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Mumakore mashoma apfuura, kwave nekukasira kuvandudzwa kwemvura yesimbi alloys yekugadzira nano-/meso-saizi porous uye inoumbwa zvimiro zvine ultra-mahombe interfaces emhando dzakasiyana siyana.Zvisinei, nzira iyi parizvino ine mipimo miviri yakakosha.Chekutanga, inogadzira bicontinuous zvimiro zvine yakakwira-odha topology yeakaganhurwa huwandu hweakaumbwa alloy.Chechipiri, chimiro chine hukuru hukuru hwebhainda nekuda kwekuwedzera kukuru panguva yekuparadzaniswa kwepamusoro-tembiricha.Pano, isu tinoratidza computation uye nekuyedza kuti zvipimo izvi zvinogona kukurirwa nekuwedzera chinhu kune simbi inonyungudika inosimudzira yepamusoro-soro topology nekudzikamisa kudonha kwezvinhu zvisingaite panguva yekubatanidzwa.Tevere, tinotsanangura kutsvaga uku nekuratidza kuti kufambiswa kwakawanda kwezvinhu zvisingagoneki mumvura inonyungudika kunokanganisa zvakanyanya kushanduka kwechikamu chakasimba uye topology yezvivakwa panguva yekubhururuka.Mhedzisiro yacho inoratidza mutsauko wakakosha pakati pemasimbi emvura uye kubviswa kwetsvina ye electrochemical, uye zvakare gadza nzira nyowani yekuwana zvivakwa kubva kumvura simbi ine zviyero zvakapihwa uye topology.
Kutumwa kwakashanduka kuita tekinoroji ine simba uye inogoneka pakugadzira nano-/meso-yakavhurika pores uye anoumbwa zvimiro zvine ultra-high interfacial pamusoro pezvinhu zvakasiyana-siyana zvinoshanda uye zvimiro zvakaita secatalysts1,2, masero emafuta3,4, electrolytic capacitors5, 6, zvinhu zvinodzivirira kukuvadzwa kwemwaranzi 7, bhatiri rekushandisa rakawedzera kugadzikana 8, 9 kana zvinhu zvinoumbwa zvine mamichina akanakisa 10, 11. Mumhando dzakasiyana-siyana, kutumwa kunosanganisira kunyungudika kwakasarudzika kwechimwe chinhu chepakutanga chisina kurongeka. alloy” mumhoteredzo yekunze, izvo zvinotungamira pakurongeka patsva kwezvinhu zvisina kunyunguduka zvinosanganiswa netopology isiri-diki, yakasiyana netopology yealloy yekutanga., Kuumbwa kwezvinhu.Kunyange zvazvo yakajairika electrochemical delegation (ECD) vachishandisa maelectrolytes sezvo nharaunda iri yakanyanya kudzidzwa kusvika parizvino, nzira iyi inoganhura masisitimu ekugovera (akadai seAg-Au kana Ni-Pt) kune ayo ane zvinhu zvinoyevedza (Au, Pt) uye ane mutsauko wakakura wakakwana mukuderedza kugona kupa porosity.Danho rakakosha rekukunda kudzikamisa uku kwave kuwanikwa zvakare kweiyo liquid metal alloying nzira13,14 (LMD), iyo inoshandisa alloys emvura simbi (semuenzaniso, Cu, Ni, Bi, Mg, nezvimwewo) nezvimwe zvinhu zviri munharaunda. .(semuenzaniso TaTi, NbTi, FeCrNi, SiMg, zvichingodaro)6,8,10,11,14,15,16,17,18,19.LMD uye kubviswa kwayo kwesimbi yakaoma alloy (SMD) kusiyanisa kunoshanda pakudziya kwakadzika kana base simbi yakaoma20,21 zvichikonzera kuumbwa kwezvikamu zviviri kana kupfuura zvinopindirana mushure mekucheka kwemakemikari kwechikamu chimwe.Aya matanho anogona kushandura kuita ma pores akazaruka.zvimiro.Nzira dzekugovera dzakavandudzwa zvakare nekuunzwa kuchangoburwa kwevapor phase delegation (VPD), iyo inoshandisa misiyano mukutsikirira kwemhute yezvinhu zvakasimba kuumba yakavhurika nanoporous zvimiro kuburikidza nekusarudza evaporation yechinhu chimwe chete22,23.
Panguva yemhando yepamusoro, ese aya maitiro ekubvisa tsvina anogovana maviri akakosha akajairika maficha eakarongeka akarongeka ekubvisa muitiro.Chekutanga, uku ndiko kunyungudika kwakasarudzika kwezvinhu zvataurwa pamusoro apa alloying (senge B mune yakapusa alloy AXB1-X) munzvimbo yekunze.Chechipiri, chakatanga kucherechedzwa muzvidzidzo zvekutanga zvekuyedza uye zvedzidziso paECD24, ndiko kupararira kwechinhu chisina kunyungudika A pamwe nekubatana pakati pealloy nemhoteredzo panguva yekubviswa kwetsvina.Diffusion inokwanisa kuumba matunhu ane atomic-hupfumi kuburikidza nekuita kwakafanana nekuora kwespinodal mune alloys akawanda, kunyangwe ichiganhurwa neiyo interface.Pasinei nekufanana uku, nzira dzakasiyana dzekubvisa alloy dzinogona kuburitsa akasiyana morphologies nezvikonzero zvisina kujeka18.Nepo ECD ichikwanisa kugadzira zvimiro zvine chekuita nepamusoro-soro zvezvikamu zveatomu (X) zvezvinhu zvisina kunyungudutswa (zvakadai seAu muAgAu) zvakaderera se5%25, zvidzidzo zvemakomputa uye zvekuedza zveLMD zvinoratidza kuti nzira iyi inoita seyakafanana inongogadzira zvimiro zvine chekuita nemusoro. .Semuenzaniso, kune yakakura zvikuru X, iyo inobatanidzwa bicontinuous chimiro inenge 20% munyaya yeTaTi alloys yakasanganiswa neCu melts (ona Fig. 2 in ref. 18 yekuenzanisa-ne-parutivi neECD dzakasiyana-siyana uye LMD fomu X. )Kusiyana uku kunotsanangurwa ne theoretically nea diffusion-coupled growth mechanism yakasiyana ne interfacial spinodal decomposition uye yakafanana zvikuru ne eutectic-coupled growth26.Munzvimbo yekubvisa tsvina, kupararira-kwakabatana kukura kunobvumira A-rich filaments (kana flakes mu 2D) uye B-rich liquid nzira kuti dzikure pamwe nekupararira panguva yekubvisa tsvina15.Kukura kwevaviri kunotungamira kune yakarongedzerwa topologically isina kusungwa chimiro mukati mechikamu cheX uye inodzvanywa muchikamu chezasi cheX, uko chete zvitsuwa zvisina kusungwa zvakapfuma muA phase zvinogona kuumba.Pachikuru X, kukura kwakasungirirwa kunove kusina kugadzikana, kuchifarira kuumbwa kweakanyatso sungirirwa 3D zvimiro zvinochengetedza kuvimbika kwechimiro kunyangwe mushure mechikamu chimwe chete.Sezvineiwo, chimiro chekutarisa chinogadzirwa neLMD17 kana SMD20 (Fe80Cr20) XNi1-X alloys yakacherechedzwa kuyedza X kusvika 0.5, zvichiratidza kuti kukura-kwakabatana kukura inzira inowanikwa kweLMD neSMD kwete iyo inowanzoitika porous ECD haina. iva nechimiro chakasarudzika chekugadzirisa.
Kuti tijekese chikonzero chemusiyano uyu pakati peECD neNMD morphology, takaita nhanho yemumunda uye zvidzidzo zvekuyedza zveNMD yeTaXTi1-X alloys, umo disolution kinetics yakagadziridzwa nekuwedzera zvinhu zvakanyungudutswa kumvura yemhangura.Takagumisa kuti kunyange zvazvo zvose ECD neLMD zvichidzorwa nekusarudza kuparara uye kupararira kwemukati, maitiro maviri aya anewo misiyano inokosha inogona kutungamirira kune morphological kusiyana18.Kutanga, iyo peel kinetics muECD inodzorwa neiyo interface ine inogara ichipepeta kumberi velocity V12 sebasa reiyo inoshandiswa voltage.Izvi ndezvechokwadi kunyange kana chikamu chiduku chezvimedu zvinoramba (eg Pt muAg-Au) zvinowedzerwa kune alloy yevabereki, iyo inodzorera interfacial fluidity, inochenesa uye inodzikamisa zvinhu zvisina kusanganiswa, asi zvimwe zvinoramba zvakafanana morphology 27.Topologically zvakabatanidzwa zvimiro zvinowanikwa chete pazasi X pazasi V, uye kuchengetwa kwezvinhu zvinosanganiswa 25 yakakura kuchengetedza yakasimba vhoriyamu chikamu chakakura zvakakwana kudzivirira kupatsanuka kwechimiro.Izvi zvinoratidza kuti chiyero chekuparara maererano nekupararira kwemukati kunogona kuita basa rinokosha mukusarudza morphological.Kusiyana neizvi, kinetics yekubvisa alloy muLMD inodzorwa15,16 uye chiyero chinodzikira nekukurumidza nenguva \(V \ sim \sqrt{{D}_{l}/t}\), apo Dl ndiyo chinhu chinokanganisa. kune iyo fluid diffusion coefficient ..
Chechipiri, panguva yeECD, kunyungudika kwezvinhu zvisingagoneki mu electrolyte kwakadzikira zvakanyanya, saka zvinongokwanisa kupararira pamwe chete neiyo alloy-electrolyte interface.Kusiyana neizvi, muLMD, iyo "immiscible" zvinhu (A) yeAXB1-X precursor alloys kazhinji ine zvishoma, kunyangwe zvishoma, kunyungudika kunyungudika.Kunyungudika kudiki uku kunogona kuverengerwa kubva mukuongororwa kweiyo ternary phase diagraph yeCuTaTi ternary system inoratidzwa muSupplementary Figure 1. Kunyungudika kunogona kuverengerwa nekugadzira mutsara we liquidus uchipesana nekuenzana kweTa neTi padivi remvura reiyo interface (\( {c}_{ {{{{{\rm{Ta)))))))}}}} ^{l}\ ) uye \({c}_{{{{({\rm{Ti}}} }}}} }^ {l}\), zvichiteerana, patembiricha yekutumwa (Supplementary Fig. 1b) solid-liquid interface Local thermodynamic equilibrium inochengetwa panguva yealloying, }}}}}}^{l}\) inenge nguva dzose uye kukosha kwayo kunoenderana ne X. Supplementary Figure 1b inoratidza kuti \({c}_{{{{{{{\rm{Ta}}}}}}})}^{l}\) inowira muchikamu 10 -3 − 10 ^{l}\) akaenzana ne15.16.Uku "kudonhedza" kwezvinhu zvisingaverengeki mualloy kunogona kukanganisa kuumbwa kwechimiro chechimiro chepamberi pa delamination kumberi, nekuchinja kwacho, izvo zvinogona kubatsira mukuparara uye kukoromoka kwechimiro nekuda kwekupararira kwehuwandu.
Kuti tiongorore zvakasiyana mupiro we (i) chiyero chakaderedzwa chekubvisa alloy V uye (ii) chiyero chakaderedzwa chekupinda kwezvinhu zvisingagoneki mukunyunguduka, takapfuurira mumatanho maviri.Kutanga, nekuda kwe (V \ sim \ sqrt{{D}_{l}/t}\), nekudzidza morphological evolution yechimiro chebundle pamberi, zvaive zvichibvira kudzidza mhedzisiro yekudzikisa V zvakakwana.nguva huru.Naizvozvo, isu takaongorora mhedzisiro iyi nekumhanyisa chikamu chemunda masimulation kwenguva yakareba kupfuura zvidzidzo zvakapfuura, izvo zvakaratidza kuvepo kweiyo topologically isina kubatanidzwa kurongeka zvimiro zvakaumbwa nekupararira-kwakabatana kukura kweiyo X15 yepakati.Chechipiri, kuitira kuti tiongorore mhedzisiro yezvinhu zvisingagoneke pakudzikisa chiyero chekudonha, isu takawedzera Ti neAg kumhangura yakanyunguduka kuti iwedzere uye ideredze chiyero chekubuda, zvichiteerana, uye tikadzidza mhedzisiro inokonzeresa morphology, segregation kinetics, uye kugoverwa kwevasungwa mu melt.delegated Cu inonyunguduka kuburikidza nekuverenga uye zviedzo mukati meiyo alloy chimiro.Isu takawedzera Ti mawedzero kubva pa10% kusvika 30% kune midhiya kubvisa iyo Cu melt.Kuwedzerwa kweTi kunowedzera iyo Ti yekumisikidza pamucheto weiyo yakatumirwa layer, iyo inoderedza iyo Ti yekumisikidza gradient mukati meiyi dhizaini uye inoderedza chiyero chekunyungudika.Inowedzerawo chiyero chekuvuza kweTa nekuwedzera \({c}_{{{({\rm{Ti}}}}}}}}}^{l}\), saka \({c}_{{{{{ {\rm{Ta}}}}}}} ^{l}\) (Supplementary Fig. 1b) Nhamba yesirivha yatinowedzera inosiyana kubva pa10% kusvika ku30%. kunyungudika kwezvinhu zvinosanganiswa mukunyunguduka, isu takatevedzera iyo CuAgTaTi quaternary system senge inoshanda (CuAg) TaTi ternary system umo kunyungudika kweTi neTa kunoenderana nekusangana kweAg muCuAg kunyungudika (ona Cherechedzo) 2 uye Supplementary. Fig 2-4).Kuwedzerwa kweAg hakuwedzere kuwanda kweTi pamucheto weiyo yakatumirwa chimiro.Zvakadaro, sezvo kunyungudika kweTi muAg kwakadzikira pane kuya kweCu, izvi zvinoderedza \({c}_{{{{\rm{Ta}}}}}}}}^{l}\) (Supplementary Fig. . 1 ) 4b) uye chiyero chekuvuza Ta.
Mhedzisiro yesimulation yemunda wechikamu inoratidza kuti kukura kwakabatana kunove kusina kugadzikana kwenguva yakareba zvakakwana kusimudzira kuumbwa kwetopologically yakabatana zvimiro kumberi kwekuora.Isu tinoyedza kusimbisa iyi mhedziso nekuratidza kuti iyo yepasi peiyo Ta15T85 alloy, iyo inoumba padhuze ne delamination kumberi pane imwe nhanho yeku delamination, inoramba yakasungirirwa kumusoro mushure mekumisikidzwa kwechikamu checopper-rich.Mhedzisiro yedu zvakare inoratidza kuti chiyero chekuvuza chine mhedzisiro yakakura pakushanduka kwe morphological nekuda kwekutakurisa kwakapararira kwekutakura kwezvinhu zvisingaite mumvura inonyungudika.Zvinoratidzwa pano kuti mhedzisiro iyi, iyo isipo muECD, inokanganisa zvakanyanya kutariswa kwezvimiro zvezvinhu zvakasiyana muchikamu chakatumirwa, chikamu chechikamu chakasimba, uye topology yeLMD chimiro.
Muchikamu chino, isu tinotanga kupa mhedzisiro yekudzidza kwedu nechikamu ndima simulation yemhedzisiro yekuwedzera Ti kana Ag kuCu inonyungudika zvichikonzera akasiyana morphologies.Pamusoro pemuonde.Mufananidzo 1 unopa mhedzisiro ye-matatu-dimensional modelling yechikamu chemunda weTaXTi1-X alloys akawanikwa kubva kuCu70Ti30, Cu70Ag30 uye yakachena mhangura inonyunguduka ine yakaderera atomu yezvinhu zvisingagoneke kubva pa5 kusvika 15%.Mitsara miviri yekutanga inoratidza kuti kuwedzerwa kwezvose zviri zviviri Ti uye Ag zvinokurudzira kuumbwa kwezvinyorwa zvakasungirirwa zvepamusoro zvichienzaniswa nechimiro chisina kusungwa cheCu pure (mutsara wechitatu).Nekudaro, kuwedzera kweTi, sezvaitarisirwa, kwakawedzera kudonha kweTa, nekudaro kudzivirira kuderedzwa kweakaderera X alloys (Ta5Ti95 uye Ta10Ti90) uye kukonzera kuparara kukuru kweiyo exfoliated porous layer panguva yeTa15Ti85 delamination.Pane zvinopesana, kuwedzerwa kweAg (mutsara wechipiri) kunobatsira pakuumbwa kwechimiro chepamusoro chepamusoro chezvikamu zvose zvechigadziko chinokonzerwa nekuparara kuduku kwechikamu chakapiwa.Kuumbwa kweiyo bicontinuous chimiro kunowedzera kuratidzwa muFig.1b, iyo inoratidza mifananidzo yechimiro chakatumwa nekuwedzera kudzika kwedelamination kubva kuruboshwe kuenda kurudyi uye mufananidzo weiyo solid-liquid interface pakudzika kwepamusoro (kure kurudyi mufananidzo).
3D nhanho yemunda simulation (128 × 128 × 128 nm3) inoratidza zvinoshamisa mhedzisiro yekuwedzera solute kumvura inonyungudika pane yekupedzisira morphology yearoyi yakapihwa.Mucherechedzo wepamusoro unoratidza kuumbwa kweiyo alloy yevabereki (TaXTi1-X) uye mucherechedzo wakamira unoratidza kunyunguduka kweCu-based softening medium.Nzvimbo dzine yakakwira Ta yekumisikidza muchimiro chisina tsvina inoratidzwa mubrown, uye iyo yakasimba-yemvura interface inoratidzwa mubhuruu.b Matatu-dimensional simulation yechikamu chechikamu cheiyo isina kuvharwa Ta15Ti85 precursor alloy muCu70Ag30 melt (190 × 190 × 190 nm3).Mafuremu matatu ekutanga anoratidza dunhu rakasimba rechimiro chakatumwa pakadzika kwakasiyana nhumwa, uye furemu yekupedzisira inongoratidza chete solid-liquid interface pakudzika kwepamusoro.Bhaisikopo rinoenderana ne(b) rinoratidzwa muSupplementary Movie 1.
Mhedzisiro yekuwedzera solute yakawedzera kuongororwa ne2D chikamu chemunda simulations, iyo yakapa rumwe ruzivo nezve interfacial mode kuumbwa kumberi kwe delamination uye yakabvumira kupinda kune hurefu hukuru uye nguva zvikero kupfuura 3D simulations kuyera delamination kinetics.Pamusoro pemuonde.Mufananidzo 2 unoratidza mifananidzo yekufananidzira kubviswa kweTa15Ti85 precursor alloy kuburikidza neCu70Ti30 uye Cu70Ag30 inonyungudika.Muzviitiko zvese izvi, kukura-kwakabatana kukura hakuna kugadzikana.Panzvimbo pekupinda vertically kupinda alloy, matipi emvura migero kufamba chaotically kuruboshwe uye rworudyi mune dzakaoma kwazvo trajectories panguva yakatsiga kukura muitiro inosimudzira akatevedzana zvivako zvinokurudzira paumbwe topologically chokuita zvivako munzvimbo 3D (Fig. 1).Nekudaro, pane musiyano wakakosha pakati peTi uye Ag zvinowedzera.Kune iyo Cu70Ti30 inonyunguduka (Fig. 2a), kudhumhana kwematanho maviri emvura kunotungamira mukubatanidzwa kweiyo solid-liquid interface, iyo inotungamira kune extrusion yeakasimba mabhaidhi akabatwa nematanho maviri kubva muchimiro uye, pakupedzisira, kuparara. .Pane zvinopesana, yeCu70Ag30 inonyunguduka (Fig. 2b), Ta kupfumisa pane iyo interface pakati peiyo yakasimba uye yemvura nhanho inodzivirira coalescence nekuda kwekuderera kweTa leakage mukunyungudika.Nekuda kweizvozvo, kudzvanywa kwechisungo kumberi kwe delamination kunodzvinyirirwa, nekudaro zvichikurudzira kuumbwa kwekubatanidza zvimiro.Zvinofadza kuti chaotic oscillatory motion of the liquid channel inogadzira maviri-dimensional maitiro ane imwe dhigirii yekuenzanisa apo cutoff inodzvinyirirwa (Fig. 2b).Zvisinei, kurongeka uku hakusi kwechikonzero chekukura kwakasimba kwechisungo.Mu 3D, kupinda kusina kugadzikana kunogadzira iyo isiri-coaxial yakabatana bicontinuous structure (Fig. 1b).
Snapshots ye2D chikamu munda simulations yeCu70Ti30 (a) uye Cu70Ag30 (b) inonyungudika yakanyungudutswa kuTa15Ti85 alloy inoratidza kusagadzikana kupararira-kwakabatana kukura.Mifananidzo inoratidza kudzika kwakasiyana kwekubvisa tsvina yakayerwa kubva pakatanga chinzvimbo che flat solid/ liquid interface.Iwo maseti anoratidza akasiyana mareji ekudhumhana kwenzira yemvura, zvichitungamira mukusungwa kweakasimba mabhandi uye kuchengetedza kweCu70Ti30 uye Cu70Ag30 inonyungudika, zvichiteerana.Iyo domain wide yeCu70Ti30 ndeye 1024 nm, Cu70Ag30 ndeye 384 nm.Iro bhendi remavara rinoratidza kusungwa kweTa, uye mavara akasiyana anosiyanisa pakati penzvimbo yemvura (yakasviba bhuruu), base alloy (mwenje bhuruu), uye isina alloyed chimiro (chinenge chitsvuku).Mabhaisikopo eiyi simulations anoratidzwa muSupplemental Mafirimu 2 uye 3, ayo anosimbisa nzira dzakaoma dzinopinda mumatanho emvura panguva isina kugadzikana yekupararira-yakabatana kukura.
Mimwe mhedzisiro ye2D chikamu chemunda simulation inoratidzwa muFig.3.Girafu yehudzamu hwe delamination maringe nenguva (kutenuka kwakaenzana neV) mumuonde.3a inoratidza kuti kuwedzerwa kweTi kana Ag kuCu kunyunguduka kunononoka kuparadzanisa kinetics, sezvaitarisirwa.Pamusoro pemuonde.3b inoratidza kuti kudzikira uku kunokonzerwa nekudzikira kweiyo Ti yekumisikidza gradient mumvura mukati meiyo yakatumirwa layer.Zvinoratidzawo kuti kuwedzera kweTi (Ag) kunowedzera (kunoderera) kuwanda kweTi padivi remvura reiyo interface (\({c}_{{{{{{{\rm{Ti)))))")) ))) ^{l \) ), izvo zvinotungamira mukudonha kweTa, kuyerwa nechikamu cheTa chakanyungudutswa sekushanda kwenguva (Fig. 3c), iyo inowedzera (inoderera) nekuwedzera kweTi (Ag). )Mufananidzo 3d unoratidza kuti kune ese ari maviri solutes, chikamu chevhoriyamu chezvakaoma chinoramba chiri pamusoro pechikumbaridzo chekugadzirwa kwebicontinuous topologically related structures28,29,30.Ipo kuwedzera Ti mukunyungudika kunowedzera kuvuza kweTa, zvakare kunowedzera kuchengetwa kweTi mune yakasimba binder nekuda kwechikamu chakaenzana, nekudaro ichiwedzera chikamu chevhoriyamu kuchengetedza kubatana kwechimiro pasina tsvina.Maverengero edu anowanzo kubvumirana nezviyero zvekuyedzwa zvevhoriyamu chikamu che delamination kumberi.
Iyo chikamu chemunda simulation yeTa15Ti85 alloy inoverengera akasiyana mhedzisiro yeTi neAg yekuwedzera kune Cu inonyungudika pane alloy ekubvisa kinetics akayerwa kubva pakudzika kwekubvisa alloy senge basa renguva (a), iyo Ti yekumisikidza chimiro mumvura pane imwe mvura. alloy kubvisa kudzika kwe400 nm (negative kudzika kunowedzera mukunyunguduka kunze kweiyo alloy chimiro (alloy kumberi kuruboshwe) b Ta leakage inopesana nenguva (c) uye chidimbu chakasimba muchimiro chisina kusanganiswa maringe nekunyunguduka kuumbwa (d) Kuunganidzwa kwezvimwe zvinhu. mukunyunguduka kunorongwa pamwe chete neabscissa (d) (Ti - mutsara wakasvibirira, Ag - mutsara wepepuru uye kuedza).
Sezvo kumhanya kwe delamination kumberi kuchidzikira nekufamba kwenguva, kushanduka kwe morphology panguva ye delamination kunoratidza mhedzisiro yekudzikisa kukurumidza kwe delamination.Muchikamu chakapfuura chidzidzo chemumunda, takaona eutectic-senge yakabatana kukura zvichikonzera kuenderana topologically isina kusungwa zvimiro panguva yekubviswa kweTa15Ti85 precursor alloy nemhangura yakachena inonyungudika15.Zvisineyi, nhanho refu dzechikamu chimwechete chesimulation show (ona Supplementary Movie 4) kuti kana iyo yekuparara yekumberi ichiita diki zvakakwana, kukura kwakabatana kunova kusagadzikana.Kusagadzikana kunozviratidza mu lateral rocking of flakes, iyo inodzivisa kurongeka kwavo uye, nokudaro, inosimudzira kuumbwa kwemaitiro epamusoro-soro.Shanduko kubva pakukura kwakadzikama kusvika kune kusagadzikana kuzununguka kukura kunoitika pedyo ne xi = 250 nm pamwero we4.7 mm/s.Pane zvinopesana, iyo inoenderana delamination kudzika xi yeCu70Ti30 melt inenge 40 nm pamwero mumwe chete.Nokudaro, isu hatina kukwanisa kuona shanduko yakadaro pakubvisa alloy neCu70Ti30 melt (ona Supplementary Movie 3), nokuti kuwedzera 30% Ti kunyunguduka kunoderedza zvakanyanya kinetics yekubvisa alloy.Chekupedzisira, kunyangwe kukura kwakabatana-kwakabatana kusina kugadzikana nekuda kwekunonoka delamination kinetics, chinhambwe λ0 chezvisungo zvakaoma kumberi kwe delamination chinototeera \({\lambda }_{0}^{2}V=C\) mutemo wekumira. kukura15,31 uko C inogara iripo.
Kuti uedze fungidziro yechikamu chemunda simulation, kuedza kwekubvisa alloy kwakaitwa nemasample akakura uye nguva refu yekubvisa alloy.Mufananidzo 4a dhiyabhorosi dhayagiramu inoratidza makiyi maparamita eiyo yakatumirwa chimiro.Hudzamu hwese hwe delamination hwakaenzana ne xi, chinhambwe kubva kumuganhu wekutanga wechikamu chakasimba uye chemvura kusvika kumberi kwe delamination.hL chinhambwe kubva kune yekutanga solid-liquid interface kusvika kumucheto kweiyo yakatumirwa chimiro isati yaiswa.HL yakakura inoratidza Ta leakage yakasimba.Kubva pamufananidzo weSEM wemuenzaniso wakapihwa, tinogona kuyera saizi hD yechimiro chakatumirwa tisati tapinda.Zvisinei, sezvo kunyunguduka kuchisimbisawo pakupisa kwekamuri, zvinokwanisika kuchengetedza chimiro chakagoverwa pasina zvisungo.Naizvozvo, isu takamisa kunyunguduka (mhangura yakapfuma chikamu) kuti tiwane shanduko uye tikashandisa hC kuyera ukobvu hweshanduko chimiro.
a Schematic diagram yekushanduka kwe morphology panguva yekubviswa kwetsvina uye kutsunga kwe geometric parameters: leakage layer thickness Ta hL, ukobvu hwe delaminated structure hD, ukobvu hwekubatanidza chimiro hC.(b), (c) Kuedzwa kusimbiswa kwechikamu chemusimu wekutevedzera mhedzisiro inoenzanisa SEM muchinjika zvikamu uye 3D etched morphology yeTa15Ti85 alloy yakagadzirwa kubva yakachena Cu (b) uye Cu70Ag30 inonyunguduka, ichipa topological zvisungo zvine maunifomu bond saizi Maumbirwo (c), sikeri bar. 10 µm.
Zvikamu zvakachinjika zvezvivakwa zvakapihwa zvinoratidzwa mufig.4b, c inosimbisa iyo huru yakafanotaurwa mhedzisiro yekuwedzera Ti uye Ag kuCu inonyungudika pane iyo morphology uye kinetics yeakatumirwa alloy.Pamusoro pemuonde.Mufananidzo 4b unoratidza nzvimbo yepasi yeSEM ​​yakachekwa (kuruboshwe) yeTa15T85 alloy yakasanganiswa nekunyudzwa mumhangura yakachena kwegumi kusvika pakadzika xi ~ 270 μm.Pachiyero chinoyerwa chenguva yekuyedza, inova maodha akati wandei ehukuru kupfuura muchikamu chesimulations, iyo decoupling yepamberi velocity iri pasi peiyo yataurwa pamusoro pechikumbaridzo velocity ye4.7 mm / s, pazasi iyo yakagadzikana eutectic bond kukura kunova kusagadzikana.Naizvozvo, chimiro chiri pamusoro pepeel kumberi chinotarisirwa kuve topologically yakabatana.Pamberi pe etching, iyo yakatetepa yeayo alloy yakanyungudika zvachose (hL = 20 μm), iyo yaisanganiswa neTa leakage (Table 1).Mushure memakemikari etching yemhangura-yakapfuma chikamu (kurudyi), chete chidimbu chitete cheyakatumirwa alloy (hC = 42 µm) yasara, zvichiratidza kuti yakawanda yechimiro chakatumirwa chakarasika hunhu panguva yekucheka uye yakanga isiri, sezvaitarisirwa, yakasungirirwa kumusoro. Mufananidzo 1a)., mufananidzo wekurudyi mumutsetse wechitatu).Pamusoro pemuonde.4c inoratidza iyo yakazara SEM muchinjiko chikamu uye 3D mifananidzo ye etching yeTa15Ti85 alloy yakabviswa nekunyudzwa muCu70Ag30 melt for 10 s kusvika pakadzika inosvika mazana maviri µm.Sezvo hudzamu hwe peel hunofungidzirwa kuti huchawedzera ne \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\) diffusion controlled kinetics (ona Supplementary Note 4) 15 16, Nekuwedzera kwe30% Ag kuCu melt, kuderera kwehupamhi hwekuparadzanisa kubva 270 μm kusvika 220 μm inopindirana nekuderera kwePeclet nhamba p nechikamu che1.5.Mushure mekugadzirwa kwekemikari yeCu/Ag yakapfuma chikamu (kurudyi), chimiro chese chakatumwa chinochengeta chimiro chekuvimbika (hC = 200 µm), zvichiratidza kuti ichokwadi chakafanotaurwa chepamusoro-soro chakabatanidzwa bicontinuous chimiro (Mufananidzo 1, kurudyi mufananidzo) mutsara wechipiri uye wakazara. mutsara wepasi).Yese zviyero zveiyo yakatumirwa base alloy Ta15T85 mune akasiyana melts inopfupikiswa muTafura.1. Isu tinopawo zvigumisiro zveTa10Ti90 base alloys isina kusanganiswa mune zvakasiyana-siyana zvinonyunguduka, zvichisimbisa mhedziso dzedu.Kuyerwa kweiyo leakage layer gobvu Ta yakaratidza kuti chimiro chakanyungudutswa muCu70Ag30 melt (hL = 0 μm) idiki pane icho chiri muCu nyungudika yakachena (hL = 20 μm).Pane zvinopesana, kuwedzera kweTi kune kunyunguduka kunonyungudutsa zvimiro zvisina kusimba zvakasanganiswa (hL = 190 μm).Kudzikira kwekunyungudika kwechimiro chakatumwa pakati peiyo yakachena Cu yakanyunguduka (hL = 250 μm) uye Cu70Ag30 inonyunguduka (hL = 150 μm) inonyanya kutaurwa mune yakatumirwa alloys yakavakirwa paTa10Ti90.
Kuti tinzwisise zvinokonzerwa nekunyunguduka kwakasiyana, takaita imwezve yehuwandu hwekuongorora kwemigumisiro yekuedza mumufananidzo 5 (onawo Supplementary Data 1).Pamusoro pemuonde.Figures 5a–b anoratidza akayerwa concentration kuparadzirwa kwezvinhu zvakasiyana-siyana pamwe nhungamiro exfoliation mu exfoliation kuedza yakachena Cu melt (Fig. 5a) uye Cu70Ag30 melt (Fig. 5b).Iko kusungirirwa kwezvinhu zvakasiyana-siyana kwakarongerwa chinhambwe d kubva ku delamination kumberi kusvika kumucheto kwe delamination layer mune yakasimba binder uye nhanho yaive mvura (yakapfumiswa muCu kana CuAg) panguva ye delamination.Kusiyana neECD, uko kuchengetwa kwezvinhu zvinosanganiswa kunotsanangurwa nehuwandu hwekuparadzaniswa, muLMD, kusungirirwa mubhainda rakasimba kunotarirwa nenharaunda ye thermodynamic equilibrium pakati pezvikamu zvakasimba uye zvemvura uye, nekudaro, kugarisana kwesimba uye. liquid phases.Alloy State Diagrams.Nekuda kwekuparara kweTi kubva pachigadziko alloy, iyo Ti yekumisikidza inodzikira nekuwedzera d kubva ku delamination kumberi kusvika kumucheto kwe delamination layer.Nekuda kweizvozvo, iyo Ta yakawedzera nekuwedzera d pamwe nebundle, iyo yaienderana nechikamu chemunda simulation (Supplementary Fig. 5).Iyo Ti yekumisikidza muCu70Ag30 inonyungudika inodonha zvakanyanya kupfuura mune yakachena Cu inonyunguduka, inoenderana neinononoka alloy yekubvisa mwero.Iwo akayerwa concentration profiles muFigs.5b inoratidzawo kuti reshiyo yehuwandu hweAg neCu mumvura haina kunyatsoenderana nechikamu cheiyo alloy yakatumirwa, nepo mukuenzanisa kwechikamu chechikamu ichi chiyero chaifungidzirwa kuti chinogara chiripo mukufananidza kwekunyungudika se. a pseudo-element Cu70Ag30.Kunyangwe iyi mutsauko wehuwandu, iyo chikamu chemumunda modhi inobata yakanyanya kunaka mhedzisiro yekuwedzera Ag pakudzvinyirira Ta kuvuza.Kunyatso kuenzanisa kwehuwandu hwemaconcentration gradients ezvese zvinhu zvina mumabhainda akasimba uye zvinwiwa zvinoda imwe yemhando yezvikamu zvina zveiyo TaTiCuAg chikamu dhayagiramu, iyo iri kupfuura chiyero chebasa iri.
Yakayerwa maprofiles ekutarisa zvichienderana nechinhambwe d kubva kune delamination pamberi peTa15Ti85 alloy mu (a) yakachena Cu inonyungudika uye (b) Cu70Ag30 nyungudika.Kuenzaniswa kwechidimbu chevhoriyamu yakayerwa yezvakaoma ρ(d) zvechimiro chakapihwa (mutsetse wakasimba) nefungidziro yekufungidzira inoenderana neiyo equation isina kuvuza Ta (dashed line).(1) (c) Inflate equation kufanotaura.(1) Equation yakagadziriswa pamberi pe delamination.(2) Kureva kuti, Ta leakage inotariswa.Eresa avhareji yebhondi hupamhi λw uye chinhambwe λs (d).Mabhawa ekukanganisa anomiririra kutsauswa kwakajairwa.
Pamusoro pemuonde.5c inoenzanisa chikamu chevhoriyamu chakayerwa chezvakaoma ρ(d) (mutsetse wakasimba) kune chaiwo wakapihwa Cu uye Cu70Ag30 zvimiro kubva mukunyunguduka nefungidziro yefungidziro (dashed line) inowanikwa kubva mukuchengetedza hukuru uchishandisa yakayerwa Ta concentration mune yakasimba binder \({{ c }_ {Ta}^{s}(d)\) (Fig. 5a,b) uye furatira kubuda kweTa uye kutakurwa kweTa pakati pezvisungo zvine hudzamu hwakasiyana hwekuparadzanisa.Kana Ta akachinja kubva kusimba kuenda kumvura, ese eTa ari mu base alloy anofanirwa kugovaniswa kuita yakasimba binder.Saka, mune chero chikamu chechimiro chiri kure chinoenderana negwaro rekubviswa kwealloy, kuchengetedza kwehuwandu kunoreva kuti \({c}_{Ta}^{s}(d){S}_{s}(d) )={c}_ {Ta}^{0}(d){S}_{t}\), apo \({c}_{Ta}^{s}(d)\) uye \({c} }_{Ta }^ {0}\) ndiwo maconcentrations eTa ari pachinzvimbo d mubhainda uye matrix alloy, zvichiteerana, uye Ss(d) neSt ndidzo nzvimbo dzakachinjika dzebhainda rakaoma uye nharaunda yese iri kure, zvichiteerana.Izvi zvinofanotaura chikamu chevhoriyamu chezvakaoma muchikamu chiri kure.
Izvi zvinogona kushandiswa zviri nyore kune chimiro cheiyo chakapihwa chakachena Cu uye Cu70Ag30 inonyunguduka uchishandisa inoenderana \({c}_{Ta}^{s}(d)\)) macurves anoenderana netambo yebhuruu.Aya mafungidziro akaiswa pamusoro peFig. 5c achiratidza kuti kufuratira Ta leakage ikufanotaura kwakashata kwekugoverwa kwechikamu chevhoriyamu.Leak-isina kuwanda kuchengetedza inofanotaura kuderera kwe monotonic muchikamu chevhoriyamu nekuwedzera d, iyo inocherechedzwa zvine mutsindo mune yakachena Cu inonyungudika, asi kwete muCu70Ag30 inonyungudika, apo ρ(d) ine hushoma.Uye zvakare, izvi zvinotungamira kune kwakakosha overestimation yevhoriyamu zvikamu padivi rekuparadzanisa kune ese anonyungudika.Kune idiki inoyerwa d ≈ 10 µm, yakafanotaurwa ρ kukosha kwezvose zviri kunyunguduka inodarika 0.5, ukuwo yakayerwa ρ kukosha kweCu uye Cu70Ag30 inonyungudika yakakwira zvishoma pane 0.3 uye 0.4, zvichiteerana.
Kuti tisimbise basa guru reTa kuvuza, isu tinobva taratidza kuti mutsauko wehuwandu pakati pezvakayerwa uye zvakafanotaurwa ρ kukosha padhuze nekuparara kwekumberi kunogona kubviswa nekunatsa fungidziro yedu yekufungidzira kuti ibatanidze kuvuza uku.Kuti izvi zviitike, ngativerengei nhamba yese yeTa maatomu inoyerera ichibva kune yakasimba ichipinda mumvura kana iyo yakaora pamberi inofamba ichienda kure kure Δxi = vΔt munguva yenguva Δt Δxi = vΔt, apo \ (v={\ dot{x) )) _{i }( t )\) - delamination rate, kudzika uye nguva zvinogona kutorwa kubva kuhukama hunozivikanwa \({x}_{i}(t)=\sqrt{4p{D}_{l}t } \) deaeration.Mutemo wepanzvimbo wekuchengetedza huremu pamberi pekupatsanurwa (d ≈ 0) unoita kuti ΔN = DlglΔtSl/va, apo gl ndiyo inoyerera yeTa maatomu mumvura, va ndiyo vhoriyamu yeatomu inowirirana neconcentration inotsanangurwa se chidimbu cheatomu, uye Sl = St - Ss inzvimbo yakachinjika-chikamu cheiyo chiteshi chemvura kumberi kwe delamination.Concentration gradient gl inogona kuverengerwa nekufungidzira kuti concentration yeTa atoms ine value yenguva dzose \({c}_{Ta}^{l}\) painterface uye idiki kwazvo pakunyunguduka kunze kweiyo exfoliated layer, iyo inopa \( {g}_ {l}={c}_{Ta}^{l}/{x}_{i}\) Saka, \({{\Delta}}}N=({{\ Delta} {x}_{i} {S}_{l}/{v}_{a}){c}_{Ta}^{l}/(2p)\).Kana kumberi kwaenda kure kure Δxi, chikamu chakasimba chakaenzana nenhamba yese yeTa maatomu yakabviswa kubva pachigadziko chealloy, \({{\Delta}}{x}_{i}{S}_{t} { c }_{Ta}^ { 0}/{v}_{a}\), kuhwerengedzo yenhamba yeTa maatomu arikubuda mumvura, ΔN, uye akabatanidzwa mune yakasimba binder\({{\Delta} } {x}_{i}{S}_{s {c}_{Ta}^{s}/{v}_{a}\).Iyi equation, pamwe chete nekutaura kwepamusoro kwe ΔN uye hukama St = Ss + Sl uye zvikamu pa delamination mberi.
Mumuganho we zero kunyungudika kweTa maatomu, izvo zvinodzikisira kune kufanotaura kwekutanga kusavapo kwekuvuza, \(\rho ={c}_{Ta}^{0}/{c}_{Ta}^{s} \)mvura ( \({c }_{Ta}^{l}=0\)).Kushandisa kukosha \\ ({c}_{Ta}^{l}\ about 0.03\) kubva pazviyero zvekuedza (zvisina kuratidzwa muFig. 5a, b) uye nhamba dzePeclet p ≈ 0.26 uye p ≈ 0.17 uye solids concentrations \ ( {c}_{Ta}^{s}\ ingangoita 0.3\) uye \({c}_{Ta}^{s}\ ingangoita 0.25\) yeCu neCu70Ag30 inonyunguduka, zvichiteerana , tinowana kukosha kwakafanotaurwa the melt, ρ ≈ 0.38 uye ρ ≈ 0.39.Aya mafungidziro ari muhuwandu muchibvumirano chakanaka nezviyero.Misiyano yese (yakafanotaurwa 0.38 vs. yakayerwa 0.32 ye pure Cu yakanyunguduka uye 0.39 yakafanotaurwa vs. yakayerwa 0.43 yeCu70Ag30 kunyunguduka) inogona kutsanangurwa nehuyero hukuru kusava nechokwadi kwekudzika kwakanyanya kweTa muzvinwiwa (\( {c }_{Ta }^ {l}\ ingangoita 0.03\)), iyo inotarisirwa kuve yakati kurei mukunyungudika kwakachena kwemhangura.
Kunyangwe zviedzo zvazvino zvakaitwa pane chaiwo ma base alloys uye melt zvinhu, isu tinotarisira kuti mhedzisiro yeongororo yezviyedzo izvi ichabatsira kuburitsa equations.(2) Wide kushandiswa kune dzimwe LMD doping systems uye dzimwe nzira dzakabatana dzakadai seSolid State Impurity Removal (SSD).Kusvika ikozvino, pesvedzero yekuvuza kwezvinhu zvisingaite pane LMD chimiro haina kufuratirwa zvachose.Izvi zvinonyanya kukonzerwa nekuti mhedzisiro iyi haina kukosha muECDD, uye kusvika zvino zvave zvichifungidzirwa zvisina musoro kuti NMD yakafanana neREC.Zvakadaro, musiyano wakakosha pakati peECD neLMD ndewekuti muLMD kunyungudika kwezvinhu zvisingasanganisike muzvinwiwa kunowedzera zvakanyanya nekuda kwekuwanda kwezvinhu zvinosanganiswa padivi remvura ({c}_{Ti} ^{ l}\)), iyo inozowedzera kuwanda kwezvinhu zvisingagoneki (\({c}_{Ta}^{l}\)) padivi remvura rechimiro uye inoderedza chikamu chevhoriyamu chakafanotaurwa neiyo solid state equation. .(2) Kuvandudzwa uku kunokonzerwa nekuti iyo solid-liquid interface panguva yeLMD iri munharaunda thermodynamic equilibrium, saka yakakwirira \({c}_{Ti}^{l}\) inobatsira kuvandudza \({c} _ {Ta} ^{l}\ Saizvozvo, yakakwirira \({c}_{Ti}^{s}\) inobvumira Cu kuti ibatanidzwe mumabhaidha akaomarara, uye kusungirirwa kweCu yakasimba mumasungiro aya kunosiyana kubva pa10% zvishoma nezvishoma. kuderera kuhukoshi hazvigoneke pamucheto weiyo diki yakatumwa layer (Supplementary Fig. 6) .Mukupesana, kubviswa kwe electrochemical yeAg kubva kuAgAu alloys neECD ndeye kusiri-equilibrium reaction isingawedzere solubility yeAu mu. iyo electrolyte.Kuwedzera kune LMD, isu tinotarisirawo kuti migumisiro yedu inoshandiswa kune yakasimba dhiraivha, apo muganhu wakasimba unotarisirwa kuchengetedza nzvimbo ye thermodynamic equilibrium panguva yekubviswa kwealloy.Iyi tarisiro inotsigirwa nechokwadi chokuti kuchinja kwechikamu chevhoriyamu. yezvakaoma muchikamu chakapihwa chechimiro cheSSD chakaonekwa, zvichireva ini, kuti panguva yenhumwa pane kuparara kweiyo yakasimba ligament, ine chekuita nekudonha kwezvinhu zvisingaite.
Uye iyo equation.(2) Kuti kufanotaura kuderera kukuru kwechikamu chakasimba kumberi kwekubvisa alloy nekuda kwekudonha kweTa, zvinofanirwawo kufunga nezve Ta kutakura munzvimbo yekubvisa alloy kuitira kuti unzwisise kugovaniswa kwechikamu chakasimba munharaunda yese. alloy kubvisa layer, iyo inopindirana nemhangura yakachena uye Cu70Ag30 inonyungudika.KuCu70Ag30 melt (mutsara mutsvuku muFig. 5c), ρ(d) ine hushoma hunosvika hafu yechikamu chakapihwa.Uhwu hushoma hunokonzerwa nenyaya yekuti huwandu hweTa huri mubhainda rakaoma padyo nemupendero weiyo dhizaini yakakura kupfuura yepasi alloy.Kureva kuti, d ≈ 230 μm \({S}_{s}(d){c}_{Ta}^{s}(d)\, > \,{S}_{t}{c} _ { Ta}^{0}\), kana kuti kuenzana zvachose, kuyerwa ρ(d) = Ss(d)/St ≈ 0.35 yakakura kudarika equation inofanofungidzira.(1) Hapana kubvinza\({c}_{Ta}^{0}/{c}_{Ta}^{s}(d)\approx. 0.2\).Izvi zvinoreva kuti chikamu cheTa chinopukunyuka chinotakurwa kubva kumberi kwekuparadzaniswa kuenda kunzvimbo iri kure kubva kumberi uku, ichipararira mumvura uye pamwe neiyo yakasimba-yemvura interface, kwainozoiswazve.
Kuiswa patsva uku kune zvinopesana neTa leakage kupfumisa Ta hard binders, uye kugova kwechikamu chakaoma kunogona kutsanangurwa zvine mutsindo sechiyero cheTa leakage uye kudzokorora.Kune iyo Cu70Ag30 inonyunguduka, iyo Ag yekumisikidza mumvura inowedzera nekuwedzera d (yebrown dotted mutsara muFig. 5b) kuderedza Ta kuvuza nekudzikira Ta solubility, izvo zvinotungamira mukuwedzera mu ρ (d) nekuwedzera d mushure mekusvika zvishoma. .Izvi zvinochengetedza chikamu chakasimba chakakura zvakakwana kudzivirira kupatsanuka nekuda kwekuvharirwa kweiyo hard bond, izvo zvinotsanangura kuti sei zvimiro zvakapihwa muCu70Ag30 zvinonyunguduka zvinochengeta kutendeseka kwechimiro mushure mekucheka.Kusiyana neizvi, kune mhangura yakachena inonyunguduka, kuvuza uye kuiswa patsva kunoda kudzima imwe neimwe kunze, zvichikonzera kudzikiswa zvishoma nezvishoma kwezvakaoma pazasi pechikamu chechikamu chechikamu chakapihwa, kuchisiya chete chitete chakatetepa chinochengetedza kuvimbika kwechimiro padyo nemuganho weiyo. delegated layer.(Mufananidzo 4b, Tafura 1).
Kusvika pari zvino, ongororo dzedu dzakanyanya kutarisisa kutsanangura simba rakasimba rekudonhedza kwezvimiro zvinokanganisika mune inobvisa svikiro pachikamu chakasimba uye topology yezvimiro zvakatumwa.Ngatitendeukei kune mhedzisiro yekuvuza uku pakudzika kweiyo bicontinuum chimiro mukati meiyo yakatumirwa layer, inowanzoitika panguva yeLMD nekuda kwekupisa kwakanyanya.Izvi zvakasiyana neECD apo kukoromoka kunenge kusipo panguva yekubviswa kwealloy, asi kunogona kukonzerwa nekunyunguduka pakudziya kwepamusoro mushure mekubviswa kwealloy.Kusvika pari zvino, kukoromoka panguva yeLMD kwakaenzanisirwa pasi pefungidziro yekuti inoitika nekuda kwekupararira kwezvinhu zvisingagoneki pamwe chete neiyo solid-liquid interface, yakafanana neyepamusoro diffusion-mediated coarsening yeannealed nanoporous ECD zvimiro.Saka, saizi yebhondi yakagadziridzwa uchishandisa yakajairwa scaling mitemo capillary kuwedzera.
uko tc ndiyo nguva yekukora, inotsanangurwa senguva yakapfuura mushure mekufamba kwe delamination kumberi pakadzika xi mukati me delamination layer (apo λ ine kukosha kwekutanga kwe λ00) kusvika pakupera kweyedzero ye delamination, uye scaling index n = 4 inoparadzanisa pamusoro.Eq inofanira kushandiswa nekuchenjerera.(3) Dudzira zviyero zve λ uye chinhambwe d chechimiro chekupedzisira pasina kusvibiswa pakupera kwekuyedza.Izvi zvinokonzerwa nekuti dunhu riri pedyo nekumucheto kwenzvimbo yakapihwa rinotora nguva yakareba kuti rikure kupfuura dunhu riri pedyo nekumberi.Izvi zvinogona kuitwa nekuwedzera equations.(3) Kukurukurirana netc uye d.Hukama uhwu hunogona kuwanikwa zviri nyore nekufanotaura kudzika kwekubviswa kwealloy sebasa renguva, \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\), izvo zvinopa tc(d) = te − tf(d), apo te ndiyo nguva yechiyedzo chose, \({t}_{f}(d)={(\sqrt{4p{D}_{l}) {t}_{ e } }-d)}^{2}/(4p{D}_{l})\) ndiyo nguva yekuti delamination yemberi isvike pakadzika yakaenzana nekudzika kwekupedzisira kubvisa d.Batanidza chirevo ichi che tc(d) muequation.(3) Predict λ(d) (ona imwe chinyorwa 5).
Kuti tiedze fungidziro iyi, takaita zviyero zvehupamhi uye chinhambwe pakati pemasumbu pamativi akazara emuchinjiko wezvimiro zvakapihwa zvinoratidzwa muSupplementary Figure 9 kune yakachena Cu uye Cu70Ag30 inonyungudika.Kubva mumutsara scans perpendicular kuenda ku delamination direction pamadaro akasiyana d kubva ku delamination kumberi, takawana avhareji yehupamhi λw(d) yeTa-rich masumbu uye avhareji chinhambwe λs(d) pakati pemasumbu.Izvi zviyero zvinoratidzwa mufig.5d uye ichienzaniswa nekufanotaura kweiyo equation.(3) muSupplementary Fig. 10 yemhando dzakasiyana dze n.Kuenzanisa kunoratidza kuti indekisi yekupararira kwepamusoro ye n = 4 inopa kufanotaura kwakashata.Kufembera uku hakuna kuvandudzwa zvakanyanya nekusarudza n = 3 yeakawanda diffusion-mediated capillary coarsening, iyo munhu angangotarisira kupa yakaringana nekuda kweTa kuvuza mumvura.
Uku kusawirirana kwehuwandu pakati pedzidziso uye kuedza hazvishamise, sezvo Eq.(3) inotsanangura kukora kwecapillary pachikamu chevhoriyamu chinogara chiripo ρ, nepo paLMD chikamu chezvakaoma ρ hachigarike.ρ inoshandura nzvimbo mukati mechikamu chakabviswa pamagumo ekubvisa alloy, sezvinoratidzwa mufig.5c.ρ inoshandukawo nenguva panguva yekubviswa kwetsvina pakadzika kubviswa kudzika, kubva paukoshi hwemberi yekubvisa (iyo inenge isingachinji nenguva uye nokudaro yakazvimiririra pa tf uye d) kusvika pachiyero chakayerwa che ρ (d) inoratidzwa muFig. 5c inoenderana nenguva yekupedzisira.Kubva muonde.3d, inogona kufungidzirwa kuti iyo yekuora yepamberi maitiro ingangoita 0.4 uye 0.35 yeAgCu uye yakachena Cu inonyungudika, zvichiteerana, iyo mune zvese zviitiko yakakwirira kupfuura kukosha kwekupedzisira kwe ρ panguva te.Izvo zvakakosha kuti uzive kuti kudzikira kwe ρ nenguva pane yakatarwa d imhedzisiro yakananga yekuvapo kweiyo concentration gradient yemiscible element (Ti) mumvura.Sezvo kuwanda kweTi muzvinwiwa kunoderera nekuwedzera d, kuenzana kweTi muzvinhu zvakasimba zvakare kuderera kwebasa re d, izvo zvinotungamirira mukuparara kweTi kubva kune zvakasimba zvisungo uye kuderera kwechikamu chakasimba nekufamba kwenguva.Iko shanduko yenguva mu ρ inobatwawo nekudonha uye kudzokororwa kweTa.Nekudaro, nekuda kwekuwedzera kwemhedzisiro yekuparara uye kudzoreredzwa, isu tinotarisira kuti kukoromoka panguva yeLMD kuchaita, sekutonga, kunoitika pane zvisingaverengeki vhoriyamu zvikamu, izvo zvinozotungamira mukushanduka kwemaitiro mukuwedzera kune capillary coarsening, asiwo nekuda kwekupararira mukati. zvinwiwa uye kwete chete pamuganhu wakasimba-mvura.
Equation chokwadi.(3) Bond hupamhi uye nzvimbo yezviyero zve 3 ≤ n ≤ 4 haina kuverengerwa (Supplementary Fig. 10), zvichiratidza kuti kuparara uye kudzoreredzwa kwete nekuda kwekuderedzwa kwechimiro kunobata basa guru mukuedza kwezvino.Pakukoira kwecapillary, λw ne λs zvinotarisirwa kuve nekutsamira kumwechete pana d, ukuwo Fig. 5d inoratidza kuti λs inowedzera ne d nekukasira kudarika λw ye pure Cu uye Cu70Ag30 inonyunguduka.Nepo coarsening dzidziso inotora muakaundi kuparara uye redeposition inofanira kutariswa kutsanangura zviyero izvi quantitatively, musiyano uyu unotarisirwa qualitatively, sezvo kuparara zvachose kwezvisungo zviduku kunobatsira kuwedzera kwechinhambwe pakati pezvisungo.Mukuwedzera, iyo λs yeCu70Ag30 inonyunguduka inosvika pakukosha kwayo kumucheto kwechigadziko pasina alloy, asi chokwadi chokuti λs yemhangura yakachena inonyunguduka inoramba ichiwedzera monotonically inogona kutsanangurwa nekuwedzera kweAg concentration mumvura, apo. d rinoshandiswa kutsanangura ρ(d) muFig. 5c nonmonotonic maitiro.Kuwedzera iyo Ag concentration nekuwedzera d inodzvinyirira Ta kuvuza uye binder dissolution, izvo zvinotungamira mukudzikira mu λs mushure mekusvika kune yakanyanya kukosha.
Chekupedzisira, cherechedza kuti zvidzidzo zvekombuta zvecapillary coarsening pane inogara vhoriyamu chikamu chinoratidza kuti kana chikamu chevhoriyamu chinowira pazasi pechikumbaridzo chingangoita 0.329.30, iyo dhizaini zvidimbu panguva yekukora.Mukuita, chikumbaridzo ichi chinogona kunge chakadzikira zvishoma nekuti kupatsanurwa uye kupindirana kwejenasi kudzikiswa kunoitika pachiyero chenguva chinoenzaniswa kana kuti chikuru kupfuura nguva yese yekubvisa alloy muchiyedzo ichi.Idi rekuti zvimiro zvakapihwa muCu70Ag30 zvinonyunguduka zvinochengeta hunhu hwazvo kunyangwe ρ(d) iri pazasi pe 0.3 muavhareji dhi inoratidza kuti kupatsanurwa, kana kuripo, kunoitika zvishoma.Iyo vhoriyamu chikamu chepakati pepakati pekupatsanurwa chinogona zvakare kuenderana nekuparara uye kudzoreredza.
Chidzidzo ichi chinoburitsa mhedziso huru mbiri.Kutanga, uye zvakanyanya kuita, iyo topology yezvimiro zvakatumirwa zvinogadzirwa neLMD inogona kudzorwa nekusarudza iyo yakanyungudika.Nekusarudza kunyunguduka kudzikisa kunyungudika kweiyo immiscible element A yeAXB1-X base alloy mukunyunguduka, kunyangwe ichishomeka, chimiro chakapihwa zvakanyanya chinogona kugadzirwa chinochengeta kubatana kwayo kunyangwe pakadzika kudzika kwepasi chinhu X uye kutendeseka kwechimiro. .Zvaimbozivikanwa kuti izvi zvaigoneka kuECD25, asi kwete yeLMD.Mhedziso yechipiri, iyo inonyanya kukosha, ndosaka muLMD kutendeseka kwechimiro kunogona kuchengetedzwa nekugadzirisa svikiro rekugovera, iro rinonakidza pacharo uye rinogona kutsanangura zvakaonekwa zveTaTi alloy yedu muCu uye CuAg yakachena inonyungudika mukati, asi zvakare mu. zvakanyanya kujekesa zvakakosha, zvaisambofungidzirwa kusiyana pakati peECD neLMD.
MuECD, kubatana kwechimiro kunochengetedzwa nekuchengetedza kubviswa kwetsvina padanho rakaderera X, rinoramba riripo nekufamba kwenguva kwesimba rekutyaira rakagadziriswa, diki zvakakwana kuchengetedza zvakakwana miscible element B mubhainda rakasimba panguva yekubvisa tsvina kuchengetedza. solids volume.chikamu che ρ chakakura zvakakwana kudzivirira kupatsanurwa25.MuLMD, mwero wekubvisa alloy \(d{x}_{i}(t)/dt=\sqrt{p{D}_{l}/t}\) inodzikira nekufamba kwenguva nekuda kwediffusion limited kinetics.Nokudaro, pasinei nerudzi rwekunyunguduka kunobata chete Peclet nhamba p, delamination rate inokurumidza kusvika pamutengo muduku zvakakwana kuchengetedza huwandu hwakakwana hweB mubhainda rakasimba, rinoratidzwa zvakananga pakuti ρ pa delamination. kumberi kunoramba kuri kuenderana nenguva.Chokwadi uye pamusoro pechikumbaridzo chekuparadzanisa.Sezvinoratidzwa nechikamu chesimulation simulation, chiyero chepeel chinokurumidza kusvika kune kukosha kudiki zvakakwana kukanganisa kukura kweeutectic bond, nekudaro kufambisa kuumbwa kweiyo topologically bonded zvimiro nekuda kwe lateral rocking motion ye lamellae.Saka, musiyano mukuru wakakosha pakati peECD neLMD uri mukushanduka kwedealmination kumberi kuburikidza nemukati meiyo layer mushure mekutsemuka uye ρ, kwete delamination rate.
MuECD, ρ uye yekubatanidza inoramba yakamira mukati mese kure.MuLMD, mukupesana, zvese zvinosiyana mukati mechikamu, icho chinoratidzwa zvakajeka muchidzidzo chino, chinoronga kusangana kweatomu uye kugoverwa kwe ρ mukudzika kwezvimiro zvakapihwa zvakagadzirwa neLMD.Pane zvikonzero zviviri zvekuchinja uku.Chekutanga, kunyangwe pazero solubility muganhu A, iyo concentration gradient B mumvura, iyo isipo muDZE, inoita kuti concentration gradient A mune yakasimba binder, iri mukuenzana kwemakemikari nemvura.Iyo gradient A, zvakare, inokwevera gradient ρ mukati medhiza pasina tsvina.Chechipiri, kubuda kweA mumvura nekuda kwekusanyungudika kusiri zero kunowedzera kuchinjika kwenzvimbo ye ρ mukati meiyi layer, nekudzikira kunyungudika kunobatsira kuchengeta ρ yakakwirira uye yakawanda yunifomu kuchengetedza kubatana.
Chekupedzisira, shanduko yehukuru hwebhondi uye yekubatanidza mukati meiyo yakatumirwa layer panguva yeLMD yakanyanya kuomarara kupfuura iyo yepasi diffusion-inogumira capillary coarsening pane inogara vhoriyamu chikamu, sezvaimbofungwa nekufananidza nekukoira kweannealed nanoporous ECD zvimiro.Sezvinoratidzwa pano, kukoromoka muLMD kunoitika muchikamu chespatiotemporally chakasiyana chakasimba uye chinowanzo kukanganiswa nekufambiswa kweA uye B munzvimbo yemvura kubva kune delamination kumberi kusvika kumucheto kweiyo disjointed layer.Mitemo yekuyera yecapillary coarsening inoganhurwa nepamusoro kana kuwanda kupararira haigone kuverengera shanduko muhupamhi uye chinhambwe pakati pemasumbu mukati mechikamu chakatumwa, tichifungidzira kuti kutakura kweA neB kunoenderana neiyo fluid concentration gradients inotamba mabasa akaenzana kana akafanana.Zvinonyanya kukosha pane kudzikisa nzvimbo yeiyo interface.Kuvandudzwa kwedzidziso inorangarira idzi pesvedzero dzakasiana-siana itariro inokosha yenguva yemberi.
Titanium-tantalum mabhinari alloys akatengwa kubva kuArcast, Inc (Oxford, Maine) achishandisa 45 kW Ambrell Ekoheat ES induction magetsi uye mvura-yakatonhorera crucible yemhangura.Mushure mekupisa kwakawanda, alloy imwe neimwe yakavharwa kwemaawa masere pakupisa mukati me200 ° C. yekunyungudika kuti iwane homogenization uye kukura kwezviyo.Masamples akachekwa kubva kune iyi master ingot akaiswa mavara-welded kune Ta waya uye akamiswa kubva paruoko rwerobhoti.Mabhati esimbi akagadzirwa nekudziya musanganiswa we40 g Cu (McMaster Carr, 99.99%) neAg (Kurt J. Lesker, 99.95%) kana maTi particles ane simba guru achishandisa 4 kW Ameritherm Easyheat induction heat system kusvikira yapera zvachose.mabhati.kunyatsopisa kunyunguduka.Deredza simba uye rega bhati rikurudzire uye rienzanise kwehafu yeawa pakuita tembiricha ye1240 ° C.Ipapo ruoko rwerobhoti runodzikiswa, sampuli inonyudzwa mubhavhu kwenguva yakatemerwa uye inobviswa kuti itonhodze.Kupisa kwese kweiyo alloy billet uye LMD yakaitwa mumhepo yekuchena argon (99.999%).Mushure mekubvisa alloy, zvikamu zvemuchinjikwa zvemasampuli zvakakwenenzverwa uye zvakaongororwa uchishandisa optical microscopy uye scanning electron microscopy (SEM, JEOL JSM-6700F).Elemental analysis yakaitwa ne energy dispersive X-ray spectroscopy (EDS) muSEM.Hutatu-dimensional microstructure yemasamples akapihwa yakaonekwa nekunyungudusa chikamu chakaomeswa chemhangura mune 35% nitric acid solution (analytical giredhi, Fluka).
Iyo yekufananidza yakaitwa uchishandisa iyo yakambogadzirwa modhi yemunda weiyo decoupling chikamu cheiyo ternary alloy15.Iyo modhi inoenderana nekushanduka kwechikamu chechikamu ϕ, iyo inosiyanisa pakati peiyo yakasimba uye yemvura nhanho, kune iyo yekumisikidza ndima ye alloying zvinhu.Simba rose rakasununguka rehurongwa rinoratidzwa se
apo f(φ) ndiyo yakapetwa kaviri chipingamupinyi chinogoneka chine minima pa φ = 1 uye φ = 0 inoenderana nezvakaoma uye zvinwiwa, zvichiteerana, uye fc(φ, c1, c2, c3) ndiyo kemikari inopa kune vhoriyamu rusununguko inotsanangura kusimba kwesimba. ye thermodynamic properties alloy.Kutevedzera kudzoreredzwa kweCuTi yakachena kana CuTi inonyunguduka muTaTi alloys, isu tinoshandisa yakafanana fomu fc(φ, c1, c2, c3) uye paramita sezviri mureferensi.15. Kuti tibvise maTaTi alloys ane CuAg melts, isu takarerutsa iyo quaternary system (CuAg) TaTi kune inoshanda ternary system ine maparamendi akasiyana zvichienderana neAg concentration, sezvakatsanangurwa muSupplementary Note 2. Evolution equations yendima yechikamu uye iyo nzvimbo yevasungwa yakawanikwa mune akasiyana fomu mune fomu
Kupi \({M}_{ij}={M}_{l}(1-\phi){c}_{i}\kuruboshwe({\delta}_{ij}-{c}_{j} \kurudyi)\) ndiyo atomic mobility matrix, uye Lϕ inotonga kinetics yeatomu yakanamatira pane yakasimba-mvura interface.
Data yekuedza inotsigira mhedzisiro yeongororo iyi inogona kuwanikwa mune yekuwedzera data faira.Simulation parameters inopihwa mune yekuwedzera ruzivo.Yese data inowanikwawo kubva kune vakasiyana vanyori pakukumbira.
Wittstock A., Zelasek W., Biner J., Shamwari SM uye Baumer M. Nanoporous goridhe catalysts kune yakaderera tembiricha inosarudza gas-phase oxidative coupling yemethanol.Sayenzi 327, 319–322 (2010).
Zugic, B. et al.Dynamic recombination inosarudza inokonzeresa chiitiko che nanoporous goridhe-silver alloy catalysts.National alma mater.16, 558 (2017).
Zeis, R., Mathur, A., Fritz, G., Lee, J. uye Erlebacher, J. Platinum-yakavharwa nanoporous goridhe: inoshanda yakaderera pt kurodha electrocatalyst yePEM mafuta masero.Journal #165, 65–72 (2007).
Snyder, J., Fujita, T., Chen, MW uye Erlebacher, J. Oxygen kuderedza mu nanoporous metal-ion liquid composite electrocatalysts.National alma mater.9, 904 (2010).
Lang, X., Hirata, A., Fujita, T. uye Chen, M. Nanoporous hybrid metal/oxide electrodes for electrochemical supercapacitors.National nanotechnology.6, 232 (2011).
Kim, JW et al.Optimization ye fusion ye niobium nesimbi inonyungudika kugadzira porous zvimiro zve electrolytic capacitors.Journal.84, 497–505 (2015).
Bringa, EM etc. Zvinhu zve nanoporous zvinoshingirira kumwaranzi here?Nanolet.12, 3351–3355 (2011).