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Duplex 2205 igwe anaghị agba nchara (DSS) nwere ezigbo nguzogide corrosion n'ihi usoro ihe owuwu ya, mana ikuku CO2 nwere mmanụ na gas na-esiwanye ike na-ebute ogo corrosion dị iche iche, ọkachasị pitting, nke na-eyi egwu nchekwa na ntụkwasị obi nke mmanụ na eke. ngwa gas.mmepe nke gas.N'ime ọrụ a, a na-eji ule imikpu na nyocha nke electrochemical jikọtara ya na laser confocal microscopy na X-ray photoelectron spectroscopy.Nsonaazụ gosiri na nkezi okpomọkụ dị oke egwu maka pitting 2205 DSS bụ 66.9 Celsius.Mgbe okpomọkụ dị elu karịa 66.9 ℃, ike imebi pitting, oge nkwụsịtụ na ikike nke corrosion onwe ya na-ebelata, nha passivation ugbu a njupụta na-abawanye, na pitting uche na-abawanye.Site na mmụba ọzọ na okpomọkụ, radius nke capacitive arc 2205 DSS na-ebelata, nkwụsi ike elu na nkwụghachi ụgwọ ụgwọ ji nwayọọ nwayọọ na-ebelata, na njupụta nke ndị na-enye onyinye na ndị na-anabata ya na oyi akwa nke ngwaahịa na n + p-bipolar e ji mara nakwa. na-abawanye, ọdịnaya nke Cr oxides n'ime oyi akwa nke ihe nkiri na-ebelata, na-abawanye ọdịnaya nke Fe oxides na oyi akwa nke elu, mgbasa nke oyi akwa ihe nkiri na-abawanye, nkwụsi ike na-ebelata, ọnụ ọgụgụ nke olulu na pore size na-abawanye.
N'ihe gbasara mmepe akụ na ụba ngwa ngwa na mmepe mmekọrịta ọha na eze na ọganihu mmekọrịta ọha na eze, ọchịchọ nke mmanụ na mmanụ gas na-aga n'ihu na-eto eto, na-amanye mmanụ na gas mmepe iji nwayọọ nwayọọ gbanwee gaa n'ebe ndịda ọdịda anyanwụ na n'ụsọ oké osimiri nwere ọnọdụ na gburugburu ebe obibi siri ike karị, ya mere ọnọdụ ọrụ nke tubing downhole na-akawanye njọ..Mbibi 1,2,3.N'ebe nyocha mmanụ na gas, mgbe mmụba nke CO2 4 na salinity na chlorine ọdịnaya 5, 6 n'ime mmiri a na-emepụta, ọkpọkọ carbon steel 7 nkịtị na-adabara nnukwu corrosion, ọbụlagodi ma ọ bụrụ na a na-agbanye ihe mgbochi corrosion n'ime eriri ọkpọkọ. enweghị ike imechi corrosion nke ọma nchara enweghị ike imezu ihe achọrọ maka ịrụ ọrụ ogologo oge na gburugburu CO28,9,10 na-emebi emebi.Ndị nyocha ahụ tụgharịrị gaa na igwe anaghị agba nchara duplex (DSS) nwere nguzogide corrosion ka mma.2205 DSS, ọdịnaya nke ferrite na austenite na ígwè bụ ihe dị ka 50%, nwere ọmarịcha n'ibu Njirimara na corrosion eguzogide, elu passivation film bụ ok, nwere magburu onwe edo corrosion eguzogide, price bụ ala karịa nke nickel dabeere alloys 11. , 12. Ya mere, 2205 DSS na-ejikarị dị ka arịa nrụgide na gburugburu ebe obibi corrosive, mmanụ nke ọma casing na corrosive CO2 gburugburu ebe obibi, mmiri nju oyi maka condensing usoro n'ụsọ oké osimiri mmanụ na chemical ubi 13, 14, 15, ma 2205 DSS nwekwara ike inwe corrosive perforation. na-eje ozi.
Ka ọ dị ugbu a, a na-eme ọtụtụ ọmụmụ banyere CO2- na Cl-pitting corrosion 2205 DSS na mba na mba ọzọ [16,17,18].Ebrahimi19 chọpụtara na ịgbakwunye nnu potassium dichromate na ngwọta NaCl nwere ike igbochi 2205 DSS pitting, na ịba ụba nke potassium dichromate na-abawanye okpomọkụ dị egwu nke 2205 DSS pitting.Otú ọ dị, ikike nke 2205 DSS na-abawanye n'ihi mgbakwunye nke ụfọdụ ntinye nke NaCl na potassium dichromate ma na-ebelata site na ịba ụba NaCl.Han20 na-egosi na na 30 ruo 120 ° C, nhazi nke ihe nkiri na-agafe agafe 2205 DSS bụ ngwakọta nke oyi akwa dị n'ime Cr2O3, oyi akwa FeO, na ọgaranya Cr;mgbe okpomọkụ na-ebili ruo 150 Celsius, ihe nkiri passivation na-agbaze., Ọdịdị dị n'ime ya na-agbanwe na Cr2O3 na Cr (OH) 3, na oyi akwa na-agbanwe na Fe (II, III) oxide na Fe (III) hydroxide.Peguet21 chọpụtara na olulu S2205 igwe anaghị agba nchara na ngwọta NaCl anaghị adịkarị n'okpuru okpomọkụ pitting dị oke egwu (CPT) kama na mgbanwe mgbanwe okpomọkụ (TTI).Thiadi22 kwubiri na ka ntinye uche nke NaCl na-abawanye, nguzogide corrosion nke S2205 DSS na-ebelata nke ukwuu, na ihe na-adịghị mma nke etinyere ya, na-akawanye njọ nguzogide corrosion nke ihe.
N'isiokwu a, a na-eji nyocha ike ike, impedance spectroscopy, ikike na-adịgide adịgide, Mott-Schottky curve na optical microscopy eletrọnịkị iji mụọ mmetụta nke salinity dị elu, nnukwu Cl-iche na okpomọkụ na àgwà corrosion nke 2205 DSS.na photoelectron spectroscopy, nke na-enye usoro ihe ndabere maka ọrụ nchekwa nke 2205 DSS na gburugburu mmanụ na gas nwere CO2.
A na-ahọrọ ihe nnwale ahụ site na ngwọta mesoo ígwè 2205 DSS (ọkwa ígwè 110ksi), na ihe mejupụtara kemịkal bụ isi egosiri na tebụl 1.
Ogo nke ihe nlele electrochemical bụ 10 mm × 10 mm × 5 mm, a na-ehichapụ ya na acetone iji wepụ mmanụ na ethanol zuru oke na akpọnwụ.A na-ere azụ nke mpempe ule iji jikọọ ogologo waya ọla kọpa kwesịrị ekwesị.Mgbe ịgbado ọkụ, jiri a multimeter (VC9801A) ịlele eletrik conductivity nke welded ule ibe, na mgbe ahụ na-adịghị arụ ọrụ n'elu na epoxy mechie.Jiri 400 #, 600 #, 800 #, 1200 #, 2000 # silicon carbide mmiri sandpaper iji polishing elu ọrụ na igwe polishing na 0.25um polishing agent ruo mgbe elu roughness Ra≤1.6um, na n'ikpeazụ ọcha na-etinye na thermostat. .
A na-eji ụlọ ọrụ electrochemical nke Priston (P4000A) nwere usoro electrode atọ.Platinum electrode (Pt) nke nwere mpaghara 1 cm2 jere ozi dị ka electrode inyeaka, a na-eji DSS 2205 (nke nwere mpaghara 1 cm2) dị ka electrode na-arụ ọrụ, na electrode ntụaka (Ag/AgCl) bụ. eji.A kwadebere ihe ngwọta ihe nlereanya a na-eji na ule dị ka (Table 2).Tupu ule ahụ, a na-agafe ihe ngwọta N2 dị elu (99.99%) maka 1 h, wee nyefee CO2 maka 30 min iji deoxygenate ngwọta., na CO2 na ngwọta bụ mgbe niile na ọnọdụ nke saturation.
Nke mbụ, tinye ihe nlele ahụ na tank nke nwere ngwọta ule, ma tinye ya na mmiri mmiri na-ekpo ọkụ mgbe niile.Okpomọkụ ntọala mbụ bụ 2 Celsius C, a na-achịkwa ịrị elu okpomọkụ na ọnụego 1 Celsius C / min, a na-achịkwa oke okpomọkụ.na 2-80 Celsius C.Celsius.Nnwale ahụ na-amalite na ike na-adịgide adịgide (-0.6142 Vs.Ag/AgCl) na ule ule bụ usoro Ọ.Dị ka ọkọlọtọ pitting okpomọkụ dị oke egwu si dị, ọ nwere ike mara ya.A na-akpọ ọnọdụ okpomọkụ nke njupụta dị ugbu a na-eru 100 μA/cm2 okpomọkụ dị egwu.Okpomọkụ dị oke egwu maka olulu bụ 66.9 Celsius C.A na-ahọrọ okpomọkụ nke ule maka ntụgharị polarization na ụdị impedance ka ọ bụrụ 30 ° C, 45 ° C, 60 ° C na 75 ° C, n'otu n'otu, a na-emegharị ule ahụ ugboro atọ n'okpuru otu ọnọdụ nlele ahụ iji belata ihe ndị nwere ike ime.
A metal sample ekpughere ihe ngwọta bụ nke mbụ polarized na a cathode nwere ike (-1.3 V) maka 5 min tupu anwale potentiodynamic polarization curve iji kpochapụ ihe nkiri oxide kpụrụ n'elu ọrụ nke sample, na mgbe ahụ na-emeghe sekit nwere ike. 1 h ruo mgbe voltaji corrosion agaghị eguzobe.Atụnyere ọnụ ọgụgụ nyocha nke ike ike polarization curve ka ọ bụrụ 0.333mV/s, na ike nyocha oge ka atọrọ ka -0.3 ~ 1.2V vs. OCP.Iji hụ na izi ezi nke ule ahụ, a na-emeghachi otu ọnọdụ ule ugboro 3.
Ngwanrọ nyocha nke impedance - Versa Studio.Ebu ụzọ mee ule a n'ebe enwere ike imeghe oghere, njupụta nke voltaji ọgba aghara ọzọ ka atọrọ ka ọ bụrụ 10 mV, na nha nha ka edobere na 10–2–105 Hz.ụdịdị dị iche iche data mgbe ule.
Usoro nnwale oge dị ugbu a: họrọ ikike ngafe dị iche iche dabere na nsonaazụ nke mgbagharị anodic polarization, tụọ usoro ọ na-enwe mgbe niile, ma dabara n'usoro logarithm okpukpu abụọ iji gbakọọ mkpọda mkpọda dabara adaba maka nyocha ihe nkiri.usoro nke e guzobere ihe nkiri passivating.
Mgbe voltaji sekit mepere emepe kwụsie ike, mee nnwale Mott-Schottky curve.Nnwale ike nyocha nso 1.0 ~ -1.0V (vS.Ag/AgCl), nyocha nyocha 20mV/s, ugboro ule setịpụrụ na 1000Hz, mgbama mkpali 5mV.
Jiri X-ray photoelectron spectroscopy (XPS) (ESCALAB 250Xi, UK) iji nwalee nhazi na ọnọdụ kemịkalụ nke ihe nkiri passivation elu mgbe emechara ihe nkiri 2205 DSS wee rụọ nhazi data kacha mma site na iji sọftụwia dị elu.atụnyere ọdụ data nke atomic spectra na akwụkwọ ndị metụtara ya23 na calibrated site na iji C1s (284.8 eV).Ihe e ji mara ọdịdị nke corrosion na omimi nke olulu dị na nlele ahụ site na iji microscope dijitalụ dị omimi (Zeiss Smart Zoom5, Germany).
A nwalere ihe nlele ahụ n'otu ikike ahụ (-0.6142 V rel. Ag / AgCl) site na usoro nwere ike na-eme mgbe niile ma na-edekọ ihe mgbochi corrosion ugbu a na oge.Dị ka ọkọlọtọ ule CPT si dị, njupụta nke ugbu a polarization ji nwayọọ nwayọọ na-abawanye na okpomọkụ na-abawanye.1 na-egosi oke okpomoku dị egwu nke 2205 DSS na ngwọta emepụtara nke nwere 100 g/L Cl na CO2 juputara.Enwere ike ịhụ na na obere okpomọkụ nke ngwọta, njupụta dị ugbu a anaghị agbanwe agbanwe na oge nyocha na-abawanye.Na mgbe okpomọkụ nke ngwọta na-abawanye na uru ụfọdụ, njupụta dị ugbu a na-abawanye ngwa ngwa, na-egosi na ọnụego nke mgbasa nke ihe nkiri na-agafe agafe na-abawanye na mmụba nke okpomọkụ nke ngwọta.Mgbe okpomọkụ nke ngwọta siri ike na-abawanye site na 2 ° C ruo ihe dịka 67 ° C, njupụta nke 2205DSS dị ugbu a na-abawanye ruo 100µA/cm2, na nkezi ikpo ọkụ dị egwu nke 2205DSS bụ 66.9 ° C, nke dị ihe dịka 16.6 ° C. dị elu karịa 2205DSS.ọkọlọtọ 3.5 wt.% NaCl (0.7 V) 26.Okpomọkụ pitting dị oke egwu na-adabere na ike etinyere n'oge a na-atụ ya: ka ike etinyere na-agbada, ka ahụ ka a na-atụle okpomọkụ dị oke egwu.
Ịkụnye usoro okpomọkụ dị egwu nke 2205 duplex igwe anaghị agba nchara n'ime ngwọta simulated nwere 100 g/L Cl- yana CO2 jupụtara.
Na fig.2 na-egosi ac impedance plots nke 2205 DSS na simulated ngwọta nwere 100 g/L Cl- na juputara CO2 na dị iche iche okpomọkụ.Enwere ike ịhụ na eserese Nyquist nke 2205DSS na okpomọkụ dị iche iche na-agụnye nnukwu ugboro ugboro, n'etiti etiti na obere nkwụsị nkwụsị-ike arcs, na ndị na-eguzogide-ike arcs abụghị semicircular.Radius nke arc capacitive na-egosipụta uru nguzogide nke ihe nkiri na-agafe agafe na uru nke nkwụghachi ụgwọ ụgwọ n'oge mmeghachi omume electrode.A na-anabatakarị na ka radius nke capacitive arc na-ebuwanye ibu, ka mma nguzogide corrosion nke mkpụrụ metal na ngwọta27.N'ebe okpomọkụ dị 30 Celsius C, radius nke capacitive arc na eserese Nyquist na akụkụ akụkụ na eserese nke modul impedance |Z|Bode bụ nke kachasị elu na 2205 DSS corrosion bụ nke kasị ala.Ka okpomọkụ ngwọta na-abawanye, |Z|modul impedance, arc radius na iguzogide ihe ngwọta na-ebelata, na mgbakwunye, akụkụ akụkụ ahụ na-ebelatakwa site na 79 Ω ruo 58 Ω na mpaghara etiti etiti, na-egosi ọnụ ọgụgụ dị elu na nnukwu oyi akwa dị n'ime na oyi akwa dị elu (porous) bụ isi. atụmatụ nke inhomogeneous pasive film28.Ya mere, ka okpomọkụ na-ebili, ihe nkiri na-agafe agafe nke e mere n'elu nke metal substrate na-agbaze ma na-agbaze, nke na-ebelata ihe nchebe nke mkpụrụ ahụ ma na-emebi nguzogide corrosion nke ihe29.
Iji sọftụwia ZSimDeme dabara na data spectrum impedance, a na-egosipụta sekit dabara adaba na Fig 330, ebe Rs bụ nguzogide simulated ngwọta, Q1 bụ ikike ihe nkiri, Rf bụ nguzogide nke ihe nkiri na-agafe agafe, Q2 bụ okpukpu abụọ. oyi akwa capacitance, na Rct bụ nkwụghachi ụgwọ nnyefe.Site na nsonaazụ dabara na tebụl.3 na-egosi na ka okpomọkụ nke ngwọta simulated na-abawanye, uru nke n1 na-ebelata site na 0.841 ruo 0.769, nke na-egosi mmụba nke ọdịiche dị n'etiti ndị na-emepụta ihe mkpuchi abụọ na mbelata njupụta.Nkwụsị nnyefe ụgwọ Rct ji nwayọọ nwayọọ na-ebelata site na 2.958 × 1014 ruo 2.541 × 103 Ω cm2, nke gosipụtara mbelata nke nta nke nta nke ntachi obi nke ihe.Nguzogide nke ngwọta Rs belatara site na 2.953 ruo 2.469 Ω cm2, na capacitance Q2 nke ihe nkiri na-agafe agafe na-ebelata site na 5.430 10-4 ruo 1.147 10-3 Ω cm2, conductivity nke ngwọta mụbara, nkwụsi ike nke ihe nkiri na-agafe agafe belatara. , na ngwọta Cl-, SO42-, wdg) na ọkara na-abawanye, nke accelerates mbibi nke passivating film31.Nke a na-eduga na mbelata nke ihe nkiri Rf (site na 4662 ruo 849 Ω cm2) yana mbelata nguzogide polarization Rp (Rct + Rf) nke kpụrụ n'elu igwe anaghị agba nchara duplex.
Ya mere, okpomọkụ nke ngwọta na-emetụta nguzogide corrosion nke DSS 2205. N'ebe dị ala nke ngwọta, usoro mmeghachi omume na-eme n'etiti cathode na anode n'ihu Fe2 +, nke na-enye aka na mgbasa ngwa ngwa na corrosion. anode, nakwa dị ka passivation nke film kpụrụ n'elu, ọzọ zuru ezu na elu Njupụta, ukwuu iguzogide ụgwọ nyefe n'etiti ngwọta, slows ala mgbasa nke metal matrix na-egosipụta mma corrosion eguzogide.Dị ka okpomọkụ nke ngwọta na-abawanye, ndị na-eguzogide ụgwọ nyefe Rct na-ebelata, ọnụego nke mmeghachi omume n'etiti ions na ngwọta accelerates, na ọnụego nke mgbasa nke ion ike ike accelerates, nke mere na mbụ corrosion ngwaahịa na-mere ọzọ n'elu. mkpụrụ si n'elu nke metal substrate.Ihe nkiri na-agafe agafe nke dị gịrịgịrị na-ebelata ihe nchebe nke mkpụrụ ahụ.
Na fig.Ọnụọgụ 4 na-egosi usoro mgbagha nke nwere ike ịdị ike nke 2205 DSS na ngwọta simulated nwere 100 g/L Cl- na CO2 jupụtara na okpomọkụ dị iche iche.Enwere ike ịhụ site na ọnụ ọgụgụ ahụ na mgbe ike dị na -0.4 ruo 0.9 V, akụkụ anode na okpomọkụ dị iche iche nwere mpaghara passivation doro anya, na ikike nke onwe ya dị ihe dịka -0.7 ruo -0.5 V. Dị ka njupụta na-abawanye ugbu a ruo 100 μA/cm233 akụkụ anode ka a na-akpọkarị ike pitting (Eb ma ọ bụ Etra).Ka okpomọkụ na-ebili, oge ngafe na-ebelata, ikike nke ime onwe ya na-ebelata, njupụta nke corrosion ugbu a na-emekarị ka ọ dịkwuo elu, na polarization curve na-agbada n'aka nri, nke na-egosi na ihe nkiri nke DSS 2205 guzobere na ngwọta simulated na-arụ ọrụ. ọrụ.Ọdịnaya nke 100 g/l Cl- na CO2 juru eju, na-abawanye mmetụta nke pitting corrosion, na-emebi ngwa ngwa site na ion ike ike, nke na-eduga n'ịbawanye corrosion nke matrix metal na mbelata nguzogide corrosion.
Enwere ike ịhụ site na Tebụl 4 na mgbe okpomọkụ na-ebili site na 30 ° C ruo 45 ° C, ikike nke overpassivation kwekọrọ na-ebelata ntakịrị, mana njupụta nke ugbu a nke nha nha nha na-abawanye nke ukwuu, na-egosi na nchebe nke ihe nkiri na-agafe agafe n'okpuru ndị a. ọnọdụ na-abawanye na okpomọkụ na-abawanye.Mgbe okpomoku ruru 60 Celsius C, ikike nke ikpo ọkụ kwekọrọ na-ebelata nke ukwuu, omume a na-apụtakwa ìhè ka okpomọkụ na-ebili.Ekwesiri iburu n'uche na na 75 Celsius, ọnụ ọgụgụ dị ịrịba ama na-agafe agafe ugbu a na-apụta na ọnụ ọgụgụ a, na-egosi ọnụnọ nke corrosion metastable n'elu ihe atụ.
Ya mere, na mmụba nke okpomọkụ nke ngwọta, ọnụọgụ oxygen na-agbaze na ngwọta na-ebelata, uru pH nke ihe nkiri ahụ na-ebelata, na nkwụsi ike nke ihe nkiri na-agafe agafe na-ebelata.Tụkwasị na nke ahụ, ka okpomọkụ nke ngwọta dị elu, ọrụ nke ions na-eme ihe ike na ngwọta dị elu na ọnụ ọgụgụ nke mmebi nke elu ihe nkiri oyi akwa nke mkpụrụ.Oxides guzobere na fim oyi akwa mfe ịdapụ na-emeghachi omume na cations na fim oyi akwa na-etolite soluble ogige, na-amụba ohere nke pitting.Ebe ọ bụ na oyi akwa ihe nkiri ahụ emegharịrị dị ntakịrị, mmetụta nchebe na mkpụrụ ahụ dị ala, nke na-eme ka corrosion nke metal metal na-abawanye.Nsonaazụ nke nnwale polarization dị ike dabara na nsonaazụ nke spectroscopy impedance.
Na fig.Onyonyo 5a na-egosi na ọ na-agbagọ maka 2205 DSS n'ụdị ngwọta nwere 100 g/L Cl- na CO2 juru eju.A na-enweta njupụta nke passivation dị ugbu a dị ka ọrụ nke oge mgbe polarization na okpomọkụ dị iche iche maka 1 h na ike nke -300 mV (n'ihe metụtara Ag / AgCl).Enwere ike ịhụ na usoro njupụta dị ugbu a nke 2205 DSS n'otu ikike na okpomọkụ dị iche iche bụ otu ihe ahụ, usoro ahụ ji nwayọọ nwayọọ na-ebelata ka oge na-aga ma na-adị ire ụtọ.Dị ka okpomọkụ ji nwayọọ nwayọọ na-abawanye, passivation ugbu njupụta nke 2205 DSS mụbara, bụ nke kwekọrọ na ya pụta polarization, nke gosikwara na-echebe àgwà nke ihe nkiri oyi akwa na metal substrate mbelata na-amụba ngwọta okpomọkụ.
Ọkpụkpụ polarization nwere ike nke 2205 DSS n'otu ikike imepụta ihe nkiri yana okpomoku dị iche iche.(a) Njupụta dị ugbu a na oge, (b) Logarithm uto ihe nkiri na-agafe agafe.
Nyochaa mmekọrịta dị n'etiti njupụta dị ugbu a na oge na okpomọkụ dị iche iche maka otu ike ịmepụta ihe nkiri, dị ka egosiri na (1)34:
Ebe m bụ njupụta dị ugbu a na ike imepụta fim, A/cm2.A bụ mpaghara electrode na-arụ ọrụ, cm2.K bụ mkpọda nke mgbanaka dabara na ya.t oge, s
Na fig.5b na-egosi logI na logt curves maka 2205 DSS na okpomọkụ dị iche iche n'otu ikike imepụta ihe nkiri.Dị ka akwụkwọ akụkọ data,35 mgbe akara mkpọda K = -1, fim oyi akwa kpụrụ n'elu nke mkpụrụ bụ denser na nwere mma corrosion iguzogide metal substrate.Na mgbe ahịrị kwụ ọtọ slopes K = -0.5, ihe nkiri oyi akwa kpụrụ n'elu bụ rụrụ, nwere ọtụtụ obere oghere ma na-adịghị mma corrosion iguzogide na metal mkpụrụ.Enwere ike ịhụ na na 30ºC, 45°C, 60°C, na 75°C, nhazi nke oyi akwa ihe nkiri na-agbanwe site na pores siri ike gaa n'oghere tọpụrụ dịka mkpọda ahịrị ahọpụtara.Dị ka Point Defect Model (PDM) 36,37 nwere ike ịhụ na etinyere ikike n'oge ule adịghị emetụta ugbu a njupụta, na-egosi na okpomọkụ na-emetụta kpọmkwem nha nke anode njupụta ugbu a n'oge ule, otú ugbu a. na-abawanye na okpomọkụ na-abawanye.ngwọta, na njupụta nke 2205 DSS na-abawanye, na nkwụsị nke corrosion na-ebelata.
The semiconductor Njirimara nke mkpa film oyi akwa kpụrụ na DSS na-emetụta ya corrosion resistance38, ụdị semiconductor na ụgbọelu njupụta nke mkpa film oyi akwa na-emetụta cracking na pitting nke mkpa film oyi akwa DSS39,40 ebe capacitance C na E nke oyi akwa ihe nkiri dị mkpa nwere ike imeju mmekọrịta MS, a na-agbakọ ụgwọ oghere nke semiconductor n'ụzọ ndị a:
Na usoro, ε bụ ikike nke ihe nkiri na-agafe agafe na ụlọ okpomọkụ, hà nhata 1230, ε0 bụ ikike ikike, hà 8.85 × 10-14 F / cm, E bụ ụgwọ nke abụọ (1.602 × 10-19 C). ;ND bụ njupụta nke n-ụdị semiconductor inye onyinye, cm-3, NA bụ njupụta nke p-ụdị semiconductor, cm–3, EFB bụ ikike nke ewepụghị, V, K bụ Boltzmann mgbe niile, 1.38 × 10–3. .23 J/K, T - okpomọkụ, K.
Enwere ike ịgbakọ mkpọda na nkwụsị nke ahịrị dabara adaba site n'itinye nkewa ahịrị n'ahịrị n'usoro MS tụrụ, itinye uche (ND), itinye uche anabatara (NA), na ikike bandwit flat (Efb)42.
Na fig.6 na-egosi Mott-Schottky curve nke elu oyi akwa nke ihe nkiri 2205 DSS kpụrụ na ngwọta simulated nwere 100 g / l Cl- na juputara na CO2 na ike (-300 mV) maka 1 hour.Enwere ike ịhụ na ihe nkiri niile dị mkpa na-etolite na okpomọkụ dị iche iche nwere njirimara nke n+p-ụdị bipolar semiconductor.The n-ụdị semiconductor nwere ngwọta anion selectivity, nke nwere ike igbochi igwe anaghị agba nchara cations na-agbasa n'ime ngwọta site passivation film, mgbe p-ụdị semiconductor nwere cation selectivity, nke nwere ike igbochi corrosive anions na ngwọta si passivation crossings Ihe nkiri na-abịa. pụta n'elu nke mkpụrụ 26 .Enwere ike ịhụ na enwere mgbanwe dị mma n'etiti akụkụ abụọ dabara adaba, ihe nkiri ahụ dị na steeti ewepụghị, yana enwere ike iji Efb nke nwere ike iji chọpụta ọnọdụ nke eriri ike nke semiconductor wee nyochaa electrochemical ya. kwụsie ike43..
Dabere na nsonaazụ dabara adaba nke MC egosipụtara na Tebụl 5, a na-agbakọ itinye uche na-apụ apụ (ND) na nnabata nnabata (NA) yana eriri flat nwere Efb 44 nke otu usoro ịdị ukwuu.The njupụta nke etinyere ụgbọelu ugbu a tumadi na-akọwapụta ntụpọ ntụpọ na oghere chaja oyi akwa na pitting ike nke passivating nkiri.N'ịdị elu dị elu nke onye na-ebu ihe a na-etinye n'ọrụ, ọ na-adị mfe ka oyi akwa ihe nkiri na-agbaji ma dị elu karịa ihe gbasara nke puru omume nke corrosion 45.Na mgbakwunye, na mmụba nke nwayọọ nwayọọ na okpomọkụ nke ngwọta, ND emitter ntinye uche na oyi akwa ihe nkiri mụbara site na 5.273 × 1020 cm-3 ruo 1.772 × 1022 cm-3, na ntinye uche nke NA na-abawanye site na 4.972 × 1021 ruo 4.592. ×1023.cm - dị ka egosiri na fig.3, ikike dị larịị na-abawanye site na 0.021 V ruo 0.753 V, ọnụ ọgụgụ ndị na-ebu na ngwọta na-abawanye, mmeghachi omume n'etiti ions na ngwọta na-abawanye, na nkwụsi ike nke oyi akwa ihe nkiri na-ebelata.Ka okpomọkụ nke ngwọta na-abawanye, ntakịrị uru zuru oke nke mkpọda nke ahịrị dị nso, na-abawanye njupụta nke ndị na-ebu na ngwọta, ọnụ ọgụgụ dị elu nke mgbasa n'etiti ion, na ọnụ ọgụgụ dị ukwuu nke ohere ion na ion. elu nke ihe nkiri oyi akwa., si otú ibelata metal substrate, kwụsie ike na corrosion eguzogide 46,47.
Ngwakọta kemịkalụ nke ihe nkiri ahụ nwere mmetụta dị ukwuu na nkwụsi ike nke cations ígwè na arụmọrụ nke semiconductor, na mgbanwe nke okpomọkụ nwere mmetụta dị mkpa na nhazi nke ihe nkiri igwe anaghị agba nchara.Na fig.Ọgụgụ 7 na-egosi ụdịdị XPS zuru oke nke oyi akwa elu nke ihe nkiri 2205 DSS na ngwọta emepụtara nke nwere 100 g/L Cl- yana CO2 juputara.Ihe ndị bụ isi na fim ndị a na-emepụta site na ibe na okpomọkụ dị iche iche bụ otu ihe ahụ, na isi ihe dị na fim ahụ bụ Fe, Cr, Ni, Mo, O, N, na C. Ya mere, ihe ndị bụ isi nke ihe nkiri ahụ bụ Fe. , Cr, Ni, Mo, O, N na C. Akpa na Cr oxides, Fe oxides na hydroxides na obere ego nke Ni na Mo oxides.
Full XPS 2205 DSS ụdịdị a na-ewere na okpomọkụ dị iche iche.(a) 30°C, (b) 45°C, (c) 60°C, (d) 75°C.
Isi ihe mejupụtara nke ihe nkiri ahụ metụtara ihe ndị dị na thermodynamic nke ogige na ihe nkiri na-agafe agafe.Dị ka ike njide nke isi ihe na fim oyi akwa, nyere na tebụl.6, enwere ike ịhụ na a na-ekewa ọnụ ọgụgụ kachasị elu nke Cr2p3 / 2 na metal Cr0 (573.7 ± 0.2 eV), Cr2O3 (574.5 ± 0.3 eV), na Cr (OH) 3 (575.4 ± 0. 1 eV) dịka egosiputara na eserese 8a, nke oxide nke Cr mebere bụ isi ihe dị na fim ahụ, nke na-arụ ọrụ dị mkpa na nguzogide corrosion nke ihe nkiri ahụ na arụmọrụ electrochemical ya.Ọnụ ọgụgụ kasị elu nke Cr2O3 dị na oyi akwa ihe nkiri dị elu karịa nke Cr (OH) 3.Otú ọ dị, dị ka okpomọkụ ngwọta siri ike na-abawanye, ọnụ ọgụgụ nke Cr2O3 ji nwayọọ nwayọọ na-ebelata, ebe ọnụ ọgụgụ nke Cr (OH) 3 ji nwayọọ nwayọọ na-abawanye, nke na-egosi mgbanwe doro anya nke isi Cr3 + na oyi akwa ihe nkiri site na Cr2O3 ruo Cr (OH). 3, na okpomọkụ nke ngwọta na-abawanye.
Ike ejikọtara ọnụ nke ọnụ ọgụgụ dị iche iche nke Fe2p3/2 bụ isi nwere ọnụ ọgụgụ anọ nke steeti dara dara Fe0 (706.4 ± 0.2 eV), Fe3O4 (707.5 ± 0.2 eV), FeO (709.5 ± 0.1 eV) na FeOO1H (713). eV) ± 0.3 eV), dị ka egosiri na Fig. 8b, Fe na-abụkarị na ihe nkiri a kpụrụ n'ụdị Fe2+ na Fe3+.Fe2 + sitere na FeO na-achịkwa Fe (II) na ọnụ ọgụgụ ike dị ala, ebe Fe3O4 na Fe (III) ogige FeOOH na-achịkwa na elu njikọ ike dị elu48,49.Mmetụta ike nke ọnụ ọgụgụ Fe3+ dị elu karịa nke Fe2+, mana ike nke Fe3+ na-ebelata site na mmụba ngwọta okpomọkụ, na ike nke Fe2+ na-abawanye, na-egosi mgbanwe na isi ihe dị na oyi akwa ihe nkiri site na. Fe3+ ruo Fe2+ ka iwelie okpomọkụ nke ngwọta.
Ọnụ ọgụgụ kachasị elu nke Mo3d5 / 2 na-agụnye ọnọdụ abụọ kachasị elu Mo3d5 / 2 na Mo3d3 / 243.50, ebe Mo3d5 / 2 gụnyere metallic Mo (227.5 ± 0.3 eV), Mo4 + (228.9 ± 0.2 eV) na Mo6+ (229.5 ± 0.2 eV). ), ebe Mo3d3 / 2 nwekwara metallic Mo (230.4 ± 0.1 eV), Mo4 + (231.5 ± 0.2 eV) na Mo6 + (232, 8 ± 0.1 eV) dị ka e gosiri na Figure 8c, ya mere, Mo ọcha dị n'ime ihe karịrị atọ valence. steeti ihe nkiri oyi akwa.Ike ejikọtara ọnụ ọnụ ọnụ ọgụgụ dị iche iche nke Ni2p3/2 nwere Ni0 (852.4 ± 0.2 eV) na NiO (854.1 ± 0.2 eV), dị ka egosiri na Fig. 8g n'otu n'otu.Ihe njirimara N1s kacha elu nwere N (399.6 ± 0.3 eV), dịka egosiri na 8d.Njirimara O1s ọnụ ọnụ gụnyere O2- (529.7 ± 0.2 eV), OH- (531.2 ± 0.2 eV) na H2O (531.8 ± 0.3 eV), dị ka e gosiri na fig. Isi ihe nke film oyi akwa bụ (OH- na O2 -) , nke a na-ejikarị eme ihe maka oxidation ma ọ bụ hydrogen oxidation nke Cr na Fe na oyi akwa ihe nkiri.Ọnụ ọgụgụ kasị elu nke OH- mụbara nke ukwuu ka okpomọkụ si na 30°C ruo 75°C.Ya mere, na-abawanye na okpomọkụ, isi ihe mejupụtara nke O2- na film oyi akwa mgbanwe si O2- ka OH- na O2-.
Na fig.Onyonyo 9 na-egosi nhụsianya dị n'elu microscopic nke sample 2205 DSS mgbe ike na-eme ihe ike na ngwọta nlereanya nwere 100 g/L Cl- na CO2 jupụtara.Enwere ike ịhụ na n'elu ihe atụ ndị ahụ na-ekpo ọkụ na okpomọkụ dị iche iche, e nwere olulu corrosion nke ogo dị iche iche, nke a na-eme na ngwọta nke ion ike ike, na mmụba nke okpomọkụ nke ngwọta ahụ, corrosion ka njọ na-eme na elu nke samples.mkpụrụ.Ọnụ ọgụgụ nke olulu n'otu mpaghara otu na omimi nke ebe corrosion na-abawanye.
Corrosion akụkụ nke 2205 DSS na ngwọta nlereanya nwere 100 g/l Cl- na juputara CO2 na okpomọkụ dị iche iche (a) 30°C, (b) 45°C, (c) 60°C, (d) 75°C.
Ya mere, mmụba nke okpomọkụ ga-eme ka ọrụ nke akụkụ ọ bụla nke DSS dịkwuo elu, yana ime ka ọrụ nke ions na-eme ihe ike na gburugburu ebe obibi na-eme ihe ike, na-eme ka mmebi ụfọdụ dị n'elu ihe atụ, nke ga-eme ka ọrụ pitting dịkwuo elu., na nhazi nke olulu corrosion ga-abawanye.Ọnụ ọgụgụ nke mmepụta ngwaahịa ga-abawanye na nguzogide corrosion nke ihe ga-ebelata51,52,53,54,55.
Na fig.10 na-egosi morphology na pitting omimi nke ihe nlele 2205 DSS polarized nwere nnukwu omimi miri emi nke igwe onyonyo dijitalụ anya.Site na fig.10a na-egosi na obere olulu corrosion pụtakwara n'akụkụ nnukwu olulu, na-egosi na ihe nkiri na-agafe agafe n'elu ihe nlele ahụ mebiri nke ọma site na nhazi nke olulu corrosion na njupụta dị ugbu a, na omimi kachasị elu bụ 12.9 µm.dị ka e gosiri na foto 10b.
DSS na-egosi nguzogide corrosion ka mma, isi ihe kpatara ya bụ na fim ahụ kpụrụ n'elu igwe a na-echebe nke ọma na ngwọta, Mott-Schottky, dị ka nsonaazụ XPS dị n'elu na akwụkwọ ndị metụtara ya 13,56,57,58, ihe nkiri ahụ bụ isi. gafere ihe ndị a Nke a bụ usoro oxidation nke Fe na Cr.
Fe2 + na-agbaze ngwa ngwa ma gbasaa na interface 53 n'etiti ihe nkiri ahụ na ngwọta, usoro mmeghachi omume cathodic bụ nke a:
Na steeti ahụ mebiri emebi, a na-emepụta ihe nkiri ihe eji eme ihe nke nwere okpukpu abụọ, bụ nke na-enwekarị oyi akwa dị n'ime nke ígwè na chromium oxides na elu hydroxide oyi akwa, na ions na-etolitekarị na pores nke ihe nkiri ahụ.Ngwakọta kemịkalụ nke ihe nkiri na-agafe agafe na-ejikọta ya na ihe ndị dị na semiconductor, dị ka ihe ngosi Mott-Schottky na-egosi, na-egosi na ihe mejupụtara nke ihe nkiri na-agafe agafe bụ n + p-ụdị ma nwee àgwà bipolar.Nsonaazụ XPS na-egosi na oyi akwa mpụta nke ihe nkiri na-agafe agafe bụ nke kachasị nke Fe oxides na hydroxides na-egosipụta n-ụdị semiconductor Njirimara, na oyi akwa dị n'ime bụ nke Cr oxides na hydroxides na-egosipụta p-ụdị semiconductor Njirimara.
2205 DSS nwere nnukwu resistivity n'ihi ọdịnaya Cr17.54 dị elu ma na-egosipụta ogo dị iche iche nke pitting n'ihi microscopic galvanic corrosion55 n'etiti ihe owuwu duplex.Pitting corrosion bụ otu n'ime ụdị corrosion a na-ahụkarị na DSS, na okpomọkụ bụ otu n'ime ihe ndị dị mkpa na-emetụta omume nke pitting corrosion ma nwee mmetụta na usoro thermodynamic na kinetic nke mmeghachi omume DSS60,61.Dị ka ọ na-adịkarị, na ngwọta simulated nke nwere nnukwu Cl- na CO2 jupụtara, okpomọkụ na-emetụtakwa nhazi nke pitting na mmalite nke cracks n'oge nrụgide corrosion cracking n'okpuru nrụgide corrosion cracking, na okpomọkụ dị egwu nke pitting kpebisiri ike iji nyochaa. ihe mgbochi corrosion.DSS.Ihe, nke na-egosipụta mmetụta uche nke matrix metal na okpomọkụ, a na-ejikarị eme ihe dị ka ihe dị mkpa na nhọrọ ihe na ngwa injinia.Nkezi okpomọkụ dị oke egwu nke 2205 DSS na ngwọta simulated bụ 66.9°C, nke dị 25.6°C dị elu karịa nke Super 13Cr igwe anaghị agba nchara nwere 3.5% NaCl, mana omimi pitting kacha ruru 12.9µm62.Nsonaazụ nke electrochemical gara n'ihu gosi na mpaghara kwụ ọtọ nke akụkụ akụkụ na ugboro ole dị warara na oke okpomọkụ na-abawanye, yana ka akụkụ akụkụ ahụ na-ebelata site na 79° ruo 58°, uru |Z|na-ebelata site na 1.26×104 ruo 1.58×103 Ω cm2.Nkwụsị nnyefe ụgwọ Rct belatara site na 2.958 1014 ruo 2.541 103 Ω cm2, nkwụsị ngwọta Rs belatara site na 2.953 ruo 2.469 Ω cm2, nkwụsị ihe nkiri Rf belatara site na 5.430 10-4 cm2 ruo 1.147 10-3 cm2.The conductivity nke ike ike ngwọta na-abawanye, nkwụsi ike nke metal matrix film oyi akwa na-ebelata, ọ dissolves na cracks mfe.Njupụta nke corrosion nke onwe ya na-abawanye site na 1.482 ruo 2.893 × 10-6 A cm-2, na ikike nke imebi onwe ya belata site na -0.532 ruo -0.621V.Enwere ike ịhụ na mgbanwe nke okpomọkụ na-emetụta iguzosi ike n'ezi ihe na njupụta nke oyi akwa ihe nkiri.
N'ụzọ megidere nke ahụ, a elu ịta nke Cl- na a jupụta ngwọta nke CO2 ji nwayọọ nwayọọ na-amụba adsorption ikike nke Cl- n'elu nke passivating film na-amụba okpomọkụ, nkwụsi ike nke passivation film na-aghọ ejighị n'aka, na-echebe mmetụta na. mkpụrụ osisi na-esiwanye ike ma ike ịrị elu na-abawanye.N'okwu a, ọrụ nke ion corrosive na ngwọta na-abawanye, ikuku oxygen na-ebelata, na ihe nkiri dị n'elu nke ihe ndị ahụ mebiri emebi na-esiri ike ịgbake ngwa ngwa, nke na-eme ka ọnọdụ dịkwuo mma maka mgbasawanye nke ion corrosive n'elu.Mbelata ihe onwunwe63.Robinson et al.[64] gosiri na na-abawanye na okpomọkụ nke ngwọta, na-eto eto nke olulu na-eme ngwa ngwa, na ọnụego nke mgbasa nke ions na ngwọta na-abawanye.Mgbe okpomọkụ na-ebili ruo 65 Celsius C, mgbasa nke oxygen na ngwọta nwere Cl-ions na-ebelata usoro mmeghachi omume cathodic, ọnụ ọgụgụ nke pitting na-ebelata.Han20 nyochara mmetụta okpomọkụ na omume corrosion nke igwe anaghị agba nchara 2205 duplex na gburugburu CO2.Nsonaazụ gosiri na mmụba nke okpomọkụ mụbara ọnụ ọgụgụ nke ngwaahịa corrosion na mpaghara nke oghere shrinkage n'elu ihe ahụ.N'otu aka ahụ, mgbe okpomọkụ na-ebili na 150 Celsius, ihe nkiri oxide dị n'elu na-agbaji, na njupụta nke craters bụ nke kachasị elu.Lu4 nyochara mmetụta nke okpomọkụ na omume corrosion nke igwe anaghị agba nchara 2205 duplex site na ngafe ruo n'ọrụ na mpaghara geothermal nwere CO2.Nsonaazụ ha na-egosi na n'ime ule ule n'okpuru 150 Celsius, ihe nkiri a kpụrụ akpụ nwere njirimara amorphous, na interface dị n'ime nwere oyi akwa bara ụba na nickel, na okpomọkụ nke 300 Celsius C, ngwaahịa corrosion na-arụpụta nwere nhazi nanoscale. .-polycrystalline FeCr2O4, CroOOH na NiFe2O4.
Na fig.11 bụ ihe osise nke usoro corrosion na nhazi ihe nkiri nke 2205 DSS.Tupu eji ya, 2205 DSS na-emepụta ihe nkiri na-agafe agafe na ikuku.Mgbe emechara ya na gburugburu ebe obibi nke na-eme ka ihe ngwọta nwere ngwọta nwere nnukwu ọdịnaya nke Cl- na CO2, elu ya na-agba gburugburu ngwa ngwa site na ion dị iche iche na-eme ihe ike (Cl-, CO32-, wdg).).J. Banas 65 bịara ná nkwubi okwu na na gburugburu ebe CO2 bụ n'out oge ugbu a, nkwụsi ike nke passivating film n'elu ihe ga-ebelata ka oge na-aga, na kpụrụ carbonic acid na-eme ka mụbaa conductivity nke ion na passivating. oyi akwa.ihe nkiri na osooso mgbasa nke ion na ihe nkiri passivating.ihe nkiri na-akpali akpali.N'ihi ya, ihe nkiri oyi akwa na sample elu bụ na ike ike nha nha ogbo nke mgbasa na repassivation66, Cl-ebelata ọnụego e guzobere n'elu ihe nkiri oyi akwa, na obere pitting olulu na-apụta n'akụkụ akụkụ nke ihe nkiri ahụ, dị ka. egosiri na onyonyo 3. Gosi.Dịka egosiri na eserese 11a na b, obere olulu corrosion na-akwụghị ọtọ na-apụta n'otu oge.Ka okpomọkụ na-ebili, ọrụ nke ion corrosive na ngwọta na oyi akwa ihe nkiri na-abawanye, na omimi nke obere olulu ndị na-adịghị akwụsi ike na-abawanye ruo mgbe ihe nkiri ahụ na-abanye kpamkpam, dị ka egosiri na Figure 11c.Site na mmụba ọzọ na okpomọkụ nke usoro mgbasa ozi, ọdịnaya nke CO2 gbazere na ngwọta na-abawanye ngwa ngwa, nke na-eduga n'ịbelata uru pH nke ngwọta ahụ, mmụba nke njupụta nke obere olulu corrosion kacha nta na-adịghị akwụ ụgwọ na elu SPP. , Ihe omimi nke olulu mmiri mbụ na-agbasawanye ma na-amụbawanye, na ihe nkiri na-agafe agafe n'elu ihe nlele Ka ọkpụkpụ na-ebelata, ihe nkiri ahụ na-agafe agafe na-adịkarị mfe ịkụnye dị ka e gosiri na Figure 11d.Na nsonaazụ electrochemical gbakwunyere na mgbanwe nke okpomọkụ nwere mmetụta ụfọdụ na iguzosi ike n'ezi ihe na njupụta nke ihe nkiri ahụ.Ya mere, enwere ike ịhụ na corrosion na ngwọta juputara na CO2 nwere oke Cl- dị nnọọ iche na corrosion na ngwọta nwere obere mkpokọta Cl-67,68.
Usoro corrosion 2205 DSS na nhazi na mbibi nke ihe nkiri ọhụrụ.(a) Usoro 1, (b) Usoro 2, (c) Usoro 3, (d) Usoro 4.
Okpomọkụ dị oke egwu nke 2205 DSS na ngwọta simulated nwere 100 g / l Cl na CO2 juputara bụ 66.9 ℃, na omimi pitting kachasị bụ 12.9 µm, nke na-ebelata nguzogide corrosion nke 2205 DSS ma na-abawanye mmetụta nke pitting.mmụba okpomọkụ.
Oge nzipu: Feb-16-2023