 F / cm, E nuburyo bwa kabiri (1.602 × 10–19 C) ;ND ni ubucucike bwabaterankunga n-ubwoko bwa semiconductor, cm - 3, NA nubucucike bwakirwa bwa p-semiconductor, cm - 3, EFB nubushobozi bwa bande, V, K ni Boltzmann ihoraho, 1.38 × 10–3 .23 J / K, T - ubushyuhe, K.
Ahantu hahanamye no guhuza umurongo washyizweho hashobora kubarwa muguhuza gutandukanya umurongo kugipimo cya MS cyapimwe, gushyira hamwe (ND), kwemerwa kwemerwa (NA), hamwe nubushobozi buke (Efb) 42.
Ku mutini.6 yerekana umurongo wa Mott-Schottky wubuso bwa firime ya 2205 DSS yakozwe mubisubizo bigereranijwe birimo 100 g / l Cl- kandi byuzuyemo CO2 kubishobora (-300 mV) kumasaha 1.Birashobora kugaragara ko ibice byose byoroheje byakozwe mubushyuhe butandukanye bifite ibiranga n + p-ubwoko bwa bipolar semiconductor.N-semiconductor ifite igisubizo cya anion ihitamo, irashobora kubuza ibyuma bitagira umuyonga gukwirakwizwa mugisubizo binyuze muri firime ya passivation, mugihe p-ubwoko bwa p-semiconductor ifite cation ihitamo, ishobora gukumira anion yangirika mugukemura ibibazo byambukiranya pasiporo Filime iraza hanze hejuru ya substrate 26.Birashobora kandi kugaragara ko hariho inzibacyuho yoroshye hagati yimirongo ibiri ikwiranye, firime iri mumurongo uhagaze, kandi ubushobozi bwa Efb bushobora gukoreshwa kugirango hamenyekane aho ingufu zingufu za semiconductor zihagaze no gusuzuma amashanyarazi yacyo gushikama43..
Ukurikije ibisubizo bya MC bikwiranye n'ibisubizo bigaragara mu mbonerahamwe ya 5, ibarura ryasohotse (ND) hamwe no kwakira abantu (NA) hamwe na bande ya tekinike ya Efb 44 yuburyo bumwe bwabazwe.Ubucucike bwikinyabiziga gikoreshwa cyane cyane buranga inenge zingingo zumwanya wumwanya hamwe nubushobozi bwo gushira firime ya pasiporo.Iyo urwego rwinshi rwikwirakwizwa rwikoreshwa, niko byoroshye firime ya firime kandi niko bishoboka cyane ko ruswa ishobora kwangirika45.Byongeye kandi, hamwe no kwiyongera gahoro gahoro ubushyuhe bwigisubizo, ubwinshi bwa emitter ya ND murwego rwa firime bwiyongereye buva kuri 5.273 × 1020 cm-3 bugera kuri 1.772 × 1022 cm-3, naho abashyitsi ba NA biyongera kuva kuri 4.972 × 1021 bagera kuri 4.592 × 1023.cm - nkuko bigaragara ku mutini.3, ubushobozi bwa bande bushobora kwiyongera kuva 0.021 V kugeza kuri 0,753 V, umubare wabatwara mugisubizo uriyongera, reaction hagati ya ion mugisubizo irakomera, kandi ituze rya firime iragabanuka.Nkuko ubushyuhe bwigisubizo bwiyongera, nigiciro gito cyuzuye cyumusozi wumurongo ugereranije, niko ubwinshi bwabatwara mubisubizo, niko umuvuduko wo gukwirakwizwa hagati ya ion, kandi niko umubare munini wimyanya ya ion kuri Ubuso bwa firime., bityo kugabanya ibyuma byubutaka, gutuza no kurwanya ruswa 46,47.
Imiterere yimiti ya firime igira ingaruka zikomeye kumyuma yicyuma no mumikorere ya semiconductor, kandi ihinduka ryubushyuhe rifite ingaruka zikomeye mugushinga firime idafite ingese.Ku mutini.Igicapo 7 cerekana XPS yuzuye yubuso bwa firime ya 2205 DSS mugisubizo cyagereranijwe kirimo 100 g / L Cl– hamwe na CO2 yuzuye.Ibyingenzi byingenzi muri firime zakozwe na chip ku bushyuhe butandukanye usanga ahanini ari bimwe, kandi ibyingenzi bigize firime ni Fe, Cr, Ni, Mo, O, N, na C. Kubwibyo, ibice byingenzi bigize firime ni Fe , Cr, Ni, Mo, O, N na C. Ibikoresho birimo Cr oxyde, Fe oxyde na hydroxide hamwe na oxyde ya Ni na Mo.
Byuzuye XPS 2205 DSS yerekanwe mubushyuhe butandukanye.(a) 30 ° С, (b) 45 ° С, (c) 60 ° С, (d) 75 ° С.
Ibice nyamukuru bigize firime bifitanye isano nubushyuhe bwa termodinamike yimvange muri firime passivating.Ukurikije imbaraga zihuza ibintu byingenzi murwego rwa firime, byatanzwe kumeza.6, birashobora kugaragara ko impinga ziranga Cr2p3 / 2 zigabanijwemo ibyuma Cr0 (573.7 ± 0.2 eV), Cr2O3 (574.5 ± 0.3 eV), na Cr (OH) 3 (575.4 ± 0. 1 eV) nkuko yerekanwe ku gishushanyo cya 8a, aho okiside ikozwe na Cr element aricyo kintu nyamukuru kigaragara muri firime, igira uruhare runini mukurwanya ruswa ya firime no mumashanyarazi yayo.Ugereranije ubukana bwa Cr2O3 murwego rwa firime burenze ubwa Cr (OH) 3.Nyamara, uko ubushyuhe bukomeye bwibisubizo bwiyongera, impuzandengo ya Cr2O3 igabanuka gahoro gahoro, mugihe impinga ya Cr (OH) 3 igenda yiyongera buhoro buhoro, ibyo bikaba byerekana ihinduka rigaragara rya Cr3 + nyamukuru murwego rwa firime kuva Cr2O3 ikagera kuri Cr (OH) 3, kandi ubushyuhe bwigisubizo buriyongera.
Ingufu zihuza impinga yibiranga Fe2p3 / 2 ahanini igizwe nimpinga enye za leta ya metero ya Fe0 (706.4 ± 0.2 eV), Fe3O4 (707.5 ± 0.2 eV), FeO (709.5 ± 0.1 eV) na FeOOH (713.1 eV) ± 0.3 eV), nkuko bigaragara ku gishushanyo cya 8b, Fe igaragara cyane muri firime yakozwe muburyo bwa Fe2 + na Fe3 +.Fe2 + kuva kuri FeO yiganje Fe (II) hejuru yingufu zingana, mugihe Fe3O4 na Fe (III) ibice bya FeOOH byiganje hejuru yingufu zingana 48,49.Ubukomezi bugereranije bwa mpinga ya Fe3 + burenze ubw'ubwa Fe2 +, ariko ubukana bugereranije bwimpinga ya Fe3 + buragabanuka hamwe nubushyuhe bwikigereranyo bwiyongera, kandi ubukana bugereranije bwimpanuka ya Fe2 + bwiyongera, byerekana impinduka yibintu nyamukuru murwego rwa firime kuva Fe3 + kugeza kuri Fe2 + kugirango wongere ubushyuhe bwigisubizo.
Impinga ziranga Mo3d5 / 2 zigizwe ahanini nimyanya ibiri yimisozi Mo3d5 / 2 na Mo3d3 / 243.50, naho Mo3d5 / 2 ikubiyemo ibyuma bya Mo (227.5 ± 0.3 eV), Mo4 + (228.9 ± 0.2 eV) na Mo6 + (229.4 ± 0.3 eV) ), mugihe Mo3d3 / 2 nayo irimo ibyuma bya Mo (230.4 ± 0.1 eV), Mo4 + (231.5 ± 0.2 eV) na Mo6 + (232, 8 ± 0.1 eV) nkuko bigaragara ku gishushanyo cya 8c, bityo ibintu bya Mo bibaho muri valence irenga itatu. imiterere ya firime.Ingufu zihuza impinga ziranga Ni2p3 / 2 zigizwe na Ni0 (852.4 ± 0.2 eV) na NiO (854.1 ± 0.2 eV), nkuko bigaragara ku gishushanyo cya 8g.Ikiranga N1s kigizwe na N (399.6 ± 0.3 eV), nkuko bigaragara ku gishushanyo cya 8d.Impinga ya O1s iranga O2- (529.7 ± 0.2 eV), OH- (531.2 ± 0.2 eV) na H2O (531.8 ± 0.3 eV), nkuko bigaragara ku gishushanyo. Ibice nyamukuru bigize firime ni (OH- na O2 -) , zikoreshwa cyane cyane muri okiside cyangwa hydrogen okiside ya Cr na Fe murwego rwa firime.Ubushyuhe bwo hejuru bwa OH- bwiyongereye cyane uko ubushyuhe bwiyongereye kuva 30 ° C bugera kuri 75 ° C.Kubwibyo, hamwe no kwiyongera kwubushyuhe, ibintu nyamukuru bigize O2- murwego rwa firime ihinduka kuva O2- kugeza OH- na O2-.
Ku mutini.Igicapo 9 cerekana microscopique yubuso bwa morphologie yintangarugero 2205 DSS nyuma yingufu zishobora kuba polarisiyasi mugisubizo cyicyitegererezo kirimo 100 g / L Cl– hamwe na CO2 yuzuye.Birashobora kugaragara ko hejuru yicyitegererezo cya polarisiyumu mubushyuhe butandukanye, hariho ibyobo byangirika byingero zitandukanye, ibi bibaho mugisubizo cya ion zikaze, kandi hamwe no kwiyongera kwubushyuhe bwigisubizo, ruswa ikabije iba kuri Ubuso bw'icyitegererezo.substrate.Umubare wibyobo byobo kuri buri gace hamwe nuburebure bwibigo byangirika byiyongera.
Imirongo ya ruswa ya 2205 DSS mubisubizo byicyitegererezo birimo 100 g / l Cl– hamwe na CO2 yuzuye mubushyuhe butandukanye (a) 30 ° C, (b) 45 ° C, (c) 60 ° C, (d) 75 ° C c.
Kubwibyo, kwiyongera kwubushyuhe bizongera ibikorwa bya buri kintu kigize DSS, kimwe no kongera ibikorwa bya ion yibasiye ibidukikije bikabije, bitera kwangirika kurwego runaka rwicyitegererezo, bizamura ibikorwa byo gutobora., no gushiraho ibyobo byangirika biziyongera.Igipimo cyo gukora ibicuruzwa kiziyongera kandi kurwanya ruswa yibikoresho bizagabanuka 51,52,53,54,55.
Ku mutini.10 yerekana morphologie hamwe nubujyakuzimu bwa sisitemu ya 2205 DSS ikozwe hamwe nuburebure bwikirenga bwikibanza cya optique ya microscope.Kuva ku mutini.10a yerekana ko ibyobo bito byangirika nabyo byagaragaye hafi yibyobo binini, byerekana ko firime ya passivasi hejuru yicyitegererezo yarimbuwe igice hamwe no gushiraho ibyobo byangirika mubucucike bwatanzwe, kandi ubujyakuzimu bwa metero 12,9 µm.nkuko bigaragara ku gishushanyo cya 10b.
DSS yerekana uburyo bwiza bwo kurwanya ruswa, impamvu nyamukuru nuko firime yakozwe hejuru yicyuma irinzwe neza mugukemura, Mott-Schottky, ukurikije ibisubizo XPS yavuzwe haruguru hamwe nibitabo bifitanye isano 13,56,57,58, film ahanini inyura muri ibi bikurikira Iyi niyo nzira ya okiside ya Fe na Cr.
Fe2 + byoroshye gushonga no kugwa kuri interineti 53 hagati ya firime nigisubizo, kandi inzira ya cathodic reaction nuburyo bukurikira:
Muri leta yangiritse, hashyizweho firime yuburyo bubiri igizwe, igizwe ahanini nigice cyimbere cyicyuma na chromium oxyde hamwe na hydroxide yo hanze, kandi ion zikura mumyenge ya firime.Ibigize imiti ya firime passivating bifitanye isano nimiterere yacyo ya semiconductor, nkuko bigaragazwa nu murongo wa Mott-Schottky, byerekana ko ibigize firime passivasi ari ubwoko bwa n + p kandi bifite ibimenyetso bya bipolar.Ibisubizo bya XPS byerekana ko igice cyo hanze cya firime passivating kigizwe ahanini na Fe oxyde na hydroxide yerekana imiterere ya n-semiconductor, kandi igice cyimbere kigizwe ahanini na Cr oxyde na hydroxide yerekana imiterere ya p-semiconductor.
2205 DSS ifite imbaraga nyinshi zo guhangana nubunini bwa Cr17.54 kandi ikagaragaza ibyiciro bitandukanye byo gutoboka bitewe na microscopique galvanic ruswa 55 hagati yububiko bwa duplex.Gutobora ruswa ni bumwe mu bwoko bukunze kwangirika muri DSS, kandi ubushyuhe ni kimwe mu bintu by'ingenzi bigira ingaruka ku myitwarire yo gutobora kandi bigira ingaruka ku buryo bwa termodinamike na kinetic ya DSS reaction60,61.Ubusanzwe, mubisubizo byagereranijwe hamwe na CO2 yuzuye hamwe na CO2 yuzuye, ubushyuhe nabwo bugira ingaruka kumiterere yo gutobora no gutangiza ibice mugihe cyo kwangirika kwangirika kwangirika kwangirika, kandi ubushyuhe bukomeye bwo gutobora bwiyemeje gusuzuma Kurwanya ruswa.DSS.Ibikoresho, byerekana ibyiyumvo bya matrike yicyuma kubushyuhe, bikunze gukoreshwa nkibintu byingenzi muguhitamo ibikoresho mubikorwa bya injeniyeri.Ikigereranyo cy'ubushyuhe bukabije bwa 2205 DSS mu gisubizo cyagereranijwe ni 66.9 ° C, ni hejuru ya 25,6 ° C ugereranije n’icyuma cya Super 13Cr kitagira ibyuma na NaCl 3,5%, ariko ubujyakuzimu ntarengwa bwageze kuri 12.9 µm62.Ibisubizo by'amashanyarazi byongeye kwemeza ko uturere dutambitse twa fonctionnement ya fonctionnement na frequency bigabanuka hamwe n'ubushyuhe bwiyongera, kandi uko inguni ya fase igabanuka kuva kuri 79 ° ikagera kuri 58 °, agaciro ka | Z |igabanuka kuva kuri 1.26 × 104 kugeza 1.58 × 103 Ω cm2.kwishyuza amafaranga yishyurwa Rct yagabanutse kuva kuri 2.958 1014 igera kuri 2.541 103 Ω cm2, kurwanya igisubizo amafaranga yagabanutse kuva kuri 2.953 igera kuri 2.469 Ω cm2, kurwanya firime Rf yagabanutse kuva 5.430 10-4 cm2 kugeza kuri 1.147 10-3 cm2.Ubworoherane bwibisubizo bikaze byiyongera, ituze ryicyuma cya matrix ya firime igabanuka, irashonga kandi igacika byoroshye.Ubucucike bwo kwangirika bwiyongereye kuva kuri 1.482 bugera kuri 2.893 × 10-6 A cm-2, kandi ubushobozi bwo kwangirika bwaragabanutse buva kuri -0.532 bugera kuri -0.621V.Birashobora kugaragara ko ihinduka ryubushyuhe rigira ingaruka mubusugire nubucucike bwa firime.
Ibinyuranye na byo, kwibanda cyane kuri Cl- hamwe nigisubizo cyuzuye cya CO2 byongera buhoro buhoro ubushobozi bwa adsorption ya Cl- hejuru ya firime passivasi hamwe nubushyuhe bwiyongera, ituze rya firime ya passivation iba idahindagurika, kandi ingaruka zo gukingira kuri substrate igenda igabanuka kandi ibyoroshye byo gutobora byiyongera.Muri iki gihe, ibikorwa bya ion byangirika mubisubizo byiyongera, ibirimo ogisijeni bigabanuka, kandi firime yo hejuru yibintu byangiritse biragoye gukira vuba, ibyo bikaba bituma habaho uburyo bwiza bwo gukomeza kwinjiza ioni yangirika hejuru.Kugabanya ibikoresho63.Robinson n'abandi.[64] yerekanye ko hamwe no kwiyongera k'ubushyuhe bw'igisubizo, umuvuduko wo gukura kw'ibyobo wihuta, kandi umuvuduko wo gukwirakwiza ion mu gisubizo nawo uriyongera.Iyo ubushyuhe buzamutse bugera kuri 65 ° C, gushonga kwa ogisijeni mu gisubizo kirimo Cl- ion bidindiza inzira ya cathodic reaction, umuvuduko wo gutobora uragabanuka.Han20 yakoze ubushakashatsi ku ngaruka zubushyuhe ku myitwarire ya ruswa ya 2205 duplex idafite ibyuma mu bidukikije bya CO2.Ibisubizo byerekanye ko kwiyongera k'ubushyuhe byongereye ibicuruzwa byangirika hamwe nubuso bwimyanya ndangagitsina hejuru yibikoresho.Mu buryo nk'ubwo, iyo ubushyuhe buzamutse bugera kuri 150 ° C, firime ya oxyde hejuru iracika, kandi ubucucike bwa crater ni bwo buri hejuru.Lu4 yakoze ubushakashatsi ku ngaruka z'ubushyuhe ku myitwarire ya ruswa ya 2205 duplex idafite ibyuma biva muri passivation kugeza gukora mubidukikije bya geothermal birimo CO2.Ibisubizo byabo byerekana ko ku bushyuhe bwikigereranyo buri munsi ya 150 ° C, firime yakozwe ifite imiterere iranga amorphous, naho imbere imbere harimo urwego rukungahaye kuri nikel, kandi ku bushyuhe bwa 300 ° C, ibicuruzwa bivamo ruswa bifite imiterere ya nanoscale. .-polycrystalline FeCr2O4, CrOOH na NiFe2O4.
Ku mutini.11 ni igishushanyo mbonera cyo kwangirika no gukora firime ya 2205 DSS.Mbere yo gukoresha, 2205 DSS ikora firime ishimishije mukirere.Nyuma yo kwibizwa mubidukikije bigereranya igisubizo kirimo ibisubizo birimo ibintu byinshi bya Cl- na CO2, ubuso bwacyo buzengurutswe vuba na ion zitandukanye (Cl-, CO32-, nibindi).).J. Banas 65 yaje gufata umwanzuro ko mubidukikije aho CO2 icyarimwe icyarimwe, ituze rya firime passivasi hejuru yibikoresho bizagabanuka uko ibihe bigenda bisimburana, kandi aside ya karubone ikozwe ikunda kongera ubworoherane bwa ion muri pasiporo. urwego.firime no kwihutisha gusesa ion muri firime ishimishije.firime.Rero, firime ya firime hejuru yicyitegererezo iri murwego rwo kuringaniza kuringaniza rwo guseswa no gusubizwa66, Cl- igabanya umuvuduko wo gushiraho ibice bya firime yo hejuru, kandi ibyobo bito byobo bigaragarira mubice byegeranye bya firime, nkuko yerekanwe ku gishushanyo cya 3. Erekana.Nkuko bigaragara ku gishushanyo cya 11a na b, utwobo duto duto twangirika tugaragara icyarimwe.Mugihe ubushyuhe buzamutse, ibikorwa bya ion byangirika mugukemura kuri firime ya firime biriyongera, kandi ubujyakuzimu bwibyobo bito bitajegajega byiyongera kugeza igihe igice cya firime cyinjiye rwose mucyo, nkuko bigaragara ku gishushanyo cya 11c.Hamwe no kwiyongera kwubushyuhe bwikigereranyo gishonga, ibirimo CO2 yashonze mubisubizo byihuta, biganisha ku kugabanuka kwagaciro ka pH k'igisubizo, kwiyongera k'ubucucike bw'imyobo mito mito idahungabana hejuru ya SPP , ubujyakuzimu bwibyobo byambere byangirika buraguka kandi bwimbitse, kandi firime ya passivasi hejuru yicyitegererezo Nkuko umubyimba ugabanuka, passivatif ya firime iba ikunda kwibira nkuko bigaragara ku gishushanyo cya 11d.Ibisubizo by'amashanyarazi byongeye kwemeza ko ihinduka ry'ubushyuhe rigira ingaruka runaka mubusugire n'ubucucike bwa firime.Rero, birashobora kugaragara ko kwangirika mubisubizo byuzuyemo CO2 irimo intungamubiri nyinshi za Cl- bitandukanye cyane no kwangirika mubisubizo birimo ubukana buke bwa Cl-67,68.
Inzira yo kwangirika 2205 DSS hamwe no gushiraho no gusenya firime nshya.(a) Inzira 1, (b) Inzira 2, (c) Inzira 3, (d) Inzira 4.
Impuzandengo yubushyuhe bukomeye bwa 2205 DSS mubisubizo byagereranijwe birimo 100 g / l Cl– hamwe na CO2 yuzuye ni 66.9 ℃, naho ubujyakuzimu bwa metero 12,9 µm, ibyo bikaba bigabanya ubukana bwa ruswa ya 2205 DSS kandi byongera ibyiyumvo byo gutobora.ubushyuhe bwiyongera.
Igihe cyo kohereza: Gashyantare-16-2023