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Duplex 2205 Stainless simbi (DSS) ine yakanaka corrosion resistance nekuda kweyakajairwa duplex chimiro, asi kuwedzera kuomarara CO2-ine mafuta negasi nharaunda inokonzeresa madhigirii ekuora, kunyanya gomba, izvo zvinokanganisa zvakanyanya kuchengetedzeka uye kuvimbika kweoiri uye zvakasikwa. kushandiswa kwegasi.kuvandudzwa kwegasi.Mubasa iri, bvunzo yekunyudza uye ye electrochemical test inoshandiswa pamwe chete nelaser confocal microscopy uye X-ray photoelectron spectroscopy.Mhedzisiro yacho yakaratidza kuti avhareji yekupisa tembiricha yekuisa 2205 DSS yaive 66.9 °C.Kana tembiricha yakakwira kupfuura 66.9 ℃, mukana wekuputsika kwegomba, nguva yekupfuura uye kugona kuzvidzikisira kunoderedzwa, saizi passivation yazvino density inowedzerwa, uye kunzwikwa kwegomba kunowedzerwa.Nekuwedzera kwekuwedzera kwekushisa, radius ye capacitive arc 2205 DSS inodzikira, kupikisa kwepamusoro uye kushorwa kwekutamisa kutamiswa zvishoma nezvishoma, uye kuwanda kwevanopa uye vanogamuchira vatakuri mune yefirimu layer yechigadzirwa ine n + p-bipolar maitiro zvakare. inowedzera, zvinyorwa zveCr oxides mukati memufirimu inoderera, inowedzera zvinyorwa zveFe oxides mumucheka wekunze, kuparara kwefirimu kunowedzera, kugadzikana kunoderera, nhamba yemakomba uye kukura kwepore kunowedzera.
Mumamiriro ezvinhu ekukurumidza kusimudzira hupfumi nemagariro uye kufambira mberi kwevanhu, kudiwa kwemafuta negasi zviwanikwa kuri kuramba kuchikura, zvichimanikidza kukura kwemafuta negasi kuti zvishoma nezvishoma kuchinjike kunzvimbo dzekumaodzanyemba kwakadziva kumadokero nedzemhiri kwegungwa dzine mamiriro akaomarara uye nharaunda, saka mamiriro ekushanda downhole tubing inowedzera uye yakanyanya kuoma..Kuparara 1,2,3.Mundima yekuongorora oiri negasi, kana kuwedzera kwe CO2 4 uye salinity uye chlorine zvirimo 5, 6 mumvura inogadzirwa, yakajairwa 7 carbon steel pombi inokonzereswa nekuora kwakanyanya, kunyangwe corrosion inhibitors ikapombwa mutambo yepombi, ngura haigoni kudzvinyirirwa simbi haichakwanisi kuzadzisa zvinodiwa zvekushanda kwenguva refu munzvimbo dzakaomarara dzeCO28,9,10.Vatsvagiri vakatendeukira kune duplex simbi isina tsvina (DSS) ine zvirinani corrosion resistance.2205 DSS, zviri mukati meferrite uye austenite musimbi zvingangoita makumi mashanu muzana, ine yakanakisa mechanical zvivakwa uye corrosion resistance, iyo pamusoro passivation firimu ine dense, ine yakanakisa yunifomu kusaonda, mutengo wakaderera pane wenickel-based alloys 11 , 12. Saka, 2205 DSS inowanzoshandiswa semudziyo wekumanikidza munzvimbo inoparadza, mafuta etsime casing munzvimbo inoparadza CO2, mvura inotonhorera ye condensing system mumafuta ekumahombekombe egungwa nemakemikari minda 13, 14, 15, asi 2205 DSS inogonawo kuva nekuora kunopisa. mubasa.
Parizvino, zvidzidzo zvakawanda zve CO2- uye Cl-pitting corrosion 2205 DSS zvakaitwa munyika uye kunze kwenyika [16,17,18].Ebrahimi19 yakaona kuti kuwedzera potassium dichromate munyu kune mhinduro yeNaCl inogona kuvharidzira 2205 DSS pitting, uye kuwedzera kusanganiswa kwe potassium dichromate kunowedzera tembiricha yakakosha ye2205 DSS pitting.Nekudaro, iyo pitting mukana we2205 DSS inowedzera nekuda kwekuwedzera kweimwe denderedzwa yeNaCl kune potassium dichromate uye inoderera nekuwedzera NaCl concentration.Han20 inoratidza kuti pa 30 kusvika 120 ° C, chimiro che 2205 DSS passivating firimu isanganiswa yeCr2O3 yemukati yemukati, FeO yekunze layer, uye mupfumi Cr;kana tembiricha ichikwira kusvika 150 ° C, iyo passivation firimu inonyungudika., chimiro chemukati chinoshanduka kuCr2O3 uye Cr (OH) 3, uye chikamu chekunze chinoshanduka kuFe (II,III) oxide uye Fe (III) hydroxide.Peguet21 yakaona kuti kumira kwakamira kweS2205 simbi isina tsvina muNaCl mhinduro inowanzoitika kwete pasi peiyo yakakosha tembiricha (CPT) asi mukushandurwa kwetembiricha renji (TTI).Thiadi22 yakagumisa kuti sezvo kusungirirwa kweNaCl kunowedzera, kupikisa kweS2205 DSS kunoderera zvakanyanya, uye iyo yakaipa iyo inoshandiswa inogona kushandiswa, iyo yakaipisisa yekudzivirira kwehutu hwezvinhu.
Muchinyorwa chino, simba rinogona kuongorora, impedance spectroscopy, inogara ichigona, Mott-Schottky curve uye optical electron microscopy zvakashandiswa kuongorora mhedzisiro yemunyu wakanyanya, kukwira kweCl-concentration uye tembiricha pahunhu hwekuora hwe2205 DSS.uye photoelectron spectroscopy, iyo inopa theoretical hwaro hwekushanda kwakachengeteka kwe2205 DSS munzvimbo dzemafuta uye gasi dzine CO2.
Iyo yekuyedza zvinhu inosarudzwa kubva mumhinduro yakabatwa simbi 2205 DSS (simbi giredhi 110ksi), uye iyo huru kemikari inoumbwa inoratidzwa muTafura 1.
Saizi yemuenzaniso we electrochemical ndeye 10 mm × 10 mm × 5 mm, inocheneswa neacetone kubvisa mafuta uye absolute ethanol uye yakaomeswa.Kumashure kwechidimbu chekuedza kunotengeswa kuti ubatanidze urefu hwakakodzera hwetambo yemhangura.Mushure mekuputira, shandisa multimeter (VC9801A) kutarisa magetsi emagetsi echimedu chewelded test, uye wozoisa chisimbiso chisingaiti ne epoxy.Shandisa 400#, 600#, 800#, 1200#, 2000# silicon carbide mvura sandpaper kukwenenzvera nzvimbo yebasa pamushini wekupukuta ne 0.25um polishing agent kusvika pakukasharara kwepamusoro Ra≤1.6um, uye pakupedzisira kuchenesa uye kuisa mu thermostat. .
Priston (P4000A) electrochemical workstation ine matatu-electrode system yakashandiswa.A platinamu electrode (Pt) ine nharaunda ye1 cm2 yakashanda seyebetsero electrode, DSS 2205 (ine nzvimbo ye1 cm2) yakashandiswa seyemagetsi inoshanda, uye referensi electrode (Ag/AgCl) yaishandiswa. kushandiswa.Mhinduro yemuenzaniso yakashandiswa muyedzo yakagadzirwa maererano ne(Table 2).Pamberi pekuedzwa, mhinduro yepamusoro-yakachena N2 (99.99%) yakapfuudzwa kwe1 h, uye ipapo CO2 yakapfuudzwa kwemaminitsi makumi matatu kuti deoxygenate mhinduro., uye CO2 mune mhinduro yaigara iri mumamiriro ekuzara.
Chekutanga, isa sample mutangi rine mhinduro yebvunzo, woiisa munzvimbo yekugezera mvura yekugezera nguva dzose.Iyo yekutanga yekuisa tembiricha ndeye 2 ° C, uye kukwira kwekushisa kunodzorwa pamwero we1 ° C / min, uye tembiricha inodzorwa.pa2-80°C.Celsius.Muedzo unotanga pane imwe nguva inogona kuitika (-0.6142 Vs.Ag/AgCl) uye test curve iIt curve.Zvinoenderana neyakaoma pitting tembiricha yekuyedza standard, iyo Iyo curve inogona kuzivikanwa.Tembiricha apo density iripo inokwira kusvika pa 100 μA/cm2 inonzi yakakosha pitting tembiricha.Avhareji tembiricha yakakosha yekugomba i66.9 °C.Tembiricha tembiricha yepolarization curve uye iyo impedance spectrum yakasarudzwa kuve 30 ° C, 45 ° C, 60 ° C uye 75 ° C, zvichiteerana, uye bvunzo yakadzokororwa katatu pasi pemamiriro akafanana emuenzaniso kuderedza kutsauka kunogona.
Sampu yesimbi yakafumurwa kune mhinduro yakatanga kupolarized pane cathode inogoneka (-1.3 V) kwemaminetsi mashanu isati yaedza iyo potentiodynamic polarization curve kubvisa iyo oxide firimu yakaumbwa pamusoro pebasa resample, uyezve pane yakavhurika yedunhu mukana we. 1 h kusvika iyo corrosion voltage isingagadzirwe.The scan rate of the dynamic potential polarization curve yakaiswa ku 0.333mV/s, uye scan interval potential yakaiswa ku -0.3 ~ 1.2V vs. OCP.Kuti ave nechokwadi chekururama kwekuedzwa, mamiriro akafanana ekuedzwa akadzokororwa 3 nguva.
Impedance spectrum yekuyedza software - Versa Studio.Muedzo wakatanga kuitwa pane yakatsiga yakavhurika-yedunhu mukana, iyo amplitude yealternating disturbance voltage yakaiswa ku 10 mV, uye kuyerwa kwema frequency kwakaiswa ku10-2-105 Hz.spectrum data mushure mekuedzwa.
Yazvino curve yekuyedza maitiro: sarudza akasiyana passivation kugona zvinoenderana nemhedzisiro yeanodic polarization curve, kuyera iyo curve pakugona nguva dzose, uye kodzera iyo yakapetwa kaviri logarithm curve kuti uverenge kutsetseka kweiyo yakagadzirirwa curve yekuongorora firimu.iyo nzira yekuumbwa kweiyo passivating film.
Mushure meiyo yakavhurika yedunhu voltage yadzikama, ita Mott-Schottky curve bvunzo.Edzai zvingangoita scan range 1.0 ~ -1.0V (vS.Ag/AgCl), scan rate 20mV/s, test frequency set to 1000Hz, excitation signal 5mV.
Shandisa X-ray photoelectron spectroscopy (XPS) (ESCALAB 250Xi, UK) sputter kuyedza kuumbwa uye kemikari mamiriro epamusoro passivation firimu mushure me2205 DSS kuumbwa kwefirimu uye kuita kuyerwa kwedata peak-fit processing uchishandisa software yepamusoro.zvichienzaniswa nedhatabhesi yeatomic spectra uye mabhuku ane hukama23 uye akacheneswa uchishandisa C1s (284.8 eV).Iyo morphology yecorrosion uye kudzika kwemakomba pamasamples akaratidzirwa achishandisa Ultra-deep optical digital microscope (Zeiss Smart Zoom5, Germany).
Muenzaniso wakaedzwa panguva imwechete (-0.6142 V rel. Ag / AgCl) nenzira inogara iripo uye iyo corrosion current curve yakanyorwa nenguva.Zvinoenderana neiyo CPT bvunzo chiyero, iyo polarization yazvino density zvishoma nezvishoma inowedzera nekuwedzera tembiricha.1 inoratidza tembiricha yakakosha ye2205 DSS mune imwe mhinduro ine 100 g/L Cl- uye yakazara CO2.Zvinogona kuoneka kuti pane yakadzika tembiricha yemhinduro, iyo density iripo haichinje nekuwedzera nguva yekuyedza.Uye kana kutonhora kwemushonga kwakawedzera kune imwe kukosha, uwandu hwemazuva ano hwakawedzera nokukurumidza, zvichiratidza kuti chiyero chekuparara kwefirimu inopfuura yakawedzera nekuwedzera kwekushisa kwekugadzirisa.Kana tembiricha yemushonga wakasimba ichiwedzerwa kubva pa2°C kuenda pa67°C, polarization current density ye2205DSS inowedzera kusvika pa100µA/cm2, uye avhareji yekushisa kwegomba re2205DSS i66.9°C, ingangoita 16.6°C. yakakwira kupfuura iyo 2205DSS.chiyero 3.5 wt.% NaCl (0.7 V)26.Iyo yakakosha yegomba tembiricha inotsamira pane yakashandiswa inogoneka panguva yekuyerwa: iyo yakaderera iyo inoshandiswa, iyo yakakwirira yakayerwa yakakosha pitting tembiricha.
Pitting yakakosha tembiricha curve ye2205 duplex Stainless simbi mune yakateedzerwa mhinduro ine 100 g/L Cl– uye yakaguta CO2.
Pamusoro pemuonde.2 inoratidza ac impedance plots ye2205 DSS mune yakatemerwa mhinduro ine 100 g/L Cl- uye yakazara CO2 patembiricha dzakasiyana.Zvinogona kuonekwa kuti dhayagiramu yeNyquist ye2205DSS pakupisa kwakasiyana-siyana kunosanganisira high-frequency, mid-frequency uye low-frequency resistance-capacitance arcs, uye resistance-capacitance arcs haisi semicircular.Iyo radius ye capacitive arc inoratidza kukosha kwekupokana kweiyo passivating firimu uye kukosha kwechaji yekuchinjisa kuramba panguva ye electrode reaction.Zvinowanzogamuchirwa kuti iyo yakakura radius ye capacitive arc, zviri nani kupikisa kwekuora kwesimbi substrate mumhinduro27.Patembiricha yemhinduro ye30 °C, radius yecapacitive arc padhiyagiramu yeNyquist uye kona yechikamu padhayagiramu yeimpedance modulus |Z|Bode ndiyo yepamusoro-soro uye 2205 DSS corrosion ndiyo yakaderera.Sezvo tembiricha yemhinduro inowedzera, iyo |Z|impedance modulus, arc radius uye mhinduro kuramba kuderera, uyezve, chikamu chekona zvakare chinodzikira kubva 79 Ω kusvika 58 Ω munharaunda yepakati frequency, inoratidza yakafara peak uye dense yemukati layer uye sparse (porous) yekunze layer ndiyo huru. maficha e inhomogeneous passive film28.Naizvozvo, sezvo tembiricha inokwira, iyo passivating firimu inoumbwa pamusoro pesimbi substrate inonyungudika uye inotsemuka, izvo zvinonetesa zvidziviriro zveiyo substrate uye inokanganisa kushora kweiyo zvinhu29.
Uchishandisa ZSimDeme software kuti ikwane iyo impedance spectrum data, iyo yakaenzana yakaenzana yedunhu inoratidzwa muFig. 330, apo Rs ndiyo yakatemerwa mhinduro yekupikisa, Q1 ndiyo firimu capacitance, Rf ndiko kuramba kweiyo inogadzirwa passivating firimu, Q2 ndiyo yakapetwa kaviri. layer capacitance, uye Rct ndiyo yekuchaja kutamisa kuramba.Kubva pamhedzisiro yekukodzera mutafura.3 inoratidza kuti sezvo kutonhora kwekugadzirisa kwekugadzirisa kunowedzera, kukosha kwen1 kunoderera kubva ku0.841 kusvika ku0.769, iyo inoratidza kuwedzera kwepakati pakati pemaviri-layer capacitors uye kuderera kwehuwandu.Mutero wekutamisa kuramba Rct zvishoma nezvishoma wakadzikira kubva 2.958 × 1014 kusvika 2.541 × 103 Ω cm2, izvo zvakaratidza kuderera zvishoma nezvishoma mukupokana kwekuora kwezvinhu.Kupokana kwemhinduro Rs kwakadzikira kubva 2.953 kusvika 2.469 Ω cm2, uye capacitance Q2 yefirimu inodarika yakadzikira kubva pa5.430 10-4 kusvika 1.147 10-3 Ω cm2, conductivity yemhinduro yakawedzera, kugadzikana kwefirimu rinopfuura kwakaderera. , uye mhinduro Cl-, SO42-, nezvimwewo) mukati mekuwedzera inowedzera, iyo inokurumidza kuparadzwa kwefirimu inopfuura31.Izvi zvinotungamirira kuderera kwemufirimu kuramba Rf (kubva 4662 kusvika 849 Ω cm2) uye kuderera kwepolarization resistance Rp (Rct + Rf) yakaumbwa pamusoro pe duplex simbi isina tsvina.
Nokudaro, kutonhora kwechigadziro kunokanganisa kushorwa kweDSS 2205. Pakupisa kwakadzika kwemhinduro, maitiro ekugadzirisa anoitika pakati pe cathode uye anode pamberi peFe2 +, iyo inobatsira kukurumidza kupera uye kuora kweiyo. anode, pamwe nekupfuura kwefirimu rakaumbwa pamusoro, rakazara uye rakakwirira Density, hukuru hwekupikisa kuchaja kutamiswa pakati pezvigadziriso, kunonotsa kuparara kwesimbi matrix uye inoratidzira zvirinani kusaita ngura.Sezvo tembiricha yemhinduro ichiwedzera, kuramba kubhadharisa kuchinjisa Rct kunoderera, chiyero chekuita pakati peion mumhinduro chinowedzera, uye chiyero chekupararira kweane hutsinye ion chinokura, kuitira kuti zvigadzirwa zvekutanga zvekuora zviumbwe zvakare pamusoro pe. iyo substrate kubva pamusoro pesimbi substrate.Imwe firimu yakaonda inopfuura inoderedza simba rekudzivirira re substrate.
Pamusoro pemuonde.Mufananidzo 4 unoratidza simba rinoita polarization curves ye2205 DSS mumienzaniso mhinduro dzine 100 g/L Cl- uye yakazadza CO2 patembiricha dzakasiyana.Zvinogona kuonekwa kubva pamufananidzo kuti kana iyo inogoneka iri mumhando kubva -0.4 kusvika 0.9 V, anode curves panguva dzakasiyana tembiricha vane pachena passivation matunhu, uye self-corrosion zvinogona anenge -0.7 kusvika -0.5 V. Sezvo density inowedzera ikozvino kusvika ku100 μA/cm233 iyo anode curve inowanzonzi pitting potential (Eb kana Etra).Sezvo tembiricha inokwira, nguva yekupfuura inodzikira, iyo yekuzvigadzirisa inodzikira, iyo corrosion density iripo inowedzera, uye polarization curve inoshanduka ichidzika kurudyi, izvo zvinoratidza kuti firimu rakaumbwa neDSS 2205 mune yakatemerwa mhinduro inoshanda. chiitiko.zviri mukati me100 g/l Cl- uye CO2 yakazara, inowedzera kunzwisiswa kugomba kukora, inokuvadzwa nyore nyore neiyoni ine hutsinye, izvo zvinotungamira mukuwora kwakawedzera kwesimbi matrix uye kuderera kwekusagadzikana kwekuora.
Zvinogona kuonekwa kubva Tafura 4 kuti kana tembiricha ichikwira kubva 30 ° C kusvika 45 ° C, inoenderana overpassivation simba inoderera zvishoma, asi passivation ikozvino density yehukuru hunowirirana inowedzera zvakanyanya, zvichiratidza kuti kuchengetedzwa kwefirimu rinopfuura pasi peizvi. mamiriro anowedzera nekuwedzera kwekushisa.Kana tembiricha yasvika 60°C, mukana wegomba unoenderana unodzikira zvakanyanya, uye maitiro aya anowedzera kuoneka sezvo tembiricha inokwira.Izvo zvinofanirwa kucherechedzwa kuti pa 75 ° C yakakosha yenguva pfupi yepamusoro peak inoonekwa mumufananidzo, ichiratidza kuvepo kwemetastable pitting corrosion pane iyo sample surface.
Nokudaro, nekuwedzera kwekushisa kwemushonga, huwandu hweokisijeni yakanyungudutswa mumhinduro inoderera, pH kukosha kwepamusoro pefirimu inoderera, uye kugadzikana kwefirimu inopera kunoderera.Mukuwedzera, iyo yakakwirira tembiricha yemushonga, iyo inokwirisa basa rehasha ions mune mhinduro uye yakakwirira mwero wekukuvadza kune repamusoro firimu layer ye substrate.Oxides inoumbwa muchikamu chemufirimu inodonha nyore uye inopindirana nemacations muchikamu chemufirimu kuti igadzire zvinonyungudika, zvichiwedzera mukana wekugomba.Sezvo iyo yakagadziridzwa firimu firimu inenge yakasununguka, iyo inodzivirira pa substrate yakaderera, iyo inowedzera kuora kwesimbi substrate.Mhedzisiro yeiyo dynamic polarization inogona bvunzo inoenderana nemhedzisiro ye impedance spectroscopy.
Pamusoro pemuonde.Mufananidzo 5a unoratidza Iyo inomonereka ye2205 DSS mune yemuenzaniso mhinduro ine 100 g/L Cl- uye yakazara CO2.The passivation current density sebasa renguva yakawanikwa mushure mepolarization patembiricha dzakasiyana-siyana kwe1 h pakukwanisa kwe -300 mV (inoenderana neAg/AgCl).Zvinogona kuonekwa kuti passivation yazvino density maitiro e2205 DSS panguva imwecheteyo uye tembiricha dzakasiyana zvakangofanana, uye maitiro anodzikira zvishoma nezvishoma nekufamba kwenguva uye anoita kunge akatsetseka.Sezvo tembiricha yakawedzera zvishoma nezvishoma, iyo passivation ikozvino density ye2205 DSS yakawedzera, iyo yaienderana nemhedzisiro yepolarization, iyo yakaratidzawo kuti maitiro ekudzivirira eiyo firimu layer pasimbi substrate yakadzikira nekuwedzera tembiricha yemhinduro.
Potentiostatic polarization curves ye2205 DSS panguva imwechete yekugadzira firimu inogona uye tembiricha dzakasiyana.(a) Kuwanda kwazvino maringe nenguva, (b) Passive firimu kukura logarithm.
Ongorora hukama huri pakati pepassivation yazvino density uye nguva patembiricha dzakasiyana kune imwecheteyo firimu rekugadzira firimu, sezvakaratidzwa mu (1)34:
Kwandinenge ndiri passivation yazvino density pane iyo firimu yekugadzira inogona, A/cm2.A ndiyo nzvimbo ye electrode inoshanda, cm2.K ndiko kutsetseka kwecurve yakaiswa pairi.t nguva, p
Pamusoro pemuonde.5b inoratidza logI uye logt curves ye2205 DSS pane tembiricha dzakasiyana panguva imwechete yekugadzira firimu.Maererano nezvinyorwa zvinyorwa, 35 apo mutsara wakatsetseka K = -1, iyo firimu yefirimu yakaumbwa pamusoro pe substrate ine denser uye ine zviri nani kupikisa kwesimbi kune substrate yesimbi.Uye kana mutsara wakatwasuka wakatenuka K = -0.5, iyo firimu layer yakaumbwa pamusoro yakasununguka, ine maburi madiki akawanda uye ine kushomeka kwekushomeka kwesimbi kune substrate yesimbi.Zvinogona kuonekwa kuti pa 30 ° C, 45 ° C, 60 ° C, uye 75 ° C, chimiro chemutsetse wefirimu inoshanduka kubva kune dense pores kusvika kune yakasununguka pores maererano neakasarudzwa linear slope.Maererano nePoint Defect Model (PDM)36,37 zvinogona kuonekwa kuti iyo inoshandiswa panguva yekuedzwa haikanganisi huwandu huripo, zvichiratidza kuti tembiricha inobata zvakananga kuyerwa kweanode ikozvino density panguva yekuedzwa, saka ikozvino. inowedzera nekuwedzera kwekushisa.mhinduro, uye kuwanda kwe 2205 DSS kunowedzera, uye kushorwa kwekuora kunoderera.
Iyo semiconductor zvimiro zveyakaonda firimu layer yakaumbwa paDSS inokanganisa kushomeka kwayo38, rudzi rwe semiconductor uye inotakura density yeyakaonda firimu layer inokanganisa kuputika uye kugova kweiyo nhete yefirimu layer DSS39,40 uko capacitance C uye E ye iyo inogona kutetepa firimu layer inogutsa hukama MS, iyo nzvimbo yekuchaja yesemiconductor inoverengerwa nenzira inotevera:
Mune fomula, ε ndiko kubvumirwa kwefirimu rinopfuura patembiricha yekamuri, yakaenzana ne1230, ε0 ndiyo yevacuum permittivity, yakaenzana ne8.85 × 10–14 F/cm, E ndiyo yechipiri charge (1.602 × 10–19 C) ;ND ndiko kuwanda kwen-mhando semiconductor donors, cm-3, NA ndiyo inobvuma density yep-mhando semiconductor, cm-3, EFB ndiyo flat-band inogoneka, V, K inogara Boltzmann, 1.38 × 10–3 .23 J/K, T – tembiricha, K.
Kutenuka uye kupindira kwemutsetse wakasungirirwa kunogona kuverengerwa nekukodzera mutsara kupatsanurwa kune yakayerwa MS curve, yakaiswa concentration (ND), inogamuchirwa yekumisikidza (NA), uye flat band kugona (Efb)42.
Pamusoro pemuonde.6 inoratidza mutsara weMott-Schottky wepamusoro pepamusoro pefirimu ye2205 DSS yakaumbwa mune imwe sarudzo ine 100 g / l Cl- uye yakazara ne CO2 pane inogona (-300 mV) kweawa imwe.Zvinogona kuoneka kuti ese akatetepa-firimu akaturikidzana akaumbwa pakudziya kwakasiyana ane hunhu hwe n+p-mhando bipolar semiconductors.Iyo n-type semiconductor ine mhinduro anion selectivity, iyo inogona kudzivirira Stainless simbi cations kubva mukupararira mumhinduro kuburikidza neiyo passivation firimu, nepo p-type semiconductor ine cation selectivity, iyo inogona kudzivirira iyo corrosive anions mumhinduro kubva papassivation kuyambuka Iyo firimu inouya. kunze pamusoro pe substrate 26 .Zvinogonawo kuonekwa kuti pane kushanduka kwakatsetseka pakati pemakona maviri akakodzera, firimu iri mu flat band state, uye flat band inogona Efb inogona kushandiswa kuona nzvimbo yesimba bhendi re semiconductor uye kuongorora electrochemical yayo. kugadzikana43..
Zvinoenderana neMC curve inokodzera mhedzisiro inoratidzwa muTafura 5, iyo inobuda fungidziro (ND) uye iyo yekugamuchira yekumisikidza (NA) uye iyo flat bhendi inogoneka Efb 44 yehumwe hurongwa hwehukuru hwakaverengerwa.Kuwanda kweiyo inoshandiswa inotakura ikozvino inonyanya kuratidza kukanganisa kwenzvimbo munzvimbo yekuchajisa uye kugona kwegomba kwefirimu rinopfuura.Iyo yakakwirira yehuwandu hwemutakuri wakashandiswa, iyo iri nyore iyo firimu layer inotsemuka uye inowedzera mukana we substrate corrosion45.Mukuwedzera, nekuwedzera zvishoma nezvishoma mukupisa kwemhinduro, ND emitter concentration mufirimu yefirimu yakawedzera kubva pa 5.273 × 1020 cm-3 kusvika 1.772 × 1022 cm-3, uye NA host concentration yakawedzera kubva 4.972 × 1021 kusvika 4.592 ×1023.cm - sezvakaratidzwa mumufananidzo.3, iyo flat band inogona kuwedzera kubva 0.021 V kusvika 0.753 V, nhamba yevatakuri mune mhinduro inowedzera, maitiro pakati peion mumhinduro inowedzera, uye kugadzikana kwefirimu layer kunoderera.Sezvo tembiricha yemushonga ichiwedzera, iyo idiki iyo yakazara kukosha kwemateru emutsara wepedyo, kunowedzera kuwanda kwevatakuri mumhinduro, kunowedzera mwero wekupararira pakati peion, uye kuwedzera huwandu hwezvinzvimbo zveion pane pamusoro peiyo firimu layer., nokudaro kuderedza simbi substrate, kugadzikana uye ngura kuramba 46,47.
Mushonga wemakemikari wemufirimu une simba guru pakugadzikana kwesimbi cations uye kushanda kwesemiconductors, uye kuchinja kwekushisa kune zvakakosha pakuumbwa kwefirimu yesimbi isina tsvina.Pamusoro pemuonde.Mufananidzo 7 unoratidza yakazara XPS spectrum yepamusoro pedenga re2205 DSS firimu mune yakatemerwa mhinduro ine 100 g/L Cl- uye yakazara CO2.Zvinhu zvikuru zviri mumafirimu akaumbwa nemachipisi pakupisa kwakasiyana zvakangofanana, uye zvikamu zvikuru zvemafirimu ndiFe, Cr, Ni, Mo, O, N, uye C. Naizvozvo, zvikamu zvikuru zvemufirimu firimu ndiFe. , Cr, Ni, Mo, O, N uye C. Container ine Cr oxides, Fe oxides uye hydroxides uye shoma shoma yeNi uye Mo oxides.
Yakazara XPS 2205 DSS spectra inotorwa patembiricha dzakasiyana.(a) 30°С, (b) 45°С, (c) 60°С, (d) 75°С.
Iyo huru yekuumbwa kwefirimu ine hukama neiyo thermodynamic zvimiro zvemakomponi muiyo passivating firimu.Maererano nesimba rinosunga rezvinhu zvikuru mufirimu yefirimu, yakapiwa mutafura.6, zvinogona kuonekwa kuti hunhu hwemapeaks eCr2p3/2 akakamurwa kuita simbi Cr0 (573.7 ± 0.2 eV), Cr2O3 (574.5 ± 0.3 eV), uye Cr(OH)3 (575.4 ± 0. 1 eV) se inoratidzwa muMufananidzo 8a, umo oxide yakaumbwa neCr element ndiyo chikamu chikuru mufirimu, iyo inoita basa rinokosha mukudzivisa kuora kwefirimu uye kushanda kwayo kwe electrochemical.Iyo yehukama peak kusimba kweCr2O3 mufirimu layer yakakwira kupfuura iyo yeCr(OH)3.Nekudaro, sezvo tembiricha yakasimba yemhinduro inowedzera, iyo yepamusoro peak yeCr2O3 inoderera zvishoma nezvishoma, nepo hukama hwepamusoro hweCr (OH) 3 hunowedzera zvishoma nezvishoma, izvo zvinoratidza kushandurwa kuri pachena kweiyo Cr3 + muchikamu chefirimu kubva kuCr2O3 kuenda kuCr (OH) 3, uye tembiricha yemhinduro inowedzera.
Simba rinosunga repamusoro-soro remhando yeFe2p3/2 inonyanya kuumbwa nepamusoro ina dzesimbi yenyika Fe0 (706.4 ± 0.2 eV), Fe3O4 (707.5 ± 0.2 eV), FeO (709.5 ± 0.1 eV) uye FeOO1H (713) Fe. eV) ± 0.3 eV), sezvinoratidzwa mumufananidzo 8b, Fe inonyanya kuwanikwa mufirimu yakaumbwa nenzira yeFe2 + uye Fe3 +.Fe2+ kubva kuFeO inotonga Fe (II) pane yakaderera inosunga simba peaks, nepo Fe3O4 uye Fe(III) FeOOH makomisheni anotonga pakakwirira kusunga simba peaks48,49.Kusimba kweiyo Fe3+ peak yakakwirira kupfuura yeFe2+, asi kusimba kweiyo Fe3+ peak kunoderera nekuwedzera tembiricha yemhinduro, uye kusimba kweiyo Fe2+ peak kunowedzera, zvichiratidza shanduko yechinhu chikuru muchikamu chefirimu kubva. Fe3+ kusvika Fe2+ kuwedzera tembiricha yemhinduro.
Hunhu hunoonekwa hwepamusoro hweMo3d5/2 hunonyanya kuve nenzvimbo mbiri dzepamusoro Mo3d5/2 uye Mo3d3/243.50, nepo Mo3d5/2 inosanganisira simbi Mo (227.5 ± 0.3 eV), Mo4+ (228.9 ± 0.2 eV) uye Mo. ), nepo Mo3d3/2 iinewo simbi Mo (230.4 ± 0.1 eV), Mo4+ (231.5 ± 0.2 eV) neMo6+ (232, 8 ± 0.1 eV) sezvakaratidzwa muMufananidzo 8c, saka maMoelements aripo mune anopfuura matatu valence. mamiriro emufirimu layer.Simba rinosungirirwa remhando yepamusoro yeNi2p3 / 2 inosanganisira Ni0 (852.4 ± 0.2 eV) uye NiO (854.1 ± 0.2 eV), sezvinoratidzwa mumufananidzo 8g maererano.Chimiro cheN1s peak chinosanganisira N (399.6 ± 0.3 eV), sezvinoratidzwa mumufananidzo 8d.Hunhu hweO1s peaks dzinosanganisira O2- (529.7 ± 0.2 eV), OH- (531.2 ± 0.2 eV) uye H2O (531.8 ± 0.3 eV), sezvinoratidzwa muFig. Zvikamu zvikuru zvefirimu layer ndezve (OH- uye O2 -) , iyo inonyanya kushandiswa kweiyo oxidation kana hydrogen oxidation yeCr uye Fe mune yefirimu layer.Kusimba kwepamusoro-soro kweOH- kwakawedzera zvakanyanya sezvo tembiricha yakawedzera kubva pa30°C kusvika pa75°C.Naizvozvo, nekuwedzera kwekushisa, iyo huru yezvinhu inoumbwa neO2- mufirimu layer inoshanduka kubva kuO2- kuenda kuOH- uye O2-.
Pamusoro pemuonde.Mufananidzo 9 unoratidza iyo microscopic pamusoro morphology yemuenzaniso 2205 DSS mushure mekusimba kunogona kuve polarization mumuenzaniso mhinduro ine 100 g/L Cl- uye yakazara CO2.Zvinogona kuonekwa kuti pamusoro pemasampuli akaiswa polarized pakupisa kwakasiyana, kune makomba ekuora ane madhigirii akasiyana-siyana, izvi zvinoitika mumhinduro yeayoni ane hutsinye, uye nekuwedzera kwekupisa kwemhinduro, kuparara kwakanyanya kunoitika pa pamusoro pemasampuli.substrate.Huwandu hwemakomba egomba pachikamu cheyuniti uye kudzika kwenzvimbo dzekuora kunowedzera.
Corrosion curves ye2205 DSS mumuenzaniso mhinduro dzine 100 g/l Cl– uye yakazara CO2 patembiricha dzakasiyana (a) 30°C, (b) 45°C, (c) 60°C, (d) 75°C c.
Naizvozvo, kuwedzera kwekushisa kuchawedzera chiitiko chechimwe nechimwe chikamu cheDSS, pamwe nekuwedzera chiitiko chehasha ions munzvimbo ine hutsinye, zvichikonzera imwe dhigirii yekukuvadza kune iyo sampuli yepasi, iyo inowedzera basa regomba., uye kuumbwa kwemakomba ekuora kuchawedzera.Mwero wekugadzirwa kwechigadzirwa uchawedzera uye kushorwa kweiyo zvinhu kuchadzikira51,52,53,54,55.
Pamusoro pemuonde.10 inoratidza morphology uye kudzika kwegomba kwe2205 DSS sampuli yakashongedzwa nehupamhi hwepamusoro hwemunda optical digital microscope.Kubva muonde.10a inoratidza kuti makomba madiki ekuora akaonekwawo akatenderedza makomba mahombe, zvichiratidza kuti firimu rinopfuura repamuenzaniso rakaparadzwa zvishoma nekugadzirwa kwemakomba ekuora pane yakapihwa density yazvino, uye kudzika kwegomba kwakakura kwaive 12.9 µm.sezviri mumufananidzo 10b.
DSS inoratidzira zviri nani kusadzivirirwa nekuora, chikonzero chikuru ndechekuti iyo firimu yakaumbwa pamusoro pesimbi yakanyatsochengetedzwa mumhinduro, Mott-Schottky, maererano nepamusoro XPS mhinduro uye zvinyorwa zvine hukama 13,56,57,58, iyo firimu kunyanya. inopfuura neinotevera Iyi ndiyo nzira ye oxidation ye Fe neCr.
Fe2+ inokurumidza kunyungudika uye inonamira painterface 53 pakati pefirimu nemhinduro, uye iyo cathodic reaction process yakaita seiyi:
Munyika yakasvibiswa, firimu remaviri-layer structural firimu rinoumbwa, iro rinonyanya kuve nemukati wesimbi uye chromium oxides uye yekunze hydroxide layer, uye ions inowanzokura mumapores efirimu.Mushonga wekemikari yemufirimu unofamba une hukama neiyo semiconductor zvimiro, sezvinoratidzwa neMott-Schottky curve, zvichiratidza kuti kuumbwa kweiyo passivating firimu ndeye n + p-mhando uye ine bipolar hunhu.Mhedzisiro yeXPS inoratidza kuti chikamu chekunze cheiyo passivating firimu inonyanya kuumbwa neFe oxides uye hydroxides inoratidza n-type semiconductor properties, uye mukati memukati inonyanya kuumbwa neCr oxides uye hydroxides inoratidza p-type semiconductor properties.
2205 DSS ine yakakwirira resistivity nekuda kweiyo yakakwirira Cr17.54 yemukati uye inoratidza akasiyana madhigirii egomba nekuda kwe microscopic galvanic corrosion55 pakati pe duplex zvimiro.Pitting corrosion ndeimwe yemhando dzinowanzozivikanwa dzekuora muDSS, uye tembiricha ndechimwe chezvinhu zvakakosha zvinopesvedzera maitiro epitting corrosion uye zvine chekuita neiyo thermodynamic uye kinetic maitiro eiyo DSS reaction60,61.Kazhinji, mune yakatemerwa mhinduro ine yakanyanya kuwanda kweCl- uye yakazara CO2, tembiricha inokanganisawo kuumbwa kwegomba uye kutangwa kwekutsemuka panguva yekushushikana corrosion kuputika pasi pekushushikana kwecorrosion kuputika, uye tembiricha yakakosha yegomba yakatsunga kuongorora. kupikisa ngura.DSS.Izvo zvinhu, zvinotaridza kunzwisiswa kwesimbi matrix kune tembiricha, inowanzoshandiswa seyakakosha referensi mukusarudzwa kwezvinhu mumashandisirwo einjiniya.Avhareji yakaoma pitting tembiricha ye2205 DSS mune yakatemerwa mhinduro ndeye 66.9 ° C, iri 25.6 ° C yakakwira kupfuura iyo Super 13Cr Stainless simbi ine 3.5% NaCl, asi iyo yakanyanya kudzika gomba yakasvika 12.9 µm62.Mhedzisiro yekemikari yemagetsi yakasimbisa zvakare kuti nzvimbo dzakachinjika dzepakona uye frequency dzakatetepa nekuwedzera tembiricha, uye sezvo kona yechikamu ichidzikira kubva pa79° kusvika pa58°, kukosha kwe|Z|inoderera kubva 1.26 × 104 kusvika 1.58 × 103 Ω cm2.mhosva kutamisa kuramba Rct yakaderera kubva 2.958 1014 kusvika 2.541 103 Ω cm2, mhinduro kuramba Rs yakaderera kubva 2.953 kusvika 2.469 Ω cm2, firimu kuramba Rf yakaderera kubva 5.430 10-4 cm2 kusvika 1.147 10-3 cm2.Iyo conductivity yehasha mhinduro inowedzera, kugadzikana kwesimbi matrix film layer inoderera, inonyungudika uye inotsemuka nyore.The self-corrosion current density yakawedzera kubva 1.482 kusvika 2.893 × 10-6 A cm-2, uye kuzvidzora kunogona kuderera kubva -0.532 kusvika -0.621V.Zvinogona kuonekwa kuti kuchinja kwekushisa kunokanganisa kutendeseka uye kuwanda kweiyo firimu layer.
Kusiyana neizvi, huwandu hwakanyanya hweCl- uye mhinduro yakazara ye CO2 zvishoma nezvishoma inowedzera adsorption kugona kweCl- pamusoro peiyo passivating firimu nekuwedzera tembiricha, kugadzikana kweiyo passivation firimu inove isina kugadzikana, uye inodzivirira mhedzisiro substrate inova isina simba uye mukana wekupinda mugomba unowedzera.Muchiitiko ichi, basa reiyoni inoparadza mumhinduro inowedzera, iyo okisijeni inodzikira, uye firimu repamusoro rezvinhu zvakasvibiswa rinonetsa kukurumidza kupora, izvo zvinogadzira mamwe mamiriro akanaka ekuwedzera adsorption yemaion anoparadza pamusoro.Kuderedzwa kwezvinhu63.Robinson nevamwe.[64] yakaratidza kuti nekuwedzera kwekushisa kwemhinduro, chiyero chekukura kwemakomba chinowedzera, uye chiyero chekupararira kweion mumushonga unowedzerawo.Kana tembiricha yakwira kusvika 65 °C, kunyungudika kweokisijeni mumushonga une maCl-ions kunoderedza cathodic reaction process, mwero wegomba unodzikira.Han20 yakaongorora mhedzisiro yetembiricha pamaitiro ekuora kwe2205 duplex simbi isina tsvina munzvimbo yeCO2.Mhedzisiro yacho yakaratidza kuti kuwedzera kwekushisa kwakawedzera huwandu hwezvigadzirwa zvekuora uye nzvimbo yeshrinkage cavities pamusoro pechinhu.Saizvozvo, kana tembiricha yakwira kusvika 150°C, firimu reoxide riri pamusoro rinotsemuka, uye kuwanda kwemakoronga ndiko kwakanyanya.Lu4 yakaongorora mhedzisiro yekushisa pane corrosion maitiro e2205 duplex stainless simbi kubva papassivation kuenda kune activation munzvimbo yegeothermal ine CO2.Mhedzisiro yavo inoratidza kuti pakuyedza tembiricha iri pasi pe150 ° C, iyo firimu yakaumbwa ine chimiro cheamorphous chimiro, uye yemukati interface ine nickel-rich layer, uye patembiricha ye300 ° C, inokonzeresa corrosion chigadzirwa chine nanoscale chimiro. .-polycrystalline FeCr2O4, CrOOH uye NiFe2O4.
Pamusoro pemuonde.11 idhizaini yekuora uye firimu rekugadzira maitiro e2205 DSS.Isati yashandiswa, 2205 DSS inoumba firimu rinopfuura mumhepo.Mushure mekunyudzwa munharaunda inofananidzira mhinduro ine zvigadziriso zvine huwandu hwepamusoro hweCl- uye CO2, nzvimbo yayo inokurumidza kukomberedzwa neayoni akasiyana-siyana ane hutsinye (Cl-, CO32-, nezvimwewo).)J. Banas 65 yakasvika pakugumisa kuti munzvimbo umo CO2 iripo panguva imwe chete, kugadzikana kwefirimu inofamba pamusoro pezvinhu zvichaderera nekufamba kwenguva, uye iyo yakagadzirwa carbonic acid inowedzera kuwedzera conductivity yeion mu passivating. layer.firimu uye kukurumidza kwekuparara kweion mufirimu inofamba.passivating film.Nekudaro, iyo firimu layer pamusoro pemuenzaniso wepamusoro iri mune inosimba yakaenzana nhanho yekuparara uye repassivation66, Cl- inoderedza mwero wekuumbwa kweiyo yepamusoro firimu layer, uye makomba madiki egomba anoonekwa padivi penzvimbo yefirimu, se. inoratidzwa muMufananidzo 3. Ratidza.Sezvinoratidzwa muMufananidzo 11a na b, makomba madiki asina kugadzikana anooneka panguva imwe chete.Sezvo tembiricha inokwira, kuita kweiyoni inoparadza mumhinduro pane iyo firimu layer inowedzera, uye kudzika kwemakomba madiki asina kugadzikana kunowedzera kusvika iyo firimu layer yapindwa zvachose neyakajeka, sezvakaratidzwa muMufananidzo 11c.Nekuwedzera kwekuwedzera kwekushisa kwesvikiro rekunyungudika, zviri mukati me CO2 yakanyungudutswa mumhinduro inokurumidza, izvo zvinotungamira kuderera kwepH kukosha kwemhinduro, kuwedzera kwehuremu hwemakomba madiki asina kugadzikana ekuora paSPP pamusoro. , kudzika kwemakomba ekutanga ekuora kunowedzera uye kunowedzera, uye firimu rinopfuura pamuenzaniso wepamusoro Sezvo ukobvu hunoderera, iyo passivating iyo firimu inova yakanyanya kuita gomba sezvakaratidzwa muFigure 11d.Uye mhedzisiro ye electrochemical yakasimbisa zvakare kuti shanduko yekushisa ine imwe mhedzisiro pakuvimbika uye kuwanda kwefirimu.Nokudaro, zvinogona kuonekwa kuti kuora mune zvinogadziriswa zvakazadzwa ne CO2 ine huwandu hwepamusoro hweCl- yakasiyana zvikuru nekuora mune zvinogadziriswa zvine zvishoma zvishoma zveCl-67,68.
Corrosion process 2205 DSS nekugadzirwa uye kuparadzwa kwefirimu idzva.(a) Maitiro 1, (b) Maitiro 2, (c) Maitiro 3, (d) Maitiro 4.
Avhareji yakaoma pitting tembiricha ye2205 DSS mune yakatemerwa mhinduro ine 100 g/l Cl- uye yakazara CO2 i66.9 ℃, uye iyo yakanyanya kudzika gomba i12.9 µm, iyo inoderedza kushorwa kwe2205 DSS uye inowedzera kunzwa kwekugomba.kuwedzera tembiricha.
Nguva yekutumira: Feb-16-2023