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Duplex 2205 bakin karfe (DSS) yana da kyakkyawan juriya na lalata saboda tsarin sa na yau da kullun, amma yanayin yanayin CO2 mai ɗauke da mai da iskar gas yana haifar da nau'ikan lalata, musamman ma rami, wanda ke yin barazana ga aminci da amincin mai da na halitta. aikace-aikacen gas.ci gaban gas.A cikin wannan aikin, ana amfani da gwajin nutsewa da gwajin sinadarai na lantarki a hade tare da microscopy confocal laser da X-ray photoelectron spectroscopy.Sakamakon ya nuna cewa matsakaicin matsananciyar zafin jiki don rami 2205 DSS ya kai 66.9 ° C.Lokacin da yawan zafin jiki ya fi 66.9 ℃, yuwuwar rugujewar rami, tazara tazarar wucewa da yuwuwar lalatawar kai, ana ƙara girman ƙimar wucewar halin yanzu, kuma ana haɓaka ƙimar pitting.Tare da ƙarin karuwa a cikin zafin jiki, radius na capacitive arc 2205 DSS yana raguwa, juriya da juriya na caji a hankali raguwa, da yawa na masu ba da gudummawa da masu karɓa a cikin fim ɗin samfurin tare da halayen n + p-bipolar kuma. yana ƙaruwa, abun ciki na Cr oxides a cikin Layer na ciki na fim ɗin yana raguwa, yana ƙara yawan abun ciki na Fe oxides a cikin Layer na waje, rushewar fim ɗin yana ƙaruwa, kwanciyar hankali yana raguwa, adadin ramuka da girman pore.
Dangane da saurin bunkasuwar tattalin arziki da zamantakewa da ci gaban zamantakewar al'umma, buƙatun albarkatun mai da iskar gas na ci gaba da ƙaruwa, wanda ke tilasta haɓakar mai da iskar gas sannu a hankali zuwa yankunan kudu maso yamma da na teku tare da yanayi da yanayi mai tsanani, don haka yanayin aiki na bututun ƙasa yana ƙara tsananta..Lalacewa 1,2,3.A fagen binciken mai da iskar gas, lokacin da karuwar CO2 4 da salinity da chlorine abun ciki 5, 6 a cikin ruwan da aka samar, bututun karfe 7 na carbon karfe na yau da kullun yana fuskantar mummunan lalata, koda kuwa masu hana lalata sun shiga cikin bututun kirtani. lalata ba za a iya yadda ya kamata danne karfe iya daina saduwa da bukatun na dogon lokaci aiki a cikin matsananci lalata CO28,9,10 muhallin.Masu binciken sun juya zuwa duplex bakin karfe (DSS) tare da mafi kyawun juriya na lalata.2205 DSS, da abun ciki na ferrite da austenite a cikin karfe ne game da 50%, yana da kyau kwarai inji Properties da lalata juriya, da surface passivation film ne m, yana da kyau kwarai uniform lalata juriya, farashin ne m fiye da na nickel tushen gami 11. , 12. Don haka, 2205 DSS yawanci ana amfani dashi azaman jirgin ruwa a cikin yanayi mara kyau, rijiyar mai a cikin yanayi mara kyau na CO2, mai sanyaya ruwa don tsarin haɗawa a cikin filayen mai da sinadarai 13, 14, 15, amma 2205 DSS kuma na iya samun ruɗaɗɗen perforation. cikin hidima.
A halin yanzu, yawancin nazarin CO2- da Cl-pitting corrosion 2205 DSS an gudanar da su a cikin ƙasa da waje [16,17,18].Ebrahimi19 ya gano cewa ƙara gishirin potassium dichromate zuwa maganin NaCl zai iya hana 2205 DSS pitting, kuma ƙara yawan ƙwayar potassium dichromate yana ƙara yawan zafin jiki na 2205 DSS pitting.Koyaya, yuwuwar rami na 2205 DSS yana ƙaruwa saboda ƙari na wani takamaiman taro na NaCl zuwa potassium dichromate kuma yana raguwa tare da haɓaka NaCl.Han20 ya nuna cewa a 30 zuwa 120 ° C, tsarin 2205 DSS passivating film ne cakuda Cr2O3 ciki Layer, FeO m Layer, da arziki Cr;lokacin da zafin jiki ya tashi zuwa 150 ° C, fim ɗin wucewa ya narke., Tsarin ciki ya canza zuwa Cr2O3 da Cr (OH) 3, kuma Layer na waje ya canza zuwa Fe (II, III) oxide da Fe (III) hydroxide.Peguet21 ya gano cewa tsayayyen rami na S2205 bakin karfe a cikin maganin NaCl yawanci yana faruwa baya ƙasa da matsanancin zafin jiki (CPT) amma a cikin kewayon canjin canji (TTI).Thiadi22 ya kammala da cewa yayin da maida hankali na NaCl ya karu, juriya na lalata na S2205 DSS yana raguwa sosai, kuma mafi mummunar tasirin da ake amfani da shi, mafi muni da juriya na lalata kayan.
A cikin wannan labarin, an yi amfani da bincike mai ƙarfi mai ƙarfi, spectroscopy impedance, m yuwuwar, Mott-Schottky curve da microscopy na gani na lantarki don nazarin tasirin salinity mai girma, babban Cl- maida hankali da zafin jiki akan halayen lalata na 2205 DSS.da photoelectron spectroscopy, wanda ke ba da tushen ka'idar don amintaccen aiki na 2205 DSS a cikin mahallin mai da gas mai dauke da CO2.
An zaɓi kayan gwajin daga ƙarfe 2205 DSS (karfe sa 110ksi), kuma an nuna babban abun da ke tattare da sinadaran a cikin Table 1.
Girman samfurin electrochemical shine 10 mm × 10 mm × 5 mm, an tsabtace shi tare da acetone don cire man fetur da cikakken ethanol da bushe.Ana siyar da bayan yanki na gwajin don haɗa tsayin da ya dace na wayar tagulla.Bayan walda, yi amfani da multimeter (VC9801A) don duba ƙarfin lantarki na yanki na gwajin walda, sa'an nan kuma rufe saman da ba ya aiki da epoxy.Yi amfani da 400#, 600#, 800#, 1200#, 2000# silicon carbide water sandpaper don goge aikin da ke kan injin gogewa tare da wakili mai gogewa na 0.25um har sai ƙarancin ƙasa Ra≤1.6um, kuma a ƙarshe tsaftace kuma saka a cikin thermostat. .
An yi amfani da wurin aiki na lantarki na Priston (P4000A) tare da tsarin lantarki uku.Platinum electrode (Pt) tare da yanki na 1 cm2 yayi aiki azaman lantarki mai taimako, an yi amfani da DSS 2205 (tare da yanki na 1 cm2) azaman lantarki mai aiki, kuma injin tunani (Ag / AgCl) ya kasance. amfani.An shirya maganin samfurin da aka yi amfani da shi a cikin gwajin bisa ga (Table 2).Kafin gwajin, an ƙaddamar da maganin N2 mai tsabta (99.99%) don 1 h, sa'an nan kuma CO2 ya wuce na 30 min don deoxygenate bayani., kuma CO2 a cikin maganin ya kasance koyaushe a cikin yanayin jikewa.
Da farko, sanya samfurin a cikin tanki wanda ke dauke da maganin gwaji, kuma sanya shi a cikin wanka mai zafi mai zafi.Matsakaicin yanayin saitin farko shine 2 ° C, kuma ana sarrafa hawan zafin jiki akan ƙimar 1°C/min, kuma ana sarrafa kewayon zafin jiki.a 2-80 ° C.Celsius.Gwajin yana farawa da yuwuwar yuwuwar (-0.6142 Vs.Ag/AgCl) kuma ƙirar gwajin ita ce lanƙwasa.Dangane da ƙayyadaddun ƙayyadaddun gwajin zazzabi mai mahimmanci, ana iya sanin It curve.Matsakaicin yanayin da yawan adadin yanzu ya tashi zuwa 100 μA/cm2 ana kiransa matsanancin zafin jiki.Matsakaicin zafin jiki mai mahimmanci don rami shine 66.9 ° C.An zaɓi yanayin gwaji don madaidaicin polarization da bakan impedance don zama 30 ° C, 45 ° C, 60 ° C da 75 ° C, bi da bi, kuma an maimaita gwajin sau uku a ƙarƙashin yanayin samfurin iri ɗaya don rage yiwuwar karkacewa.
Samfurin ƙarfe da aka fallasa ga maganin an fara yin polarized a yuwuwar cathode (-1.3 V) don 5 min kafin gwajin ƙarfin polarization mai ƙarfi don kawar da fim ɗin oxide da aka kafa akan farfajiyar aikin samfurin, sannan kuma a buɗe damar kewayawa 1 h har sai da wutar lantarki ba za a kafa ba.An saita ƙimar sikanin madaidaicin yuwuwar polarization zuwa 0.333mV/s, kuma an saita yuwuwar tazara zuwa -0.3 ~ 1.2V vs. OCP.Don tabbatar da daidaiton gwajin, an maimaita yanayin gwajin iri ɗaya sau 3.
Impedance spectrum gwajin software - Versa Studio.An fara gudanar da gwajin ne a madaidaiciyar yuwuwar buɗaɗɗen kewayawa, an saita girman ƙarfin wutar lantarki mai canzawa zuwa 10 mV, kuma an saita mitar auna zuwa 10-2-105 Hz.bayanan bakan bayan gwaji.
Tsarin gwajin lanƙwasa na yanzu: zaɓi damar wucewa daban-daban bisa ga sakamakon madaidaicin polarization na anodic, auna madaidaicin ƙima a koyaushe, kuma ya dace da lanƙwan logarithm biyu don ƙididdige gangaren madaidaicin madaidaiciya don nazarin fim.tsarin samar da fim din wucewa.
Bayan buɗaɗɗen wutar lantarki ya daidaita, yi gwajin lanƙwan Mott-Schottky.Gwada yuwuwar sikanin kewayon 1.0 ~ -1.0V (vS.Ag/AgCl), ƙimar duban 20mV/s, mitar gwaji saita zuwa 1000Hz, siginar tashin hankali 5mV.
Yi amfani da X-ray photoelectron spectroscopy (XPS) (ESCALAB 250Xi, UK) don sputter gwada abun da ke ciki da yanayin sinadarai na fim ɗin wucewa bayan 2205 na fim ɗin DSS da aiwatar da sarrafa ma'aunin daidaitattun bayanai ta amfani da software mafi girma.idan aka kwatanta da bayanan bayanai na spectra atomic da wallafe-wallafe masu alaƙa23 kuma an daidaita su ta amfani da C1s (284.8 eV).Halin ilimin halittar jiki na lalata da zurfin ramuka akan samfuran an kwatanta su ta amfani da na'urar hangen nesa mai zurfi mai zurfi (Zeiss Smart Zoom5, Jamus).
An gwada samfurin a daidai wannan damar (-0.6142 V rel. Ag / AgCl) ta hanyar daɗaɗɗa mai mahimmanci kuma an yi rikodin lalata halin yanzu tare da lokaci.Dangane da ma'aunin gwajin CPT, yawan adadin halin yanzu yana ƙaruwa a hankali tare da ƙara yawan zafin jiki.1 yana nuna mahimmancin zafin rami na 2205 DSS a cikin siminti na siminti mai ɗauke da 100 g/L Cl- da cikakken CO2.Ana iya ganin cewa a ƙananan zafin jiki na maganin, yawancin halin yanzu ba ya canzawa tare da ƙara lokacin gwaji.Kuma lokacin da yawan zafin jiki na maganin ya karu zuwa wani ƙima, ƙimar halin yanzu ya karu da sauri, yana nuna cewa adadin narkar da fim ɗin wucewa ya karu tare da ƙara yawan zafin jiki na maganin.Lokacin da yawan zafin jiki mai ƙarfi ya ƙaru daga 2 ° C zuwa kusan 67 ° C, ƙimar polarization na yanzu na 2205DSS yana ƙaruwa zuwa 100µA/cm2, kuma matsakaicin matsanancin zafin jiki na 2205DSS shine 66.9 ° C, wanda shine kusan 16.6 ° C. sama da 2205DSS.misali 3.5 wt.% NaCl (0.7 V) 26.Matsakaicin zafin jiki mai mahimmanci ya dogara da yuwuwar da ake amfani da shi a lokacin aunawa: ƙananan yuwuwar da aka yi amfani da shi, mafi girman ma'aunin zafin jiki mai mahimmanci.
Pitting matsanancin zafin jiki na 2205 duplex bakin karfe a cikin simintaccen bayani mai ɗauke da 100 g/L Cl- da cikakken CO2.
A kan fig.2 yana nuna ac impedance mãkirci na 2205 DSS a cikin kwaikwaiyo mafita dauke da 100 g/L Cl- da cikakken CO2 a yanayi daban-daban.Ana iya ganin cewa zane-zane na Nyquist na 2205DSS a yanayin zafi daban-daban ya ƙunshi babban mita, tsaka-tsakin tsaka-tsaki da ƙananan ƙarfin juriya, kuma ƙarfin juriya ba su da tsaka-tsaki.Radius na capacitive arc yana nuna ƙimar juriya na fim ɗin wucewa da ƙimar juriyar juriya ta caji yayin amsawar lantarki.Gabaɗaya an yarda cewa mafi girman radius na baka mai ƙarfi, mafi kyawun juriya na lalata ƙarfe a cikin bayani27.A yanayin zafi na 30 ° C, radius na baka mai ƙarfi a kan zane na Nyquist da kusurwar lokaci akan zanen modul impedance |Z|Bode shine mafi girma kuma 2205 DSS lalata shine mafi ƙanƙanta.Yayin da zafin bayani ya ƙaru, |Z|Modules na impedance, radius arc da juriya na warwarewa suna raguwa, bugu da ƙari, kusurwar lokaci kuma tana raguwa daga 79 Ω zuwa 58 Ω a cikin yankin mitar matsakaici, yana nuna kololuwa mai fa'ida da ƙarami mai zurfi na ciki da ɓangarorin waje (porous) na waje sune babba. fasali na fim ɗin mara daidaituwa.Sabili da haka, yayin da zafin jiki ya tashi, fim ɗin wucewa da aka kafa akan saman ƙarfe na ƙarfe ya narke kuma ya fashe, wanda ya raunana kaddarorin kariya na substrate kuma yana lalata juriya na lalata kayan29.
Yin amfani da software na ZSimDeme don dacewa da bayanan bakan impedance, an nuna daidai da'ira daidai a cikin siffa 330, inda Rs shine juriya na simulated, Q1 shine ƙarfin fim, Rf shine juriya na fim ɗin wucewa, Q2 shine sau biyu. Layer capacitance, kuma Rct shine juriya na canja wurin caji.Daga sakamakon dacewa a cikin tebur.3 yana nuna cewa yayin da zafin jiki na simulated bayani ya karu, ƙimar n1 ya ragu daga 0.841 zuwa 0.769, wanda ke nuna karuwa a cikin rata tsakanin capacitors biyu-Layer da raguwa a yawa.Juriya canja wurin cajin Rct a hankali ya ragu daga 2.958 × 1014 zuwa 2.541 × 103 Ω cm2, wanda ya nuna raguwa a hankali a cikin juriya na lalata kayan.Juriya na maganin Rs ya ragu daga 2.953 zuwa 2.469 Ω cm2, kuma ƙarfin Q2 na fim ɗin wucewa ya ragu daga 5.430 10-4 zuwa 1.147 10-3 Ω cm2, ƙaddamarwar maganin ya karu, kwanciyar hankali na fim ɗin wucewa ya ragu. , da kuma bayani Cl-, SO42-, da dai sauransu) a cikin matsakaici yana ƙaruwa, wanda ke haɓaka lalata fim ɗin wucewa31.Wannan yana haifar da raguwar juriyar fim ɗin Rf (daga 4662 zuwa 849 Ω cm2) da raguwar juriya na polarization Rp (Rct + Rf) da aka kafa akan saman duplex bakin karfe.
Saboda haka, yawan zafin jiki na maganin yana rinjayar juriya na lalata DSS 2205. A cikin ƙananan zafin jiki na maganin, tsarin amsawa yana faruwa a tsakanin cathode da anode a gaban Fe2 +, wanda ke taimakawa wajen rushewa da sauri da lalata. anode, kazalika da passivation na fim kafa a kan surface, mafi cikakken kuma mafi girma yawa, mafi girma juriya cajin canja wurin tsakanin mafita, slows saukar da narkar da karfe matrix da kuma nuna mafi kyau lalata juriya.Yayin da yawan zafin jiki na maganin ya karu, juriya don canja wurin Rct yana raguwa, yawan abin da ke faruwa tsakanin ions a cikin maganin yana ƙaruwa, da kuma yawan yaduwar ions mai tsanani, don haka samfurori na farko sun sake haifar da su a saman. da substrate daga saman da karfe substrate.Fim ɗin wucewa na bakin ciki yana raunana kaddarorin kariya na substrate.
A kan fig.Hoto na 4 yana nuna madaidaicin yuwuwar magudanar ruwa na 2205 DSS a cikin hanyoyin simulators mai ɗauke da 100 g/L Cl- da cikakken CO2 a yanayin zafi daban-daban.Ana iya gani daga adadi cewa lokacin da yuwuwar ya kasance a cikin kewayon daga -0.4 zuwa 0.9 V, madaidaicin anode a yanayin zafi daban-daban yana da yankuna masu wucewa a bayyane, kuma yuwuwar lalata kai shine kusan -0.7 zuwa -0.5 V. Kamar yadda yawa yana ƙaruwa a halin yanzu har zuwa 100 μA/cm233 tsarin anode yawanci ana kiransa yuwuwar rami (Eb ko Etra).Yayin da zafin jiki ya tashi, tazarar wucewa yana raguwa, yuwuwar lalatawar kai yana raguwa, ƙarancin lalata na yanzu yana ƙoƙarin haɓakawa, kuma yanayin polarization yana motsawa zuwa dama, wanda ke nuna cewa fim ɗin da DSS 2205 ya kirkira a cikin maganin simulated yana aiki. aiki.abun ciki na 100 g / l Cl- da cikakken CO2, yana ƙaruwa da hankali ga lalata lalata, ana samun sauƙin lalacewa ta hanyar ions masu ƙarfi, wanda ke haifar da ƙara lalata matrix na ƙarfe da raguwa a cikin juriya na lalata.
Ana iya gani daga tebur na 4 cewa lokacin da zafin jiki ya tashi daga 30 ° C zuwa 45 ° C, madaidaicin yiwuwar wuce gona da iri yana raguwa kaɗan, amma ƙarancin ƙarfin halin yanzu na girman daidai yana ƙaruwa sosai, yana nuna cewa kariyar fim ɗin wucewa a ƙarƙashin waɗannan. yanayi yana ƙaruwa tare da ƙara yawan zafin jiki.Lokacin da zafin jiki ya kai 60 ° C, madaidaicin yuwuwar rami yana raguwa sosai, kuma wannan yanayin yana ƙara bayyana yayin da zafin jiki ya tashi.Ya kamata a lura da cewa a 75 ° C wani gagarumin kololuwa na wucin gadi na yanzu yana bayyana a cikin adadi, yana nuna kasancewar lalatawar rami mai tsauri a saman samfurin.
Sabili da haka, tare da karuwa a cikin zafin jiki na maganin, adadin iskar oxygen da aka narkar da shi a cikin maganin ya ragu, ƙimar pH na fuskar fim ya ragu, kuma kwanciyar hankali na fim din wucewa ya ragu.Bugu da ƙari, mafi girma da zafin jiki na maganin, mafi girman aikin ions masu tayar da hankali a cikin maganin kuma mafi girma yawan lalacewa ga farfajiyar fim din na substrate.Oxides da aka kafa a cikin Layer na fim cikin sauƙin faɗuwa kuma suna amsawa tare da cations a cikin Layer ɗin fim don samar da mahadi masu narkewa, ƙara yuwuwar rami.Tun da fim ɗin da aka sake haɓakawa yana da ƙarancin sako-sako, tasirin kariya a kan ƙwanƙwasa yana da ƙasa, wanda ke ƙara lalata ƙwayar ƙarfe.Sakamakon yuwuwar gwajin polarization mai ƙarfi ya yi daidai da sakamakon spectroscopy na impedance.
A kan fig.Hoto 5a yana nuna Yana lanƙwasa don 2205 DSS a cikin samfurin samfurin da ke ɗauke da 100 g/L Cl- da cikakken CO2.An sami ƙimar wucewar halin yanzu a matsayin aikin lokaci bayan polarization a yanayin zafi daban-daban don 1 h a yuwuwar -300 mV (dangane da Ag/AgCl).Ana iya ganin cewa yanayin haɓaka halin yanzu na 2205 na DSS a daidai gwargwado da yanayin zafi daban-daban iri ɗaya ne, kuma yanayin a hankali yana raguwa tare da lokaci kuma yana ƙoƙarin zama santsi.Yayin da zafin jiki ya karu a hankali, ƙimar wucewar halin yanzu na 2205 DSS ya karu, wanda ya yi daidai da sakamakon polarization, wanda kuma ya nuna cewa halayen kariya na fim din a kan ƙananan ƙarfe ya ragu tare da ƙara yawan zafin jiki.
Ƙimar polarization mai yuwuwar 2205 DSS a cikin yuwuwar ƙirƙirar fim iri ɗaya da yanayin zafi daban-daban.(a) Yawan yawa na yanzu tare da lokaci, (b) Ci gaban fim ɗin logarithm.
Bincika alakar da ke tsakanin yawan wucewar halin yanzu da lokaci a yanayin zafi daban-daban don yuwuwar samar da fim iri ɗaya, kamar yadda aka nuna a (1)34:
Inda ni ke da ƙarancin wucewa na yanzu a yuwuwar ƙirƙirar fim, A/cm2.A shine yanki na lantarki mai aiki, cm2.K shine gangaren lanƙwan da aka dace dashi.t lokaci, s
A kan fig.5b yana nuna logI da logt curves don 2205 DSS a yanayin zafi daban-daban a yuwuwar ƙirƙirar fim iri ɗaya.Dangane da bayanan wallafe-wallafen, 35 lokacin da layin ya gangara K = -1, fim ɗin fim ɗin da aka kafa akan farfajiyar ƙasa ya fi girma kuma yana da mafi kyawun juriya ga ƙarancin ƙarfe.Kuma lokacin da madaidaiciyar layi ta gangara K = -0.5, fim ɗin fim ɗin da aka kafa a saman yana kwance, yana ƙunshe da ƙananan ramuka da yawa kuma yana da ƙarancin lalata juriya ga ƙwayar ƙarfe.Ana iya ganin cewa a 30 ° C, 45 ° C, 60 ° C, da 75 ° C, tsarin Layer na fim yana canzawa daga ramuka masu yawa zuwa ramuka mai laushi daidai da zaɓaɓɓen gangaren layi.Dangane da Model Defect Model (PDM) 36,37 ana iya ganin cewa yuwuwar da aka yi amfani da ita a yayin gwajin ba ta shafar ƙimar halin yanzu, yana nuna cewa zafin jiki kai tsaye yana rinjayar ma'aunin ƙarancin anode na yanzu yayin gwajin, don haka na yanzu. yana ƙaruwa tare da ƙara yawan zafin jiki.bayani, da yawa na 2205 DSS yana ƙaruwa, kuma juriya na lalata yana raguwa.
Abubuwan semiconductor na Layer fim na bakin ciki da aka kafa akan DSS suna shafar juriyarsa na lalata38, nau'in semiconductor da ƙarancin ɗaukar hoto na Layer ɗin fim na bakin ciki yana shafar fashewa da rami na Layer fim na bakin ciki DSS39,40 inda capacitance C da E na yuwuwar Layer fim ɗin bakin ciki yana gamsar da alaƙar MS, ana ƙididdige cajin sarari na semiconductor ta hanya mai zuwa:
A cikin dabarar, ε shine izinin izinin fim ɗin wucewa a dakin da zafin jiki, daidai yake da 1230, ε0 shine izinin ƙura, daidai da 8.85 × 10-14 F / cm, E shine cajin na biyu (1.602 × 10-19 C). ;ND shine yawan masu ba da gudummawa na nau'in nau'in semiconductor, cm-3, NA shine mai karɓa na nau'in p-type semiconductor, cm-3, EFB shine yuwuwar madaidaicin band, V, K shine madaidaicin Boltzmann, 1.38 × 10-3 .23 J/K, T - zazzabi, K.
Za'a iya ƙididdige gangara da tsangwama na layin da aka dace ta hanyar daidaita madaidaicin rabuwa zuwa ma'aunin MS mai ƙididdigewa, maida hankali mai amfani (ND), maida hankali da aka karɓa (NA), da yuwuwar band band (Efb)42.
A kan fig.6 yana nuna Mott-Schottky lankwasa na saman Layer na 2205 DSS fim da aka kafa a cikin wani simulated bayani dauke da 100 g / l Cl- kuma cikakken tare da CO2 a yuwuwar (-300 mV) na 1 hour.Ana iya ganin cewa duk siraran fim ɗin da aka kafa a yanayin zafi daban-daban suna da halayen n+p-type bipolar semiconductor.Semiconductor na nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'i na nau'in nau'in nau'i na nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in nau'in inductor yana da zaɓin zaɓi na anion, wanda zai iya hana cations na bakin ƙarfe daga watsawa cikin mafita ta hanyar fim ɗin wucewa, yayin da p-type semiconductor yana da zaɓin cation, wanda zai iya hana anions masu lalata a cikin bayani daga tsallake-tsallake Fim ɗin ya zo. fita a kan saman ma'auni 26 .Hakanan za'a iya ganin cewa akwai sassaucin tsaka-tsaki tsakanin madaidaitan madaidaicin biyu, fim ɗin yana cikin yanayin bandeji mai lebur, kuma ana iya amfani da madaidaicin band ɗin Efb don sanin matsayin rukunin makamashi na wani semiconductor da kimanta electrochemical. kwanciyar hankali43..
Dangane da sakamakon dacewa da lanƙwasa na MC wanda aka nuna a cikin Teburin 5, an ƙididdige maida hankali mai fita (ND) da karɓar taro (NA) da madaidaicin band ɗin Efb 44 na tsari iri ɗaya na girman.Girman mai ɗaukar hoto na yanzu yana nuna lahani a cikin layin cajin sararin samaniya da yuwuwar pitting na fim ɗin wucewa.Mafi girman maida hankali na mai ɗaukar hoto, mafi sauƙi Layer Layer na karya kuma mafi girman yiwuwar lalata substrate45.Bugu da ƙari, tare da karuwa a hankali a cikin zafin jiki na maganin, ƙaddamarwar ND emitter a cikin fim ɗin fim ya karu daga 5.273 × 1020 cm-3 zuwa 1.772 × 1022 cm-3, kuma ƙaddamarwar mai masaukin NA ya karu daga 4.972 × 1021 zuwa 4.592 ×1023.cm - kamar yadda aka nuna a cikin fig.3, yuwuwar bandeji mai lebur yana ƙaruwa daga 0.021 V zuwa 0.753 V, adadin masu ɗaukar hoto a cikin bayani yana ƙaruwa, haɓakawa tsakanin ions a cikin maganin yana ƙaruwa, kuma kwanciyar hankali na fim ɗin ya ragu.Yayin da yawan zafin jiki na maganin ya karu, ƙarami cikakkiyar ƙimar gangaren layin da ke kusa da shi, mafi girma yawan masu dako a cikin maganin, mafi girman adadin rarraba tsakanin ions, kuma mafi girma yawan adadin ion vaccancies akan ion. surface na fim Layer., Game da shi rage karfe substrate, kwanciyar hankali da kuma lalata juriya 46,47.
Abubuwan sinadaran na fim din yana da tasiri mai mahimmanci akan kwanciyar hankali na cations na karfe da kuma aikin semiconductor, kuma canjin yanayin zafi yana da tasiri mai mahimmanci akan samuwar fim din bakin karfe.A kan fig.Hoto na 7 yana nuna cikakken bakan XPS na saman Layer na fim ɗin 2205 DSS a cikin simintaccen bayani mai ɗauke da 100 g/L Cl- da cikakken CO2.Babban abubuwan da ke cikin fina-finan da chips suke yi a yanayin zafi daban-daban iri ɗaya ne, kuma manyan abubuwan da ke cikin fina-finan su ne Fe, Cr, Ni, Mo, O, N, da C. Don haka manyan abubuwan da ke cikin Layer ɗin fim ɗin su ne Fe. , Cr, Ni, Mo, O, N da C. Kwantena tare da Cr oxides, Fe oxides da hydroxides da ƙananan adadin Ni da Mo oxides.
Cikakken XPS 2205 DSS spectra da aka ɗauka a yanayin zafi daban-daban.(a) 30°C, (b) 45°C, (c) 60°C, (d) 75°C.
Babban abun da ke ciki na fim ɗin yana da alaƙa da halayen thermodynamic na mahadi a cikin fim ɗin wucewa.Dangane da ƙarfin dauri na manyan abubuwa a cikin fim ɗin fim, wanda aka ba a cikin tebur.6, ana iya ganin cewa halayen kyan gani na Cr2p3 / 2 an raba su zuwa karfe Cr0 (573.7 ± 0.2 eV), Cr2O3 (574.5 ± 0.3 eV), da Cr (OH) 3 (575.4 ± 0. 1 eV) kamar yadda wanda aka nuna a cikin hoto na 8a, wanda oxide da aka samar da Cr element shine babban abin da ke cikin fim din, wanda ke taka muhimmiyar rawa wajen juriya na lalata fim da kuma aikin sa na lantarki.Ƙarfin dangi na Cr2O3 a cikin fim ɗin fim ya fi na Cr (OH) 3.Koyaya, yayin da ingantaccen zafin bayani mai ƙarfi yana ƙaruwa, ƙarancin dangi na Cr2O3 a hankali yana raguwa, yayin da ƙarancin dangi na Cr (OH) 3 yana ƙaruwa a hankali, wanda ke nuna zahirin canji na babban Cr3+ a cikin fim ɗin fim daga Cr2O3 zuwa Cr (OH) 3, kuma zafin maganin yana ƙaruwa.
The dauri makamashi na kololuwa na halayyar bakan na Fe2p3/2 yafi kunshi hudu kololuwa na karfe jihar Fe0 (706.4 ± 0.2 eV), Fe3O4 (707.5 ± 0.2 eV), FeO (709.5 ± 0.1 eV) da FeOO1H (713). eV) ± 0.3 eV), kamar yadda aka nuna a cikin siffa 8b, Fe ya fi kasancewa a cikin fim din da aka kafa a cikin nau'i na Fe2 + da Fe3 +.Fe2 + daga FeO yana mamaye Fe (II) a ƙananan ƙoƙon kuzari, yayin da Fe3O4 da Fe (III) mahadi na FeOOH ke mamaye mafi girman ƙarfin ɗaurin ƙarfi48,49.Matsakaicin girman girman Fe3+ ya fi na Fe2+, amma ƙarfin dangi na Fe3+ yana raguwa tare da ƙara yawan zafin bayani, kuma ƙarfin dangi na Fe2+ yana ƙaruwa, yana nuna canji a cikin babban abu a cikin fim ɗin fim daga. Fe3+ zuwa Fe2+ don ƙara yawan zafin jiki na maganin.
Halayen kololuwar Mo3d5/2 galibi sun ƙunshi matsayi kololuwa biyu Mo3d5/2 da Mo3d3/243.50, yayin da Mo3d5/2 ya haɗa da ƙarfe Mo (227.5 ± 0.3 eV), Mo4+ (228.9 ± 0.2 eV) da Mo6+ (229.5 eV) ), yayin da Mo3d3 / 2 kuma ya ƙunshi ƙarfe Mo (230.4 ± 0.1 eV), Mo4 + (231.5 ± 0.2 eV) da Mo6 + (232, 8 ± 0.1 eV) kamar yadda aka nuna a cikin Hoto 8c, don haka abubuwan Motsa sun wanzu a cikin fiye da uku valence. yanayin fim din Layer.Ƙarfin dauri na halayen kololuwa na Ni2p3/2 sun ƙunshi Ni0 (852.4 ± 0.2 eV) da NiO (854.1 ± 0.2 eV), kamar yadda aka nuna a cikin siffa 8g bi da bi.Halayen N1s mafi girma ya ƙunshi N (399.6 ± 0.3 eV), kamar yadda aka nuna a cikin siffa 8d.Halayen O1s kololuwa sun haɗa da O2- (529.7 ± 0.2 eV), OH- (531.2 ± 0.2 eV) da H2O (531.8 ± 0.3 eV), kamar yadda aka nuna a cikin Fig. Babban abubuwan da ke cikin fim ɗin Layer sune (OH- da O2 -) , waɗanda aka fi amfani da su don oxidation ko hydrogen oxidation na Cr da Fe a cikin fim din Layer.Matsakaicin girman dangi na OH- ya ƙaru sosai yayin da zafin jiki ya ƙaru daga 30°C zuwa 75°C.Sabili da haka, tare da karuwar yawan zafin jiki, babban abun da ke ciki na O2- a cikin fim ɗin fim ya canza daga O2- zuwa OH- da O2-.
A kan fig.Hoto na 9 yana nuna ƙananan ƙwayoyin halitta na samfurin 2205 DSS bayan haɓakar yuwuwar polarization a cikin samfurin samfurin da ke ɗauke da 100 g/L Cl- da cikakken CO2.Ana iya ganin cewa a saman samfuran polarized a yanayin zafi daban-daban, akwai ramukan lalata na nau'ikan digiri daban-daban, wannan yana faruwa a cikin maganin ions masu ƙarfi, kuma tare da haɓaka yanayin zafin maganin, mafi girman lalata yana faruwa akan saman samfurori.substrate.Yawan ramukan rami a kowane yanki na yanki da zurfin cibiyoyin lalata suna ƙaruwa.
Lalacewa na 2205 DSS a cikin samfurin samfurin da ke dauke da 100 g/l Cl- da cikakken CO2 a yanayin zafi daban-daban (a) 30 ° C, (b) 45 ° C, (c) 60 ° C, (d) 75 ° C.
Sabili da haka, haɓakar zafin jiki zai ƙara yawan ayyukan kowane ɓangaren DSS, da kuma ƙara yawan ayyukan ions masu tayar da hankali a cikin yanayi mai tsanani, yana haifar da wani nau'i na lalacewa ga samfurin samfurin, wanda zai kara yawan aikin pitting., kuma samuwar ramukan lalata zai karu.Adadin samar da samfur zai karu kuma juriya na lalata kayan zai ragu51,52,53,54,55.
A kan fig.10 yana nuna ilimin halittar jiki da zurfin rami na samfurin DSS 2205 wanda aka sanya shi tare da babban zurfin filin na gani na gani na gani na gani.Daga fig.10a yana nuna cewa ƙananan ramukan lalata suma sun bayyana a kusa da manyan ramuka, yana nuna cewa fim ɗin wucewa akan saman samfurin an lalata shi ta wani yanki tare da samuwar ramukan lalata a ƙimar da aka bayar na yanzu, kuma matsakaicin zurfin rami shine 12.9 µm.kamar yadda aka nuna a hoto na 10b.
DSS yana nuna mafi kyawun juriya na lalata, babban dalilin shine fim ɗin da aka kafa akan saman ƙarfe yana da kariya sosai a cikin bayani, Mott-Schottky, bisa ga sakamakon XPS na sama da wallafe-wallafen 13,56,57,58, fim ɗin yafi dacewa. Yana wucewa ta cikin masu zuwa Wannan shine tsarin oxidation na Fe da Cr.
Fe2 + yana narkewa da sauri kuma yana haɓakawa a cikin kewayon 53 tsakanin fim ɗin da mafita, kuma tsarin ɗaukar hoto na cathodic shine kamar haka:
A cikin gurbataccen yanayi, an samar da fim ɗin tsari mai nau'i biyu, wanda galibi ya ƙunshi nau'in ƙarfe na ciki da chromium oxides da Layer hydroxide na waje, kuma ions yawanci suna girma a cikin ramukan fim ɗin.Abubuwan da ke tattare da sinadarai na fim ɗin wucewa yana da alaƙa da halayen semiconductor, kamar yadda Mott-Schottky curve ya tabbatar, yana nuna cewa abun da ke cikin fim ɗin wucewa shine nau'in n + p kuma yana da halayen bipolar.Sakamakon XPS ya nuna cewa saman Layer na fim ɗin wucewa ya ƙunshi Fe oxides da hydroxides waɗanda ke nuna kaddarorin n-type semiconductor Properties, kuma Layer na ciki ya ƙunshi Cr oxides da hydroxides da ke nuna p-type semiconductor Properties.
2205 DSS yana da babban juriya saboda babban abun ciki na Cr17.54 kuma yana nuna nau'ikan ramuka daban-daban saboda lalatawar galvanic microscopic55 tsakanin tsarin duplex.Lalacewar Pitting na ɗaya daga cikin nau'ikan lalata da aka fi sani da DSS, kuma zafin jiki yana ɗaya daga cikin mahimman abubuwan da ke tasiri ga halayen pitting lalata kuma yana da tasiri akan tsarin thermodynamic da motsi na DSS reaction60,61.Yawanci, a cikin wani bayani na simulated tare da babban taro na Cl- da cikakken CO2, yawan zafin jiki kuma yana rinjayar samuwar pitting da kuma farawa da fashewa a lokacin damuwa lalata lalata a karkashin damuwa lalata lalata, kuma an ƙaddara zafin jiki mai mahimmanci na pitting don kimantawa. da lalata juriya.DSS.Kayan, wanda ke nuna azancin matrix ɗin ƙarfe zuwa zafin jiki, ana amfani da shi azaman mahimman tunani a zaɓin kayan aiki a aikace-aikacen injiniya.Matsakaicin matsanancin zafin jiki na 2205 DSS a cikin maganin simulated shine 66.9°C, wanda shine 25.6°C sama da na Super 13Cr bakin karfe tare da 3.5% NaCl, amma matsakaicin zurfin rami ya kai 12.9 µm62.Sakamakon electrochemical ya kara tabbatar da cewa yankuna a kwance na kusurwar zamani da mitar kunkuntar tare da karuwar zafin jiki, kuma yayin da kusurwar lokaci ya ragu daga 79 ° zuwa 58 °, darajar |Z|yana raguwa daga 1.26×104 zuwa 1.58×103 Ω cm2.juriya canja wurin caji Rct ya ragu daga 2.958 1014 zuwa 2.541 103 Ω cm2, juriya na maganin Rs ya ragu daga 2.953 zuwa 2.469 Ω cm2, juriya na fim Rf ya ragu daga 5.430 10-4 cm2 zuwa 1.147 10-3 cm2.Ƙarƙashin ƙaddamar da maganin tashin hankali yana ƙaruwa, kwanciyar hankali na fim ɗin matrix na karfe yana raguwa, yana rushewa da raguwa cikin sauƙi.Ƙaƙƙarfan lalacewa na yanzu ya karu daga 1.482 zuwa 2.893 × 10-6 A cm-2, kuma yiwuwar lalata kansa ya ragu daga -0.532 zuwa -0.621V.Ana iya ganin cewa canjin yanayin zafi yana rinjayar mutunci da yawa na Layer na fim.
Akasin haka, babban taro na Cl- da cikakken bayani na CO2 sannu a hankali yana haɓaka ƙarfin adsorption na Cl- akan farfajiyar fim ɗin wucewa tare da ƙara yawan zafin jiki, kwanciyar hankali na fim ɗin wucewa ya zama mara ƙarfi, da tasirin kariya akan substrate ya zama mai rauni kuma mai sauƙi ga rami yana ƙaruwa.A wannan yanayin, aikin ions masu lalata a cikin bayani yana ƙaruwa, abun da ke cikin oxygen ya ragu, kuma fim din da aka lalata na kayan da aka lalata yana da wuya a dawo da sauri, wanda ya haifar da ƙarin yanayi mai kyau don ƙarin adsorption na ions masu lalata a saman.Rage kayan aiki63.Robinson et al.[64] ya nuna cewa tare da karuwa a cikin zafin jiki na maganin, girman girman ramukan yana haɓaka, kuma yawan yaduwar ions a cikin maganin kuma yana ƙaruwa.Lokacin da zafin jiki ya tashi zuwa 65 ° C, narkar da iskar oxygen a cikin maganin da ke dauke da Cl-ions yana rage jinkirin tsarin amsawar cathodic, ƙimar rami yana raguwa.Han20 ya bincika tasirin zafin jiki akan halayen lalata na 2205 duplex bakin karfe a cikin yanayin CO2.Sakamakon ya nuna cewa karuwar yawan zafin jiki ya karu da yawan samfurori na lalata da kuma yanki na raguwa a saman kayan.Hakazalika, lokacin da zafin jiki ya tashi zuwa 150 ° C, fim din oxide a saman ya karya, kuma yawancin craters shine mafi girma.Lu4 ya bincika tasirin zafin jiki akan halayen lalata na 2205 duplex bakin karfe daga wucewa zuwa kunnawa a cikin yanayin geothermal mai ɗauke da CO2.Sakamakon su ya nuna cewa a yanayin gwajin da ke ƙasa da 150 ° C, fim ɗin da aka kafa yana da sifa mai siffar amorphous, kuma abin da ke ciki ya ƙunshi Layer mai arziki na nickel, kuma a zafin jiki na 300 ° C, samfurin lalata yana da tsarin nanoscale. .-polycrystalline FeCr2O4, CroOOH da NiFe2O4.
A kan fig.11 zane ne na lalata da tsarin samar da fim na 2205 DSS.Kafin amfani, 2205 DSS ya samar da fim mai wucewa a cikin yanayi.Bayan da aka nutsar da shi a cikin yanayin da ke kwatanta maganin da ke dauke da mafita tare da babban abun ciki na Cl- da CO2, samansa yana kewaye da sauri da ions masu tsanani (Cl-, CO32-, da dai sauransu).).J. Banas 65 ya zo ga ƙarshe cewa a cikin wani yanayi inda CO2 ne lokaci guda ba, da kwanciyar hankali na passivating fim a kan surface na abu zai rage tare da lokaci, da kuma kafa carbonic acid o ƙarin tabbatar da ƙara conductivity na ions a cikin passivating. Layer.fim da hanzari na rushewar ions a cikin fim mai wucewa.fim ɗin wucewa.Don haka, Layer na fim ɗin akan saman samfurin yana cikin matakan ma'auni mai ƙarfi na rushewa da sake dawowa66, Cl- yana rage ƙimar samuwar Layer ɗin fim ɗin, kuma ƙananan ramukan rami suna bayyana a gefen gefen fim ɗin, kamar yadda. wanda aka nuna a Hoto 3. Nuna.Kamar yadda aka nuna a cikin Hoto na 11a da b, ƙananan ramukan lalatawa marasa ƙarfi sun bayyana a lokaci guda.Yayin da zafin jiki ya tashi, aikin ions masu lalata a cikin bayani akan Layer na fim yana ƙaruwa, kuma zurfin ƙananan ƙananan ramukan da ba su da tabbas suna ƙaruwa har sai fim din ya shiga gaba daya ta hanyar m, kamar yadda aka nuna a cikin hoto 11c.Tare da ƙarin karuwa a cikin zafin jiki na matsakaici na narkar da, abun ciki na narkar da CO2 a cikin bayani accelerates, wanda take kaiwa zuwa rage a cikin pH darajar da bayani, wani karuwa a yawa daga cikin mafi karami m lalata ramukan a kan SPP surface. , Zurfin ramukan lalata na farko yana faɗaɗa da zurfafawa, kuma fim ɗin wucewa akan saman samfurin Yayin da kauri ya ragu, wucewar fim ɗin ya zama mai saurin kamuwa da rami kamar yadda aka nuna a cikin Hoto 11d.Kuma sakamakon electrochemical ya kuma tabbatar da cewa canjin yanayin zafi yana da wani tasiri akan daidaito da girman fim ɗin.Don haka, ana iya ganin cewa lalatawa a cikin mafita cike da CO2 dauke da babban adadin Cl- ya bambanta da lalata a cikin hanyoyin da ke ɗauke da ƙananan ƙwayoyin Cl-67,68.
Tsarin lalata 2205 DSS tare da samuwar da lalata sabon fim.(a) Tsari 1, (b) Tsari 2, (c) Tsari 3, (d) Tsari 4.
Matsakaicin zafin jiki mai mahimmanci na 2205 DSS a cikin simulated bayani dauke da 100 g / l Cl- da cikakken CO2 shine 66.9 ℃, kuma matsakaicin zurfin rami shine 12.9 µm, wanda ke rage juriya na lalata na 2205 DSS kuma yana ƙaruwa da hankali ga rami.yawan zafin jiki.
Lokacin aikawa: Fabrairu-16-2023