Ua tsaug rau koj tuaj xyuas Nature.com.Koj siv lub browser version nrog kev txhawb nqa CSS tsawg.Rau qhov kev paub zoo tshaj plaws, peb xav kom koj siv qhov browser tshiab (lossis lov tes taw Compatibility Hom hauv Internet Explorer).Tsis tas li ntawd, txhawm rau xyuas kom muaj kev txhawb nqa tsis tu ncua, peb qhia lub vev xaib tsis muaj qauv thiab JavaScript.
Qhia ib lub carousel ntawm peb slides ib zaug.Siv cov nyees khawm dhau los thiab Tom ntej kom txav mus los ntawm peb qhov swb ib zaug, lossis siv cov khawm slider thaum kawg kom txav mus los ntawm peb qhov swb ib zaug.
Hauv ob peb xyoos dhau los, tau muaj kev txhim kho sai ntawm cov kua hlau alloys rau kev tsim cov nano-/meso-sized ntxeem tau thiab cov qauv sib xyaw nrog ultra-loj interfaces rau ntau yam ntaub ntawv.Txawm li cas los xij, txoj hauv kev no tam sim no muaj ob qhov kev txwv tseem ceeb.Ua ntej, nws tsim cov qauv bicontinuous nrog kev txiav txim siab topology rau ib qho kev txwv ntawm cov khoom sib xyaw alloy.Qhov thib ob, cov qauv muaj qhov loj dua ntawm cov ntawv khi vim qhov loj loj thaum lub sij hawm sib cais ntawm qhov kub thiab txias.Ntawm no, peb ua piv txwv thiab sim ua kom pom tias cov kev txwv no tuaj yeem kov yeej los ntawm kev ntxiv cov khoom rau cov hlau melts uas txhawb nqa kev txiav txim siab topology los ntawm kev txwv cov xau ntawm immiscible ntsiab thaum lub sij hawm decoupling.Tom ntej no, peb piav qhia qhov kev tshawb pom no los ntawm kev qhia tias kev hloov pauv ntau ntawm cov ntsiab lus tsis muaj nyob hauv cov kua melts muaj zog cuam tshuam rau kev hloov pauv ntawm cov khoom seem thiab cov topology ntawm cov qauv thaum lub sij hawm flaking.Cov txiaj ntsig tau nthuav tawm qhov sib txawv ntawm cov kua hlau thiab electrochemical impurity tshem tawm, thiab tseem tsim ib txoj hauv kev tshiab kom tau txais cov qauv ntawm cov kua hlau nrog qhov ntev thiab topology.
Delegation tau hloov zuj zus mus rau hauv lub zog thiab ntau yam thev naus laus zis rau kev tsim cov nano-/ meso-qhov loj me qhib qhov pores thiab cov qauv sib xyaw nrog ultra-high interfacial nto rau ntau yam kev ua haujlwm thiab cov khoom siv xws li catalysts1,2, roj hlwb3,4, electrolytic capacitors5, 6, cov ntaub ntawv tiv taus hluav taws xob puas tsuaj 7, cov khoom siv roj teeb uas muaj peev xwm ua kom muaj zog ntxiv 8, 9 lossis cov khoom sib xyaw nrog cov khoom siv zoo heev 10, 11. Nyob rau hauv ntau hom, delegation koom nrog xaiv kev sib cais ntawm ib lub ntsiab lus ntawm qhov pib tsis muaj qauv "precursor alloy" nyob rau hauv ib puag ncig sab nraud, uas ua rau lub reorganization ntawm undissolved alloying ntsiab nrog ib tug non-trivial topology, txawv ntawm lub topology ntawm thawj alloy., Kev sib xyaw ntawm cov khoom xyaw.Txawm hais tias cov txheej txheem electrochemical delegation (ECD) siv electrolytes raws li ib puag ncig yog qhov feem ntau kawm txog niaj hnub no, txoj kev no txwv cov delegating systems (xws li Ag-Au lossis Ni-Pt) rau cov uas muaj cov ntsiab lus tseem ceeb (Au, Pt) thiab muaj ib qho txaus qhov sib txawv loj hauv kev txo qhov peev xwm muab porosity.Ib kauj ruam tseem ceeb ntawm kev kov yeej qhov kev txwv no yog qhov kev tshawb pom tsis ntev los no ntawm cov kua hlau alloying method13,14 (LMD), uas siv cov hlau alloys ua kua (xws li Cu, Ni, Bi, Mg, thiab lwm yam) nrog rau lwm yam hauv ib puag ncig. .(eg TaTi, NbTi, FeCrNi, SiMg, etc.) 6,8,10,11,14,15,16,17,18,19.LMD thiab nws cov tawv hlau alloy tshem tawm (SMD) variant ua haujlwm ntawm qhov kub thiab txias thaum lub hauv paus hlau yog hard20,21 ua rau muaj kev sib xyaw ntawm ob lossis ntau qhov sib cuam tshuam theem tom qab tshuaj etching ntawm ib theem.Cov theem no tuaj yeem hloov mus rau qhov qhib qhov hws.cov qauv.Cov txheej txheem delegation tau raug txhim kho ntxiv los ntawm kev qhia tsis ntev los no ntawm vapor theem delegation (VPD), uas siv qhov sib txawv hauv vapor siab ntawm cov khoom siv los tsim cov qauv qhib nanoporous los ntawm kev xaiv evaporation ntawm ib lub ntsiab lus 22,23.
Nyob rau theem zoo, tag nrho cov txheej txheem tshem tawm impurity no qhia ob yam tseem ceeb ntawm tus kheej txheej txheem tshem tawm impurity.Ua ntej, qhov no yog qhov kev xaiv ntawm kev sib cais ntawm cov lus hais saum toj no (xws li B hauv qhov yooj yim alloy AXB1-X) nyob rau hauv ib puag ncig sab nraud.Qhov thib ob, thawj zaug tau sau tseg nyob rau hauv cov kev tshawb fawb pioneering thiab theoretical kev tshawb fawb ntawm ECD24, yog qhov diffusion ntawm undissolved element A raws qhov sib cuam tshuam ntawm cov hlau thiab ib puag ncig thaum tshem tawm cov impurities.Diffusion muaj peev xwm tsim cov cheeb tsam atomic-nplua nuj los ntawm cov txheej txheem zoo ib yam li spinodal decay nyob rau hauv tej alloys, albeit txwv los ntawm lub interface.Txawm hais tias qhov zoo sib xws, cov txheej txheem tshem tawm cov hlau sib txawv tuaj yeem tsim cov morphologies sib txawv rau qhov tsis paub meej18.Thaum ECD tuaj yeem tsim cov txheej txheem topologically ntsig txog kev txiav txim siab siab rau cov atomic feem (X) ntawm cov ntsiab lus tsis raug (xws li Au hauv AgAu) tsawg li 5% 25, ​​kev suav thiab kev sim ntawm LMD qhia tias txoj kev zoo li no tsuas yog tsim cov txheej txheem topologically. .Piv txwv li, rau X loj dua, cov qauv sib txuas sib txuas yog kwv yees li 20% nyob rau hauv cov ntaub ntawv ntawm TaTi alloys decoupled los ntawm Cu melts (saib daim duab 2 nyob rau hauv ref. 18 rau ib sab sib piv nrog ntau yam ECD thiab LMD daim ntawv X. ).Qhov tsis sib xws no yog piav qhia los ntawm kev nthuav dav-coupled kev loj hlob mechanism txawv ntawm interfacial spinodal decomposition thiab zoo ib yam li eutectic-coupled kev loj hlob26.Nyob rau hauv ib puag ncig kev tshem tawm impurity, diffusion-coupled kev loj hlob tso cai A-nplua nuj filaments (los yog flakes nyob rau hauv 2D) thiab B-nplua nuj kua raws rau co-loj hlob los ntawm diffusion thaum impurity tshem tawm15.Pair txoj kev loj hlob ua rau ib qho kev sib raug zoo topologically unbound qauv nyob rau hauv nruab nrab ib feem ntawm X thiab yog suppressed nyob rau hauv qis ib feem ntawm X, qhov twg tsuas unbound Islands nplua nuj nyob rau hauv A theem tuaj yeem tsim.Thaum loj X, kev sib koom ua ke kev loj hlob yuav tsis ruaj khov, nyiam tsim cov qauv 3D zoo kawg nkaus uas tuav cov qauv kev ncaj ncees txawm tias tom qab ib-theem etching.Interestingly, cov qauv kev taw qhia uas tsim los ntawm LMD17 los yog SMD20 (Fe80Cr20) XNi1-X alloys tau raug soj ntsuam rau X mus txog 0.5, tawm tswv yim hais tias diffusion-coupled kev loj hlob yog ib tug ubiquitous mechanism rau LMD thiab SMD es tsis yog cov feem ntau porous ECD tsis. muaj cov qauv kev sib haum xeeb uas nyiam.
Txhawm rau kom paub meej qhov laj thawj ntawm qhov sib txawv ntawm ECD thiab NMD morphology, peb tau ua theem kev simulation thiab kev tshawb fawb ntawm NMD ntawm TaXTi1-X alloys, uas cov kinetics dissolution tau hloov kho los ntawm kev ntxiv cov ntsiab lus yaj rau cov kua tooj liab.Peb tau txiav txim siab tias txawm hais tias ob qho tib si ECD thiab LMD tau tswj hwm los ntawm kev xaiv kev sib cais thiab kev sib txawv ntawm qhov sib txawv, cov txheej txheem no tseem muaj qhov sib txawv tseem ceeb uas yuav ua rau muaj qhov sib txawv ntawm morphological18.Ua ntej, kinetics tev nyob rau hauv ECD yog tswj los ntawm lub interface nrog ib tug tas li tev pem hauv ntej tshaj tawm V12 raws li ib tug muaj nuj nqi ntawm cov ntaub ntawv voltage.Qhov no muaj tseeb txawm tias ib feem me me ntawm cov khoom siv refractory (piv txwv li Pt hauv Ag-Au) ntxiv rau cov niam txiv alloy, uas ua rau lub ntsej muag fluidity, ntxuav thiab stabilizes cov khoom tsis sib xws, tab sis txwv tsis pub khaws tib yam morphology 27 .Cov txheej txheem topologically txuas tau tsuas yog nyob rau hauv qis X ntawm qis V, thiab khaws cia ntawm miscible ntsiab 25 yog qhov loj los tuav cov khoom ntim feem loj txaus los tiv thaiv kev tawg ntawm cov qauv.Qhov no qhia tau hais tias tus nqi ntawm kev sib cais nrog rau kev sib cuam tshuam ntawm qhov sib txawv tuaj yeem ua lub luag haujlwm tseem ceeb hauv kev xaiv morphological.Nyob rau hauv sib piv, lub alloy tshem tawm kinetics nyob rau hauv ib tug LMD yog diffusion tswj 15,16 thiab tus nqi txo kuj ceev nrog lub sij hawm \(V \sim \sqrt{{D}_{l}/t}\), qhov twg Dl yog lub miscibility keeb. rau cov kua diffusion coefficient..
Thib ob, thaum lub sij hawm ECD, solubility ntawm immiscible ntsiab nyob rau hauv cov electrolyte yog tsis tshua muaj heev, yog li lawv muaj peev xwm tsuas diffuse raws cov alloy-electrolyte interface.Hauv qhov sib piv, hauv LMD, cov ntsiab lus "immiscible" (A) ntawm AXB1-X precursor alloys feem ntau muaj tsawg, txawm tias txwv, yaj solubility.Qhov me ntsis solubility no tuaj yeem raug xam los ntawm kev tsom xam ntawm ternary theem daim duab ntawm CuTaTi ternary system qhia nyob rau hauv Ntxiv Daim duab 1. Solubility tuaj yeem ntsuas tau los ntawm kev npaj cov kab kua dej piv rau qhov sib npaug ntawm Ta thiab Ti ntawm cov kua sab ntawm lub interface (\( {c}_{ {{{{{{\rm{Ta)))))}}}}^{l}\ ) and \({{{{\rm{Ti}}}}} }}}} }^ {l}\), ntsig txog, ntawm qhov delegation kub (Ntxiv daim duab. 1b) solid-kua interface Local thermodynamic equilibrium yog khaws cia thaum alloying, }}}}}}^{l}\) yog kwv yees li qhov tsis tu ncua thiab nws cov nqi muaj feem xyuam rau X. Cov duab ntxiv 1b qhia tau tias \({c}_{{{{{{\rm{Ta}}}}} ))}^{l}\) poob rau hauv thaj tsam 10 -3 − 10 ^{l}\) y = 15.16.Qhov "tawg" ntawm cov ntsiab lus tsis tuaj yeem nyob rau hauv cov hlau tuaj yeem cuam tshuam rau ob qho tib si tsim ntawm cov qauv kev sib tshuam ntawm lub delamination pem hauv ntej, uas tuaj yeem ua rau kom tawg thiab coarsening ntawm cov qauv vim qhov ntim diffusion.
Txhawm rau txhawm rau txheeb xyuas qhov kev koom tes ntawm (i) txo tus nqi ntawm kev tshem tawm ntawm alloy V thiab (ii) txo tus nqi ntawm infiltration ntawm immiscible ntsiab rau hauv yaj, peb tau mus ua ob kauj ruam.Ua ntej, ua tsaug rau \(V \sim \sqrt{{D}_{l}/t}\), los ntawm kev kawm morphological evolution ntawm cov qauv ntawm lub nras pem hauv ntej, nws muaj peev xwm kawm txog qhov txo qis V txaus.lub sij hawm loj.Yog li ntawd, peb tau tshawb xyuas cov txiaj ntsig no los ntawm kev khiav cov theem simulations nyob rau lub sijhawm ntev dua li cov kev tshawb fawb yav dhau los, uas tau qhia txog qhov muaj cov txheej txheem topologically uncoupled alignment tsim los ntawm diffusion-coupled kev loj hlob ntawm X15 nruab nrab.Thib ob, txhawm rau tshawb xyuas cov txiaj ntsig ntawm cov ntsiab lus tsis tuaj yeem ntawm kev txo qis qhov xau, peb ntxiv Ti thiab Ag rau cov tooj liab yaj kom nce thiab txo tus nqi xau, raws li, thiab kawm txog qhov tshwm sim morphology, kev sib cais kinetics, thiab kev faib tawm concentration hauv lub yaj.delegated Cu yaj los ntawm kev suav thiab kev sim hauv cov qauv hlau.Peb tau ntxiv Ti ntxiv xws li 10% mus rau 30% rau kev tshaj tawm kom tshem tawm Cu yaj.Qhov sib ntxiv ntawm Ti nce Ti concentration ntawm ntug ntawm cov txheej txheem delegated, uas txo cov Ti concentration gradient nyob rau hauv cov txheej txheem no thiab txo qhov kev sib cais.Nws kuj nce Ta's leakage rate los ntawm kev nce \({c}_{{{(\rm{Ti}}}}}}}}^{l}\), ces \({c}_{{{{{(\rm{Ti}}}}}}}}) {\rm{Ta}}}}}}}}^{l}\) (Cov duab ntxiv 1b). Lub solubility ntawm alloying ntsiab nyob rau hauv lub yaj, peb tau ua qauv lub CuAgTaTi quaternary system raws li ib tug npaum (CuAg) TaTi ternary system nyob rau hauv uas lub solubility ntawm Ti thiab Ta nyob ntawm lub concentration ntawm Ag nyob rau hauv lub CuAg yaj (saib Ceeb toom) 2 thiab ntxiv. Daim duab 2–4).Qhov sib ntxiv ntawm Ag tsis nce qhov concentration ntawm Ti ntawm ntug ntawm cov qauv delegated.Txawm li cas los xij, txij li qhov solubility ntawm Ti hauv Ag qis dua Cu, qhov no txo ​​qis \({c}_{{{{\rm{Ta}}}}}}}}^{l}\) (Cov duab ntxiv . 1) 4b) thiab tus nqi xau Ta.
Cov txiaj ntsig ntawm theem kev simulations qhia tau hais tias kev sib koom ua ke kev loj hlob tsis ruaj khov nyob rau lub sijhawm ntev txaus los txhawb kev tsim cov txheej txheem topologically txuas rau ntawm qhov lwj hauv pem hauv ntej.Peb sim ua kom paub tseeb tias qhov kev txiav txim siab no los ntawm kev qhia tias lub hauv paus txheej ntawm Ta15T85 alloy, uas tsim nyob ze ntawm lub delamination pem hauv ntej ntawm ib tug tom qab theem ntawm delamination, tseem topologically bonded tom qab etching ntawm lub tooj liab-nplua nuj theem.Peb cov txiaj ntsig tseem qhia tau hais tias tus nqi xau muaj txiaj ntsig zoo rau kev hloov pauv ntawm morphological vim kev thauj khoom loj ntawm cov khoom tsis sib xws hauv cov kua yaj.Nws tau pom ntawm no tias cov nyhuv no, uas tsis muaj nyob rau hauv ECD, cuam tshuam rau cov concentration profiles ntawm ntau yam hauv cov txheej txheem delegated, feem ntawm cov khoom theem, thiab topology ntawm LMD qauv.
Hauv seem no, peb thawj zaug nthuav tawm cov txiaj ntsig ntawm peb txoj kev tshawb fawb los ntawm theem kev simulation ntawm cov txiaj ntsig ntawm kev ntxiv Ti lossis Ag rau Cu melts uas ua rau muaj qhov sib txawv ntawm morphologies.Ntawm daim duab.Daim duab 1 nthuav tawm cov txiaj ntsig ntawm peb-seem qauv ntawm theem teb ntawm TaXTi1-X alloys tau los ntawm Cu70Ti30, Cu70Ag30 thiab ntshiab tooj liab melts nrog cov ntsiab lus tsawg atomic ntawm immiscible ntsiab ntawm 5 mus rau 15%.Thawj ob kab qhia tau hais tias qhov sib ntxiv ntawm ob qho tib si Ti thiab Ag txhawb kev tsim cov txheej txheem topologically sib raug zoo piv rau cov qauv tsis sib xws ntawm cov ntshiab Cu (peb kab).Txawm li cas los xij, qhov sib ntxiv ntawm Ti, raws li kev cia siab, nce Ta to, yog li tiv thaiv delamination ntawm qis X alloys (Ta5Ti95 thiab Ta10Ti90) thiab ua rau loj heev tawg ntawm exfoliated ntxeem tau txheej thaum lub sij hawm Ta15Ti85 delamination.Ntawm qhov tsis sib xws, qhov sib ntxiv ntawm Ag (kab ob) pab txhawb rau kev tsim cov txheej txheem topologically ntsig txog tag nrho cov khoom ntawm lub hauv paus alloy nrog me ntsis dissolution ntawm delegated txheej.Kev tsim ntawm cov qauv bicontinuous kuj tau piav qhia hauv Fig.1b, uas qhia tau hais tias cov duab ntawm lub delegated qauv nrog nce qhov tob ntawm delamination ntawm sab laug mus rau sab xis thiab ib tug duab ntawm cov khoom-kua interface ntawm qhov siab tshaj plaws qhov tob (saib sab xis duab).
3D theem teb simulation (128 × 128 × 128 nm3) qhia qhov ua tau zoo ntawm kev ntxiv cov kua nplaum rau cov kua yaj ntawm qhov kawg morphology ntawm delegated alloy.Lub cim sab sauv qhia txog qhov muaj pes tsawg leeg ntawm niam txiv alloy (TaXTi1-X) thiab lub cim ntsug qhia tias muaj pes tsawg leeg ntawm Cu-based softening nruab nrab.Cov cheeb tsam uas muaj Ta concentration siab nyob rau hauv cov qauv uas tsis muaj impurities qhia nyob rau hauv xim av, thiab cov khoom-kua interface yog qhia nyob rau hauv xiav.b Peb-dimensional simulation ntawm theem teb ntawm undoped Ta15Ti85 precursor alloy nyob rau hauv lub Cu70Ag30 yaj (190 × 190 × 190 nm3).Thawj 3 thav duab qhia cov khoom siv hauv cheeb tsam ntawm cov qauv delegated ntawm qhov sib txawv delegation depths, thiab cov ncej kawg qhia tsuas yog cov khoom-kua interface ntawm qhov tob tshaj plaws.Cov yeeb yaj kiab sib raug rau (b) muaj nyob hauv Cov Yeeb Yaj Kiab Ntxiv 1.
Cov txiaj ntsig ntawm qhov sib ntxiv tau tshawb fawb ntxiv nrog 2D theem simulations, uas tau muab cov ntaub ntawv ntxiv ntawm kev sib cuam tshuam hom tsim ntawm lub delamination pem hauv ntej thiab tso cai rau kev nkag mus rau qhov ntev thiab sij hawm ntau dua li 3D simulations kom muaj nuj nqis ntawm delamination kinetics.Ntawm daim duab.Daim duab 2 qhia cov duab ntawm kev simulation ntawm kev tshem tawm ntawm Ta15Ti85 precursor alloy los ntawm Cu70Ti30 thiab Cu70Ag30 melts.Nyob rau hauv ob qho tib si, diffusion-coupled kev loj hlob yog unstable heev.Tsis txhob nkag mus rau vertically rau hauv cov hlau, cov lus qhia ntawm cov dej ntws txav chaotically sab laug thiab sab xis nyob rau hauv txoj kev nyuaj heev thaum lub sij hawm txoj kev loj hlob ruaj khov uas txhawb nqa cov kev sib raug zoo uas txhawb kev tsim cov txheej txheem topologically hauv 3D qhov chaw (Fig. 1).Txawm li cas los xij, muaj qhov sib txawv tseem ceeb ntawm Ti thiab Ag additives.Rau Cu70Ti30 yaj (Daim duab 2a), kev sib tsoo ntawm ob txoj kab ua kua ua rau kev sib koom ua ke ntawm cov khoom-kua interface, uas ua rau cov extrusion ntawm cov khoom binders ntes tau los ntawm ob txoj hauv kev los ntawm cov qauv thiab, thaum kawg, kom tawg. .Ntawm qhov tsis sib xws, rau Cu70Ag30 yaj (Daim duab 2b), Ta enrichment ntawm qhov sib cuam tshuam ntawm cov khoom thiab cov theem ua kua tiv thaiv coalescence vim qhov txo qis hauv Ta to rau hauv cov yaj.Yog li ntawd, compression ntawm daim ntawv cog lus ntawm lub delamination pem hauv ntej yog suppressed, yog li txhawb kev tsim ntawm connective lug.Interestingly, lub chaotic oscillatory tsab ntawv tsa suab ntawm cov kua channel tsim ib tug ob-dimensional qauv nrog ib tug tej yam degree ntawm kev sib raug zoo thaum lub cutoff yog suppressed (Fig. 2b).Txawm li cas los xij, qhov kev sib tw no tsis yog qhov tshwm sim ntawm kev loj hlob ruaj khov ntawm daim ntawv cog lus.Hauv 3D, kev nkag mus tsis ruaj khov tsim ib qho kev sib txuas uas tsis yog coaxial txuas nrog cov qauv (Fig. 1b).
Snapshots ntawm 2D theem teb simulations ntawm Cu70Ti30 (a) thiab Cu70Ag30 (b) melts remelted rau Ta15Ti85 alloy illustrating unstable diffusion-coupled kev loj hlob.Cov duab qhia qhov sib txawv impurity tshem tawm qhov tob ntsuas los ntawm qhov chaw pib ntawm lub tiaj tus khoom / kua interface.Cov insets qhia txawv txoj cai ntawm cov kua channel sib tsoo, ua rau lub detachment ntawm khoom binders thiab preservation ntawm Cu70Ti30 thiab Cu70Ag30 melts, feem.Qhov dav dav ntawm Cu70Ti30 yog 1024 nm, Cu70Ag30 yog 384 nm.Cov xim dawb qhia tau hais tias Ta concentration, thiab cov xim sib txawv txawv ntawm thaj av ua kua (xiav tsaus), lub hauv paus alloy (lub teeb xiav), thiab cov qauv tsis sib xws (yuav luag liab).Cov yeeb yaj kiab ntawm cov kev sim no tau nthuav tawm hauv Cov Yeeb Yaj Kiab Ntxiv 2 thiab 3, uas qhia txog txoj hauv kev nyuaj uas nkag mus rau cov kua dej thaum lub sij hawm tsis ruaj khov diffusion-coupled kev loj hlob.
Lwm cov txiaj ntsig ntawm 2D theem simulation yog qhia hauv Fig.3.Daim duab ntawm delamination qhov tob piv rau lub sijhawm (qhov nqes hav sib npaug rau V) hauv daim duab.3a qhia tau hais tias qhov sib ntxiv ntawm Ti lossis Ag rau Cu yaj ua rau qeeb ntawm kev sib cais kinetics, raws li xav tau.Ntawm daim duab.3b qhia tau hais tias qhov kev poob qis no yog tshwm sim los ntawm kev txo qis hauv Ti concentration gradient hauv cov kua hauv cov txheej txheem delegated.Nws kuj qhia tau hais tias qhov sib ntxiv ntawm Ti (Ag) nce (qis) qhov concentration ntawm Ti ntawm cov kua sab ntawm lub interface (\({c}_{{{{{{{\rm{Ti))))))) )))) ^{l \) ), uas ua rau kom ntws tawm ntawm Ta, ntsuas los ntawm feem ntawm Ta yaj hauv cov yaj raws li lub sijhawm ua haujlwm (Daim duab 3c), uas nce (qis) nrog qhov sib ntxiv ntawm Ti (Ag). ).Daim duab 3d qhia tau hais tias rau ob qho tib si solutes, qhov ntim feem ntawm cov khib nyiab tseem nyob saum qhov chaw pib rau kev tsim ntawm bicontinuous topologically ntsig txog cov qauv28,29,30.Thaum ntxiv Ti rau cov yaj ua rau kom cov dej ntws tawm ntawm Ta, nws kuj ua rau kom muaj kev tuav pov hwm ntawm Ti hauv cov khoom sib khi vim yog theem sib npaug, yog li ua kom cov ntim feem ntau kom tswj tau qhov cohesiveness ntawm cov qauv yam tsis muaj impurities.Peb cov kev suav feem ntau pom zoo nrog kev sim ntsuas ntawm qhov ntim feem ntawm delamination pem hauv ntej.
Cov theem teb simulation ntawm Ta15Ti85 alloy quantifies qhov sib txawv ntawm Ti thiab Ag ntxiv rau Cu yaj ntawm cov hlau tshem tawm kinetics ntsuas los ntawm cov hlau tshem tawm qhov tob raws li kev ua haujlwm ntawm lub sijhawm (a), Ti concentration profile hauv cov kua ntawm ib qho Alloy tshem tawm qhov tob ntawm 400 nm (tsis zoo qhov tob nthuav dav rau hauv cov yaj sab nraud ntawm cov qauv hlau (alloy pem hauv ntej sab laug) b Ta leakage piv rau lub sijhawm (c) thiab cov khoom seem hauv cov qauv tsis sib xws piv rau cov khoom sib xyaw yaj (d) Cov ntsiab lus ntawm cov ntsiab lus ntxiv nyob rau hauv yaj yog plotted raws abscissa (d).
Txij li thaum qhov ceev ntawm lub delamination pem hauv ntej txo nrog lub sij hawm, evolution ntawm lub morphology thaum lub sij hawm delamination qhia cov nyhuv ntawm kev txo cov delamination ceev.Nyob rau theem dhau los ntawm kev kawm, peb tau pom eutectic-zoo li kev sib txuas ntawm kev loj hlob uas ua rau cov txheej txheem topologically unbound thaum lub sij hawm tshem tawm ntawm Ta15Ti85 precursor alloy los ntawm ntshiab tooj liab melts15.Txawm li cas los xij, ntev ntev ntawm tib theem kev simulation ua yeeb yam (saib Cov Yeeb Yaj Kiab Ntxiv 4) tias thaum lub decomposition pem hauv ntej nrawm dhau los ua me me, qhov kev sib txuas ua ke yuav tsis ruaj khov.Lub instability manifests nws tus kheej nyob rau hauv lub lateral rocking ntawm lub flakes, uas tiv thaiv lawv cov kev sib raug zoo thiab, yog li, txhawb kev tsim ntawm topologically txuas lug.Kev hloov pauv ntawm kev ruaj khov ruaj khov mus rau qhov tsis ruaj khov rocking loj hlob tshwm sim ze xi = 250 nm ntawm tus nqi ntawm 4.7 mm / s.Ntawm qhov tsis sib xws, qhov sib thooj delamination qhov tob xi ntawm Cu70Ti30 yaj yog li 40 nm ntawm tib tus nqi.Yog li ntawd, peb tsis tuaj yeem soj ntsuam qhov kev hloov pauv no thaum tshem cov hlau nrog Cu70Ti30 yaj (saib Cov Yeeb Yam 3), vim tias ntxiv 30% Ti rau cov yaj ua rau txo cov hlau tshem tawm kinetics.Thaum kawg, txawm hais tias diffusion-coupled kev loj hlob tsis ruaj khov vim qeeb delamination kinetics, qhov kev ncua deb λ0 ntawm cov ntawv cog lus nyuaj ntawm delamination pem hauv ntej roughly ua raws li \({\lambda }_{0}^{2}V = C\) txoj cai nyob ruaj ruaj kev loj hlob 15,31 qhov twg C yog qhov tsis tu ncua.
Txhawm rau ntsuas qhov kev kwv yees ntawm theem kev simulation, kev sim tshem tawm cov hlau tau ua nrog cov qauv loj dua thiab lub sijhawm tshem tawm cov hlau ntev dua.Daim duab 4a yog ib daim duab schematic uas qhia txog qhov tseem ceeb ntawm cov qauv delegated.Tag nrho qhov tob ntawm delamination yog sib npaug rau xi, qhov kev ncua deb ntawm thawj ciam teb ntawm cov khoom thiab cov theem ua kua mus rau lub delamination pem hauv ntej.hL yog qhov kev ncua deb ntawm thawj cov khoom-kua interface mus rau ntug ntawm tus qauv delegated ua ntej etching.HL loj qhia tias muaj zog Ta to.Los ntawm SEM duab ntawm tus qauv delegated, peb tuaj yeem ntsuas qhov loj hD ntawm tus qauv delegated ua ntej etching.Txawm li cas los xij, txij li lub yaj kuj solidifies nyob rau hauv chav tsev kub, nws muaj peev xwm khaws tau ib tug delegated qauv yam tsis muaj daim ntawv cog lus.Yog li ntawd, peb etched lub yaj (tooj liab nplua nuj theem) kom tau txais cov qauv kev hloov pauv thiab siv hC los ntsuas qhov tuab ntawm cov qauv hloov pauv.
Daim duab Schematic ntawm evolution ntawm morphology thaum lub sij hawm tshem tawm impurities thiab kev txiav txim ntawm geometric tsis: leakage txheej thickness Ta hL, thickness ntawm delaminated qauv hD, thickness ntawm lub connecting qauv hC.(b), (c) Kev sim ua kom pom tseeb ntawm theem kev simulation tau muab piv rau SEM hla ntu thiab 3D etched morphology ntawm Ta15Ti85 alloy npaj los ntawm cov ntshiab Cu(b) thiab Cu70Ag30 melts, yielding topological bonds nrog uniform bond loj Structure (c), scale bar 10 µm.
Tus ntoo khaub lig seem ntawm delegated lug qhia nyob rau hauv daim duab.4b, c paub meej tias qhov kev kwv yees tseem ceeb ntawm kev ntxiv Ti thiab Ag rau Cu melts ntawm morphology thiab kinetics ntawm delegated alloy.Ntawm daim duab.Daim duab 4b qhia txog thaj tsam qis ntawm SEM txiav (sab laug) ntawm Ta15T85 alloy alloyed los ntawm immersion hauv cov tooj liab ntshiab rau 10 s mus rau qhov tob ntawm xi ~ 270 μm.Ntawm qhov ntsuas ntsuas lub sij hawm ntsuas, uas yog ntau qhov kev txiav txim ntawm qhov loj dua hauv theem sim simulations, lub decoupling pem hauv ntej tshaj tawm tau zoo hauv qab cov lus hais saum toj no tshaj tawm ntawm 4.7 mm / s, hauv qab uas ruaj khov eutectic daim ntawv cog lus yuav tsis ruaj khov.Yog li ntawd, cov qauv saum toj no tev pem hauv ntej yuav tsum tau topologically txuas tag nrho.Ua ntej etching, ib txheej nyias ntawm lub hauv paus alloy tau yaj tag (hL = 20 μm), uas yog txuam nrog Ta to (Table 1).Tom qab cov tshuaj etching ntawm tooj liab-nplua nuj theem (txoj cai), tsuas yog ib tug nyias txheej ntawm delegated alloy (hC = 42 µm) nyob, qhia tias ntau ntawm cov delegated qauv poob structural kev ncaj ncees thaum lub sij hawm etching thiab tsis, raws li xav, topologically bonded ( Fig. 1a)., daim duab rightmost nyob rau kab thib peb).Ntawm daim duab.4c qhia tag nrho SEM hla ntu thiab 3D dluab ntawm etching ntawm Ta15Ti85 alloy tshem tawm los ntawm immersion nyob rau hauv lub Cu70Ag30 yaj rau 10 s mus rau ib tug tob ntawm txog 200 µm.Txij li thaum lub tev qhov tob yog theoretically kwv yees kom nce nrog \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\) diffusion tswj kinetics (saib Cov Lus Qhia Ntxiv 4) 15 16, Nrog rau qhov sib ntxiv ntawm 30% Ag rau Cu yaj, qhov txo qis hauv qhov tob ntawm kev sib cais los ntawm 270 μm mus rau 220 μm sib raug rau qhov txo qis ntawm Piclet tus lej p los ntawm qhov zoo ntawm 1.5.Tom qab cov tshuaj etching ntawm Cu / Ag nplua nuj theem (txoj cai), tag nrho cov qauv delegated khaws cov qauv kev ncaj ncees (hC = 200 µm), qhia tau hais tias nws yog ib qho kev kwv yees topologically ua ke nrog cov qauv bicontinuous (Daim duab 1, rightmost duab) kab thib ob thiab tag nrho. hauv qab kab).Tag nrho cov kev ntsuas ntawm delegated puag alloy Ta15T85 nyob rau hauv ntau yam melts yog summarized nyob rau hauv cov lus.1. Peb kuj nthuav tawm cov txiaj ntsig rau qhov tsis sib xws ntawm Ta10Ti90 puag alloys hauv ntau yam melts, lees paub peb cov lus xaus.Kev ntsuas ntawm cov xau txheej thickness Ta qhia tau hais tias cov qauv yaj nyob rau hauv lub Cu70Ag30 yaj (hL = 0 μm) yog me dua li nyob rau hauv lub ntshiab Cu yaj (hL = 20 μm).Ntawm qhov tsis sib xws, qhov sib ntxiv ntawm Ti rau cov yaj yaj yaj ntau cov qauv tsis muaj zog (hL = 190 μm).Qhov txo qis hauv kev sib cais ntawm cov qauv delegated ntawm cov ntshiab Cu yaj (hL = 250 μm) thiab Cu70Ag30 yaj (hL = 150 μm) yog ntau tshaj tawm nyob rau hauv delegated alloys raws li Ta10Ti90.
Txhawm rau kom nkag siab txog cov txiaj ntsig ntawm cov melts sib txawv, peb tau ua ib qho kev soj ntsuam ntau ntxiv ntawm cov txiaj ntsig kev sim hauv daim duab 5 (saib cov ntaub ntawv ntxiv 1).Ntawm daim duab.Daim duab 5a–b qhia ntsuas qhov sib txawv ntawm cov khoom sib txawv raws li cov kev taw qhia ntawm exfoliation nyob rau hauv exfoliation thwmsim nyob rau hauv ntshiab Cu yaj (Fig. 5a) thiab Cu70Ag30 yaj (Fig. 5b).Cov concentrations ntawm ntau yam yog npaj tawm tsam qhov kev ncua deb d los ntawm delamination pem hauv ntej mus rau ntug ntawm txheej delamination nyob rau hauv cov khoom binder thiab theem uas yog kua (enriched hauv Cu los yog CuAg) thaum lub sij hawm delamination.Tsis zoo li ECD, qhov chaw khaws cia ntawm miscible ntsiab yog txiav txim los ntawm tus nqi ntawm kev sib cais, nyob rau hauv LMD, lub concentration nyob rau hauv ib tug khoom binder yog txiav txim los ntawm lub zos thermodynamic equilibrium ntawm cov khoom thiab kua theem thiab, yog li, lub coexistence zog ntawm cov khoom thiab ua kua theem.Alloy State Diagrams.Vim lub dissolution ntawm Ti los ntawm lub hauv paus alloy, Ti concentration txo nrog nce d los ntawm delamination pem hauv ntej mus rau ntug ntawm lub delamination txheej.Raws li qhov tshwm sim, Ta concentration tau nce nrog nce d raws li cov pob khoom, uas zoo ib yam nrog cov theem simulation (Ntxiv daim duab 5).Lub Ti concentration nyob rau hauv lub Cu70Ag30 yaj ntog ntau ntiav tshaj nyob rau hauv lub ntshiab Cu yaj, uas yog zoo ib yam nrog cov qeeb alloy tshem tawm tus nqi.Kev ntsuas concentration profiles hauv Fig.5b kuj qhia tau hais tias qhov piv ntawm cov concentrations ntawm Ag thiab Cu nyob rau hauv cov kua yog tsis raws nraim nyob rau hauv cov txheej txheem ntawm delegated alloy, thaum nyob rau hauv lub simulation ntawm lub theem teb qhov piv no yog xam tau tias yog tas mus li nyob rau hauv lub simulation ntawm lub yaj li. pseudo-element Cu70Ag30.Txawm hais tias qhov sib txawv ntawm qhov sib txawv no, cov qauv hauv theem ua haujlwm tau txais txiaj ntsig zoo tshaj plaws ntawm kev ntxiv Ag ntawm kev tawm tsam Ta to.Kev ua qauv kom muaj nuj nqis ntawm cov concentration gradients ntawm tag nrho plaub lub ntsiab lus hauv cov khoom sib khi thiab cov kua dej yuav tsum muaj cov qauv plaub feem ntau ntawm TaTiCuAg cov kab kos, uas yog dhau ntawm qhov kev ua haujlwm no.
Ntsuas concentration profiles nyob ntawm qhov deb d los ntawm delamination pem hauv ntej ntawm Ta15Ti85 alloy hauv (a) ntshiab Cu yaj thiab (b) Cu70Ag30 yaj.Kev sib piv ntawm qhov ntsuas qhov ntim feem ntawm cov khib nyiab ρ(d) ntawm cov qauv delegated (cov kab khoom) nrog cov theoretical twv ua ntej sib npaug rau qhov sib npaug tsis muaj qhov to (dashed kab).(1) (c) Inflate equation twv ua ntej.(1) Equation kho ntawm lub delamination pem hauv ntej.(2) Uas yog, Ta to yog xam.Ntsuas qhov nruab nrab daim ntawv cog lus dav λw thiab nrug λs (d).Cov kab yuam kev sawv cev rau tus qauv sib txawv.
Ntawm daim duab.5c piv cov ntsuas ntim feem ntawm cov khib nyiab ρ(d) (khoom khov kab) rau cov ntshiab delegated Cu thiab Cu70Ag30 cov qauv los ntawm cov yaj nrog cov theoretical twv (dashed kab) tau los ntawm kev txuag huab hwm coj siv qhov ntsuas Ta concentration hauv cov khoom binder \({ c }_ {Ta}^{s}(d)\) (Fig. 5a,b) thiab tsis quav ntsej txog kev xau ntawm Ta thiab kev thauj ntawm Ta ntawm daim ntawv cog lus nrog qhov sib txawv tob ntawm kev sib cais.Yog tias Ta hloov los ntawm cov khoom mus rau cov kua, tag nrho cov Ta muaj nyob rau hauv lub hauv paus alloy yuav tsum tau muab faib mus rau hauv ib tug khoom binder.Yog li, nyob rau hauv ib txheej ntawm tej thaj chaw deb qauv perpendicular mus rau cov kev taw qhia ntawm kev tshem tawm ntawm lub alloy, kev txuag ntawm huab hwm coj txhais tau tias \({c}_{Ta}^{s}(d){S}_{s}(d) )={c}_{Ta}^{0}(d){S}_{t}\), where \({c}_{Ta}^{s}(d)\) and \({c }_{Ta }^ {0}\) yog cov Ta concentrations ntawm txoj hauj lwm d nyob rau hauv lub binder thiab matrix alloy, feem, thiab Ss(d) thiab St yog cov cross-sectional cheeb tsam ntawm lub hard binder thiab tag nrho cov cheeb tsam nyob deb nroog, raws.Qhov no kwv yees qhov ntim feem ntawm cov khib nyiab nyob rau hauv tej thaj chaw deb txheej.
Qhov no tuaj yeem siv tau yooj yim rau cov qauv ntawm delegated ntshiab Cu thiab Cu70Ag30 melts siv tus coj \({c}_{Ta}^{s}(d)\) nkhaus sib haum mus rau kab xiav.Cov kev kwv yees no yog superimposed rau ntawm daim duab 5c qhia tias tsis quav ntsej Ta to yog ib qho kev kwv yees tsis zoo ntawm qhov ntim feem faib.Kev txuag hluav taws xob tsis pub muaj kev cia siab kwv yees ib qho kev txo qis hauv cov ntim feem ntau nrog nce d, uas yog pom zoo nyob rau hauv cov ntshiab Cu melts, tab sis tsis nyob rau hauv Cu70Ag30 melts, qhov twg ρ (d) muaj qhov tsawg kawg nkaus.Tsis tas li ntawd, qhov no ua rau muaj qhov tseem ceeb tshaj ntawm qhov ntim feem ntawm qhov sib cais pem hauv ntej rau ob qho tib si melts.Rau qhov tsawg tshaj plaws ntsuas d ≈ 10 µm, qhov kwv yees ρ qhov tseem ceeb rau ob qho tib si melts tshaj 0.5, thaum ntsuas ρ qhov tseem ceeb rau Cu thiab Cu70Ag30 melts yog me ntsis siab dua 0.3 thiab 0.4, feem.
Txhawm rau hais txog lub luag haujlwm tseem ceeb ntawm Ta to, peb mam li qhia tias qhov sib txawv ntawm qhov ntsuas thiab kwv yees ρ qhov tseem ceeb nyob ze ntawm qhov decomposition pem hauv ntej tuaj yeem raug tshem tawm los ntawm kev ua kom peb cov kev kwv yees kwv yees suav nrog qhov xau no.Txog rau qhov kawg no, cia peb suav tag nrho cov Ta atoms ntws los ntawm cov khoom mus rau hauv cov kua thaum lub qhov faus pem hauv ntej txav mus rau qhov deb Δxi = vΔt hauv lub sijhawm Δt Δxi = vΔt, qhov twg \(v = {\dot{x) )) _{i }( t )\) – delamination tus nqi, qhov tob thiab lub sij hawm yuav muab tau los ntawm paub kev sib raug zoo \({x}_{i}(t)=\sqrt{4p{D}_{l}t } \) kev.Txoj cai lij choj hauv zos ntawm kev txuag ntawm huab hwm coj ntawm kev sib cais pem hauv ntej (d ≈ 0) yog xws li ΔN = DlglΔtSl/va, qhov twg gl yog qhov concentration gradient ntawm Ta atoms hauv cov kua, va yog qhov ntim atomic sib xws rau cov concentration tau teev tseg. atomic feem, thiab Sl = St − Ss yog qhov chaw hla ntu ntawm cov kua channel ntawm lub delamination pem hauv ntej.Qhov concentration gradient gl tuaj yeem suav tau los ntawm kev xav tias qhov concentration ntawm Ta atoms muaj tus nqi tas li \({c}_{Ta}^{l}\) ntawm qhov sib txuas thiab me me heev hauv cov yaj sab nraum cov txheej txheem exfoliated, uas muab \( {g}_{l}={c}_{Ta}^{l}/{x}_{i}\) So, \({{\Delta}}N=({{\Delta}} { x}_{i} {S}_{l}/{v}_{a}){c}_{Ta}^{l}/(2p)\).Thaum lub hauv ntej txav mus rau qhov deb Δxi, cov khoom seem yog sib npaug rau tag nrho cov Ta atoms tshem tawm ntawm lub hauv paus alloy, \({{\Delta}}{x}_{i}{S}_{t} { c }_{Ta}^ { 0}/{v}_{a}\), rau cov lej ntawm Ta atoms xau rau hauv cov kua, ΔN, thiab suav nrog hauv cov khoom sib khi\({{ \Delta} } {x}_{i}{S}_{s }{c}_{Ta}^{s}/{v}_{a}\).Qhov kev sib npaug no, ua ke nrog cov lus qhia saum toj no rau ΔN thiab kev sib raug zoo St = Ss + Sl thiab theem ntawm delamination pem hauv ntej.
Nyob rau hauv qhov txwv ntawm xoom solubility ntawm Ta atoms, uas txo mus rau ib qho kev kwv yees thaum ntxov ntawm qhov tsis muaj leaks, \(\rho = {c}_{Ta}^{0}/{c}_{Ta}^{s} \)liquid ( \({c }_{Ta}^{l}=0\)).Siv cov txiaj ntsig \({c}_{Ta}^{l}\li 0.03\) los ntawm kev ntsuas kev sim (tsis qhia hauv daim duab 5a, b) thiab Piclet tus lej p ≈ 0.26 thiab p ≈ 0.17 thiab cov khoom sib xyaw ua ke \ ( {c}_{Ta}^{s}\approximately 0.3\) and \({c}_{Ta}^{s}\approximately 0.25\) rau Cu thiab Cu70Ag30 melts, ntsig txog, peb tau txais tus nqi kwv yees ntawm yaj, ρ≈ 0.38 thiab ρ≈ 0.39.Cov kev kwv yees no yog qhov ntau hauv kev pom zoo zoo nrog kev ntsuas.Qhov seem ntawm qhov sib txawv (kwv yees 0.38 vs. ntsuas 0.32 rau ntshiab Cu yaj thiab 0.39 kwv yees vs. ntsuas 0.43 rau Cu70Ag30 yaj) tuaj yeem piav qhia los ntawm kev ntsuas ntau dua rau qhov tsis tshua muaj Ta concentrations hauv cov kua (\( {c }_{Ta }^ {l}\kwv yees 0.03\)), uas xav tias yuav loj dua me ntsis hauv cov ntshiab tooj liab yaj.
Txawm hais tias qhov kev sim tam sim no tau ua los ntawm cov alloys tshwj xeeb thiab cov ntsiab lus yaj, peb cia siab tias cov txiaj ntsig ntawm kev soj ntsuam ntawm cov kev sim no yuav pab kom tau qhov sib npaug.(2) Kev siv dav dav rau lwm lub tshuab LMD doping thiab lwm txoj hauv kev xws li Khoom Siv Hauv Lub Xeev Impurity Tshem Tawm (SSD).Txog rau tam sim no, kev cuam tshuam ntawm kev xau ntawm cov ntsiab lus tsis raug ntawm LMD qauv tau raug tsis quav ntsej kiag li.Qhov no feem ntau yog vim qhov tseeb tias qhov kev cuam tshuam no tsis tseem ceeb hauv ECDD, thiab txog tam sim no nws tau ua tsis ncaj ncees tias NMD zoo ib yam li REC.Txawm li cas los xij, qhov sib txawv tseem ceeb ntawm ECD thiab LMD yog tias nyob rau hauv LMD lub solubility ntawm immiscible ntsiab nyob rau hauv cov kua yog heev nce vim lub siab concentration ntawm miscible ntsiab ntawm cov kua sab ntawm lub interface (\({c}_{Ti} ^{ l}\)), uas nyob rau hauv lem tsub kom lub concentration ntawm immiscible ntsiab (\({c}_{Ta}^{l}\)) ntawm cov kua sab ntawm lub interface thiab txo qhov ntim feem kwv yees los ntawm cov khoom lub xeev sib npaug. .(2) Qhov kev txhim kho no yog vim qhov tseeb tias cov khoom-kua interface thaum lub sij hawm LMD yog nyob rau hauv lub zos thermodynamic equilibrium, siab \({c}_{Ti}^{l}\) pab txhim kho \({c} _ {Ta} ^{l}\ Ib yam li ntawd, siab \({c}_{Ti}^{s}\) tso cai rau Cu mus rau hauv cov ntaub ntawv nyuaj, thiab cov concentration ntawm cov khoom Cu hauv cov binders txawv ntawm li 10% maj mam. Kev txo qis rau qhov tseem ceeb yog qhov tsis txaus ntseeg ntawm ntug ntawm lub me delegated txheej (Ntxiv daim duab 6).Tshwj xeeb, kev tshem tawm electrochemical ntawm Ag los ntawm AgAu alloys los ntawm ECD yog qhov tsis sib npaug ntawm cov tshuaj tiv thaiv uas tsis ua kom cov solubility ntawm Au hauv. cov electrolyte.Ntxiv rau LMD, peb kuj cia siab tias peb cov txiaj ntsig muaj feem xyuam rau cov khoom hauv lub xeev drives, qhov twg cov ciam teb ruaj khov yuav tsum tswj xyuas qhov sib npaug hauv zos thermodynamic sib npaug thaum lub sij hawm tshem tawm alloy.Qhov kev cia siab no tau txais kev txhawb nqa los ntawm qhov tseeb tias qhov kev hloov pauv ntawm qhov ntim feem. ntawm cov khib nyiab nyob rau hauv delegated txheej ntawm SSD qauv tau soj ntsuam, implying kuv, tias thaum lub sij hawm delegation muaj ib tug dissolution ntawm cov khoom ligament, txuam nrog cov to ntawm immiscible ntsiab.
Thiab qhov sib npaug.(2) Txhawm rau kwv yees qhov txo qis ntawm cov khoom seem ntawm cov hlau tshem tawm pem hauv ntej vim Ta to, nws tseem yuav tsum tau coj mus rau hauv tus account Ta thauj hauv cheeb tsam tshem tawm cov hlau kom nkag siab txog cov khoom seem hauv tag nrho. alloy tshem tawm txheej, uas yog raws li cov ntshiab tooj liab thiab Cu70Ag30 yaj.Rau Cu70Ag30 yaj (kab liab hauv daim duab 5c), ρ(d) muaj qhov tsawg kawg nkaus ntawm ib nrab ntawm cov txheej txheem delegated.Qhov no yam tsawg kawg nkaus yog vim lub fact tias tag nrho cov nyiaj ntawm Ta muaj nyob rau hauv lub nyuaj binder nyob ze ntawm ntug ntawm lub delegated txheej yog ntau dua nyob rau hauv lub hauv paus alloy.Ntawd yog, rau d ≈ 230 μm \({S}_{s}(d){c}_{Ta}^{s}(d)\, > \,{S}_{t}{c} _ { Ta}^{0}\), lossis sib npaug tag nrho, qhov ntsuas ρ(d) = Ss(d)/St ≈ 0.35 yog qhov loj dua li qhov sib npaug kwv yees.(1) No leakage\({c}_{Ta}^{0}/{c}_{Ta}^{s}(d)\approx. 0.2\).Qhov no txhais tau hais tias ib feem ntawm kev khiav tawm Ta yog thauj los ntawm kev sib cais pem hauv ntej mus rau thaj tsam thaj chaw deb ntawm lub hauv ntej no, diffusing hauv cov kua thiab raws cov khoom-kua interface, qhov twg nws yog redeposited.
Qhov kev kho dua tshiab no muaj qhov cuam tshuam ntawm Ta to enrich Ta hard binders, thiab qhov nyuaj feem faib tuaj yeem piav qhia tau zoo raws li qhov sib npaug ntawm Ta to thiab redeposition.Rau lub Cu70Ag30 yaj, Ag concentration nyob rau hauv cov kua nce nrog nce d (xim av dotted kab hauv daim duab 5b) kom txo Ta to los ntawm kev txo Ta solubility, uas ua rau ib tug nce nyob rau hauv ρ(d) nrog nce d tom qab mus txog qhov tsawg kawg nkaus .Qhov no tuav cov khoom loj txaus los tiv thaiv kev tawg vim yog kev sib cais ntawm daim ntawv cog lus nyuaj, uas piav qhia tias vim li cas cov txheej txheem delegated hauv Cu70Ag30 melts khaws cov qauv kev ntseeg siab tom qab etching.Nyob rau hauv sib piv, rau cov ntshiab tooj liab melts, to thiab redeposition yuav luag tag nrho ib leeg tawm, uas ua rau ib tug qeeb txo nyob rau hauv cov khib nyiab hauv qab lub fragmentation pib rau feem ntau ntawm cov delegated txheej, tawm tsuas yog ib tug nyias txheej uas khaws cov structural kev ncaj ncees nyob ze ntawm tus ciam teb ntawm lub fragmentation. delegated txheej.(Fig. 4b, Table 1).
Txog tam sim no, peb cov kev tshuaj ntsuam xyuas tau tsom mus rau kev piav qhia qhov muaj zog ntawm cov xau ntawm cov ntsiab lus tsis zoo hauv qhov nruab nrab dislocating ntawm cov khoom feem thiab cov topology ntawm delegated lug.Cia peb tam sim no tig mus rau qhov tshwm sim ntawm qhov to ntawm qhov coarsening ntawm cov qauv bicontinuum nyob rau hauv lub delegated txheej, uas feem ntau tshwm sim thaum lub sij hawm LMD vim yog kub ua hauj lwm kub.Qhov no txawv ntawm ECD qhov twg coarsening zoo li tsis muaj nyob rau hauv lub sij hawm tshem tawm ntawm cov hlau, tab sis tuaj yeem tshwm sim los ntawm annealing ntawm qhov kub siab dua tom qab tshem tawm cov hlau.Txog tam sim no, coarsening thaum lub sij hawm LMD tau ua qauv raws li qhov kev xav tias nws tshwm sim vim qhov sib txawv ntawm cov ntsiab lus tsis raug raws li cov khoom siv-kua sib cuam tshuam, zoo ib yam li cov txheej txheem diffusion-mediated coarsening ntawm annealed nanoporous ECD cov qauv.Yog li, daim ntawv cog lus me me tau ua qauv siv cov qauv kev ntsuas kev cai lij choj capillary o.
qhov twg tc yog lub sij hawm coarsening, txhais raws li lub sij hawm dhau mus tom qab qhov kev tso cai ntawm delamination pem hauv ntej ntawm qhov tob xi nyob rau hauv lub delamination txheej (qhov twg λ muaj tus nqi pib ntawm λ00) mus txog rau thaum kawg ntawm qhov kev sim delamination, thiab qhov ntsuas qhov ntsuas n = 4 diffuse qhov chaw.Eq yuav tsum tau siv nrog ceev faj.(3) Txhais qhov ntsuas ntawm λ thiab qhov deb d rau qhov kawg qauv yam tsis muaj impurities thaum kawg ntawm qhov kev sim.Qhov no yog vim lub fact tias lub cheeb tsam nyob ze ntawm lub ntug ntawm delegated txheej yuav siv sij hawm ntev dua kom loj dua lub cheeb tsam nyob ze rau pem hauv ntej.Qhov no tuaj yeem ua tiav nrog kev sib npaug ntxiv.(3) Kev sib txuas lus nrog tc thiab d.Qhov kev sib raug zoo no tuaj yeem yooj yim tau los ntawm kev kwv yees qhov tob ntawm kev tshem tawm cov hlau ua haujlwm ntawm lub sijhawm, \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\), uas muab tc(d) = te − tf(d), qhov twg te yog lub sijhawm ntawm tag nrho cov kev sim, \({t}_{f}(d)={(\sqrt{4p{D}_{l} {t}_{ e } }-d)}^{2}/(4p{D}_{l})\) yog lub sijhawm rau delamination pem hauv ntej mus txog qhov tob sib npaug rau qhov kawg delamination qhov tob rho tawm d.Txuas qhov kev qhia no rau tc(d) rau hauv kab zauv.(3) Kwv yees λ(d) (saib ntxiv 5).
Txhawm rau ntsuas qhov kev twv ua ntej no, peb tau ntsuas qhov dav thiab qhov nrug ntawm cov pob khoom ntawm tag nrho cov hla ntu ntawm cov txheej txheem delegated pom hauv Daim duab ntxiv 9 rau cov ntshiab Cu thiab Cu70Ag30 melts.Los ntawm kab scans perpendicular mus rau delamination kev taw qhia ntawm qhov sib txawv d los ntawm delamination pem hauv ntej, peb tau qhov nruab nrab dav λw(d) ntawm Ta-nplua nuj bundles thiab qhov nruab nrab nrug λs(d) ntawm bundles.Cov kev ntsuas no tau qhia hauv daim duab.5d thiab muab piv nrog cov kev kwv yees ntawm qhov sib npaug.(3) hauv Supplementary Fig. 10 rau cov nqi sib txawv ntawm n.Qhov kev sib piv qhia tau hais tias qhov diffusion qhov taw qhia ntawm n = 4 muab kev kwv yees tsis zoo.Qhov kev twv ua ntej no tsis tau zoo dua los ntawm kev xaiv n = 3 rau bulk diffusion-mediated capillary coarsening, uas ib tus neeg yuav tsis xav tias yuav muab qhov haum zoo dua vim Ta to rau hauv cov kua.
Qhov sib txawv ntawm qhov sib txawv ntawm qhov kev xav thiab kev sim tsis yog qhov xav tsis thoob, txij li Eq.(3) piav qhia txog capillary coarsening ntawm qhov ntim tsis tu ncua ρ, thaum ntawm LMD cov khoom seem ρ tsis tas li.ρ hloov spatially nyob rau hauv lub tshem tawm txheej thaum kawg ntawm lub alloy tshem tawm, raws li qhia nyob rau hauv daim duab.5c ua.ρ kuj hloov nrog lub sij hawm thaum lub sij hawm tshem tawm impurities ntawm ib tug tsau tshem tawm qhov tob, los ntawm tus nqi ntawm lub tshem tawm pem hauv ntej (uas yog kwv yees li nyob rau hauv lub sij hawm thiab yog li ywj siab ntawm tf thiab d) mus rau lub ntsuas tus nqi ntawm ρ(d) qhia nyob rau hauv daim duab. 5c sib raug rau lub sijhawm kawg.Los ntawm fig.3d, nws tuaj yeem kwv yees tias qhov kev puas tsuaj rau pem hauv ntej yog kwv yees li 0.4 thiab 0.35 rau AgCu thiab ntshiab Cu melts, feem, uas nyob rau hauv txhua rooj plaub yog siab tshaj tus nqi kawg ntawm ρ ntawm lub sij hawm te.Nws yog ib qho tseem ceeb uas yuav tsum nco ntsoov tias qhov txo qis hauv ρ nrog lub sij hawm ntawm qhov d yog qhov tshwm sim ncaj qha ntawm qhov muaj cov concentration gradient ntawm cov miscible (Ti) hauv cov kua.Txij li thaum cov concentration ntawm Ti hauv cov kua txo qis nrog nce d, qhov sib npaug ntawm Ti hauv cov khib nyiab kuj yog qhov txo qis ntawm d, uas ua rau kev tawg ntawm Ti los ntawm cov khoom binders thiab txo qis hauv cov khoom feem ntau dhau sijhawm.Lub sijhawm hloov pauv hauv ρ kuj cuam tshuam los ntawm kev xau thiab kev hloov pauv ntawm Ta.Yog li, vim muaj qhov cuam tshuam ntxiv ntawm kev sib cais thiab kev rov ua dua tshiab, peb cia siab tias coarsening thaum lub sij hawm LMD yuav, raws li txoj cai, tshwm sim ntawm qhov tsis tas mus li qhov ntim feem, uas yuav ua rau cov txheej txheem evolution ntxiv rau capillary coarsening, tab sis kuj yog vim diffusion hauv. kua thiab tsis tsuas yog nyob rau hauv ciam teb solid-kua.
Qhov tseeb sib npaug.(3) Bond wide and spacing measurements for 3 ≤ n ≤ 4 is not quantified (Supplementary Fig. 10), tawm tswv yim tias dissolution thiab redeposition tsis yog vim kev cuam tshuam cuam tshuam ua lub luag haujlwm tseem ceeb hauv kev sim tam sim no.Rau capillary coarsening, λw thiab λs yuav tsum muaj tib qhov kev vam khom rau d, thaum daim duab 5d qhia tias λs nce nrog d sai dua λw rau cov ntshiab Cu thiab Cu70Ag30 melts.Thaum lub coarsening txoj kev xav uas coj mus rau hauv tus account dissolution thiab redeposition yuav tsum tau txiav txim siab los piav qhia cov kev ntsuas no quantitatively, qhov sib txawv no yuav tsum qualitatively, txij li thaum tag nrho dissolution ntawm me me daim ntawv cog lus yuav ua rau ib tug nce nyob rau hauv qhov kev ncua deb ntawm daim ntawv cog lus.Tsis tas li ntawd, λs ntawm Cu70Ag30 yaj mus txog nws qhov siab tshaj plaws ntawm cov txheej txheem tsis muaj hlau, tab sis qhov tseeb tias λs ntawm cov ntshiab tooj liab yaj txuas ntxiv mus ntxiv monotonically tuaj yeem piav qhia los ntawm kev nce hauv Ag concentration hauv cov kua, qhov twg. d yog siv los piav txog ρ(d) hauv daim duab 5c tus cwj pwm uas tsis yog-monotonic.Ua kom cov Ag concentration nrog nce d suppresses Ta to thiab binder dissolution, uas ua rau txo qis hauv λs tom qab ncav cuag tus nqi siab tshaj.
Thaum kawg, nco ntsoov tias cov kev tshawb fawb hauv computer ntawm capillary coarsening ntawm qhov seem ntim tsis tu ncua qhia tau tias thaum lub ntim feem poob qis dua qhov pib ntawm kwv yees li 0.329.30, cov qauv tawg thaum lub sij hawm coarsening.Hauv kev xyaum, qhov chaw pib no yuav qis dua me ntsis vim tias kev sib cais thiab kev txo qis ntawm cov genus tshwm sim ntawm lub sijhawm ntsuas piv rau lossis ntau dua li lub sijhawm tshem tawm tag nrho cov alloy hauv qhov kev sim no.Qhov tseeb hais tias cov qauv delegated hauv Cu70Ag30 melts khaws lawv cov qauv kev ncaj ncees txawm tias ρ(d) yog me ntsis qis dua 0.3 hauv qhov nruab nrab ntawm d qhia tias kev tawg, yog tias muaj, tshwm sim tsuas yog qee qhov.Qhov ntim feem ntawm qhov pib rau fragmentation kuj yog nyob ntawm kev sib cais thiab rov ua dua.
Txoj kev tshawb no kos ob lub ntsiab lus xaus.Ua ntej, thiab ntau qhov ua tau zoo, lub topology ntawm cov qauv tsim los ntawm LMD tuaj yeem tswj tau los ntawm kev xaiv cov yaj.Los ntawm kev xaiv lub yaj los txo cov solubility ntawm lub immiscible lub caij A ntawm AXB1-X puag alloy nyob rau hauv lub yaj, txawm tias txwv, ib tug heev delegated qauv yuav tsim tau uas khaws nws cohesiveness txawm nyob rau hauv tsawg concentrations ntawm lub hauv pem teb caij X thiab structural kev ncaj ncees. .Nws tau paub yav dhau los tias qhov no ua tau rau ECD25, tab sis tsis yog rau LMD.Qhov thib ob xaus, uas yog qhov tseem ceeb tshaj, yog vim li cas nyob rau hauv LMD cov qauv kev ncaj ncees yuav tau khaws cia los ntawm kev hloov kho cov delegating nruab nrab, uas yog nthuav nyob rau hauv nws tus kheej thiab yuav piav qhia txog cov kev soj ntsuam ntawm peb TaTi alloy nyob rau hauv cov ntshiab Cu thiab CuAg melts nyob rau hauv , tab sis kuj nyob rau hauv nws tus kheej. Feem ntau los piav qhia qhov tseem ceeb, yav dhau los kwv yees qhov sib txawv ntawm ECD thiab LMD.
Nyob rau hauv ECD, lub cohesiveness ntawm tus qauv yog tswj los ntawm kev ua kom lub impurity tshem tawm tus nqi ntawm ib tug tsawg theem X, uas tseem nyob tas li lub sij hawm rau ib tug ruaj khov tsav, me me kom txaus miscible ntsiab B nyob rau hauv cov khoom binder thaum lub sij hawm impurity tshem tawm los tswj. khoom ntim.tus ρ feem yog loj txaus los tiv thaiv fragmentation25.Nyob rau hauv LMD, tus nqi tshem tawm cov hlau \(d{x}_{i}(t)/dt=\sqrt{p{D}_{l}/t}\) txo nrog lub sij hawm vim diffusion txwv kinetics.Yog li, tsis hais hom yaj muaj pes tsawg leeg uas cuam tshuam rau Peclet tus lej p nkaus xwb, tus nqi delamination sai sai mus txog tus nqi me me kom khaws tau tus nqi txaus ntawm B hauv cov khoom sib khi, uas yog ncaj qha cuam tshuam rau qhov tseeb tias ρ ntawm delamination. pem hauv ntej tseem nyob ib ncig ntawm lub sijhawm.Qhov tseeb thiab tshaj qhov pib fragmentation.Raws li pom los ntawm theem kev simulation, lub tev tus nqi kuj nce mus txog qhov nqi me me txaus kom tsis txhob muaj kev loj hlob ntawm eutectic daim ntawv cog lus, yog li yooj yim rau kev tsim cov txheej txheem topologically bonded vim lub lateral rocking motion ntawm lamellae.Yog li, qhov tseem ceeb ntawm qhov sib txawv ntawm ECD thiab LMD yog nyob rau hauv kev hloov pauv ntawm delamination pem hauv ntej los ntawm cov qauv sab hauv ntawm txheej tom qab sib cais thiab ρ, es tsis yog tus nqi delamination.
Hauv ECD, ρ thiab kev sib txuas tseem nyob tas li thoob plaws hauv cov chaw taws teeb.Hauv LMD, qhov sib txawv, ob qho tib si sib txawv hauv ib txheej, uas tau qhia meej meej hauv qhov kev tshawb fawb no, uas qhia txog atomic concentration thiab kev faib tawm ntawm ρ thoob plaws hauv qhov tob ntawm cov qauv tsim los ntawm LMD.Muaj ob qho laj thawj rau qhov kev hloov pauv no.Ua ntej, txawm nyob rau ntawm xoom solubility txwv A, qhov concentration gradient B nyob rau hauv cov kua, uas yog tsis nyob rau hauv lub DZE, induces ib tug concentration gradient A nyob rau hauv cov khoom binder, uas yog nyob rau hauv chemical equilibrium nrog cov kua.Lub gradient A, nyob rau hauv lem, induces ib tug gradient ρ nyob rau hauv lub txheej yam tsis muaj impurities.Qhov thib ob, qhov to ntawm A mus rau hauv cov kua vim tsis yog xoom solubility ntxiv modulates spatial variation ntawm ρ nyob rau hauv cov txheej no, nrog rau txo solubility pab kom ρ siab dua thiab ntau spatial uniform kom muaj kev sib txuas.
Thaum kawg, qhov kev hloov pauv ntawm daim ntawv cog lus loj thiab kev sib txuas hauv cov txheej txheem delegated thaum lub sij hawm LMD yog qhov nyuaj dua li qhov diffusion-txheej txheem capillary coarsening ntawm qhov ntim tsis tu ncua, raws li yav dhau los xav los ntawm kev sib piv nrog cov coarsening ntawm annealed nanoporous ECD qauv.Raws li qhia ntawm no, coarsening hauv LMD tshwm sim nyob rau hauv ib qho kev sib txawv ntawm cov khoom seem thiab feem ntau cuam tshuam los ntawm kev hloov pauv ntawm A thiab B hauv cov kua hauv lub xeev los ntawm delamination pem hauv ntej mus rau ntug ntawm cov txheej txheem disjointed.Cov kev cai scaling rau capillary coarsening txwv los ntawm qhov chaw los yog bulk diffusion tsis tuaj yeem ntsuas qhov kev hloov pauv ntawm qhov dav thiab qhov deb ntawm cov pob hauv ib txheej txheej, piv txwv tias A thiab B thauj cuam tshuam nrog cov kua dej concentration gradients ua si sib npaug lossis zoo ib yam.Tseem ceeb tshaj qhov txo qhov chaw ntawm lub interface.Txoj kev loj hlob ntawm txoj kev xav uas coj mus rau hauv tus account ntau yam kev cuam tshuam no yog qhov tseem ceeb rau yav tom ntej.
Titanium-tantalum binary alloys tau yuav los ntawm Arcast, Inc (Oxford, Maine) siv 45 kW Ambrell Ekoheat ES induction fais fab mov thiab dej-txias tooj liab crucible.Tom qab ob peb lub tshav kub, txhua cov hlau yog annealed rau 8 teev ntawm qhov kub ntawm 200 ° C. ntawm melting point kom ua tiav homogenization thiab grain loj hlob.Cov qauv txiav los ntawm tus tswv ingot no tau pom-welded rau Ta xov hlau thiab raug tshem tawm los ntawm caj npab neeg hlau.Hlau da dej tau npaj los ntawm cua sov sib tov ntawm 40 g Cu (McMaster Carr, 99.99%) nrog Ag (Kurt J. Lesker, 99.95%) los yog Ti particles ntawm lub hwj chim siab siv 4 kW Ameritherm Easyheat induction cua sov kom txog thaum tiav dissolution.da dej.tag nrho rhuab yaj.Txo lub hwj chim thiab cia da dej do thiab sib npaug rau ib nrab ib teev ntawm qhov ntsuas kub ntawm 1240 ° C.Tom qab ntawd tus neeg hlau caj npab yog qis dua, cov qauv yog raus hauv da dej rau lub sijhawm ua ntej thiab tshem tawm kom txias.Tag nrho cov cua sov ntawm cov hlau nplaum thiab LMD tau ua nyob rau hauv ib qho chaw ntawm siab purity argon (99.999%).Tom qab tshem tawm cov hlau, cov ntu ntu ntawm cov qauv raug polished thiab tshuaj xyuas siv cov khoom siv kho qhov muag thiab tshuaj ntsuam xyuas electron microscopy (SEM, JEOL JSM-6700F).Elemental tsom xam tau ua los ntawm lub zog dispersive X-ray spectroscopy (EDS) hauv SEM.Qhov peb-dimensional microstructure ntawm cov qauv delegated tau pom los ntawm kev ua kom tiav cov txheej txheem tooj liab-nplua nuj nyob rau hauv 35% nitric acid tov (qib tsom xam, Fluka).
Qhov kev simulation tau ua tiav siv cov qauv tsim yav dhau los ntawm thaj tsam ntawm theem decoupling ntawm ternary alloy15.Tus qauv hais txog cov evolution ntawm theem teb ϕ, uas txawv ntawm cov khoom thiab cov theem ua kua, mus rau lub concentration field ci ntawm alloying ntsiab.Tag nrho lub zog dawb ntawm qhov system yog qhia raws li
qhov twg f(φ) yog ob chav thaiv muaj peev xwm nrog minima ntawm φ = 1 thiab φ = 0 sib raug rau cov khib nyiab thiab kua, feem, thiab fc (φ, c1, c2, c3) yog cov tshuaj lom neeg ua rau ntim kev ywj pheej piav txog lub zog ntom ntom. ntawm thermodynamic zog alloy.Txhawm rau simulate lub remelting ntawm ntshiab Cu los yog CuTi melts rau hauv TaTi alloys, peb siv tib daim ntawv fc (φ, c1, c2, c3) thiab tsis raws li nyob rau hauv kev siv.15. Yuav kom tshem tawm TaTi alloys nrog CuAg melts, peb tau simplified lub quaternary system (CuAg) TaTi mus rau ib tug zoo ternary system nrog txawv tsis nyob rau hauv lub Ag concentration, raws li tau piav nyob rau hauv Supplementary Note 2. Cov evolution equations rau theem teb thiab cov concentration field tau txais nyob rau hauv variant daim ntawv nyob rau hauv daim ntawv
Where \({M}_{ij}={M}_{l}(1-\phi){c}_{i}\left({\delta}_{ij}-{c}_{j} \right)\) yog atomic mobility matrix, thiab Lϕ tswj cov kinetics ntawm atomic txuas ntawm cov khoom-kua interface.
Kev sim cov ntaub ntawv txhawb nqa cov txiaj ntsig ntawm txoj kev tshawb no tuaj yeem pom hauv cov ntaub ntawv ntxiv cov ntaub ntawv.Simulation tsis muaj nyob rau hauv cov ntaub ntawv ntxiv.Tag nrho cov ntaub ntawv tseem muaj los ntawm cov kws sau ntawv raws li kev thov.
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