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Eminyakeni embalwa edlule, kube nokuthuthuka okusheshayo kwezingxube zensimbi eziwuketshezi zokwenziwa kwezakhiwo ezinosayizi we-nano-/meso-obukhulu neziyinhlanganisela ezinokusebenzelana okukhulu kakhulu kwezinto ezihlukahlukene.Nokho, le ndlela okwamanje inemikhawulo emibili ebalulekile.Okokuqala, ikhiqiza izakhiwo eziqhubekayo ezine-topology ene-oda eliphezulu yohlu olulinganiselwe lokuqanjwa kwe-alloy.Okwesibili, isakhiwo sinosayizi omkhulu we-binder ngenxa yokwandiswa okuphawulekayo ngesikhathi sokuhlukaniswa kwezinga lokushisa eliphezulu.Lapha, sibonisa ngekhompyutha nangokuhlola ukuthi le mikhawulo inganqotshwa ngokwengeza into ekuncibilikeni kwensimbi ethuthukisa i-topology ye-oda eliphezulu ngokukhawulela ukuvuza kwezinto ezingahlangani ngesikhathi sokuhlangana.Okulandelayo, sichaza lokhu okutholakele ngokubonisa ukuthi ukudluliswa kokusabalalisa kwenqwaba kwezinto ezingahlangani ekuncibilikeni koketshezi kuthonya kakhulu ukuvela kwengxenye eqinile kanye ne-topology yezakhiwo ngesikhathi sokuvuleka.Imiphumela yembula umehluko obalulekile phakathi kwezinsimbi eziwuketshezi kanye nokususwa kokungcola kwe-electrochemical, futhi isungula indlela entsha yokuthola izakhiwo ezinsimbi eziwuketshezi ezinobukhulu obuthile kanye ne-topology.
Ukuthunyelwa kwezithunywa kuguqukele ekubeni ubuchwepheshe obunamandla nobuguquguqukayo bokwenziwa kwezimbotshana ezivulekile ze-nano-/meso-meso kanye nezakhiwo eziyinhlanganisela ezinobuso obuphezulu kakhulu obuphezulu bezinto ezihlukahlukene zokusebenza nezakhiwo ezifana nama-catalysts1,2, fuel cell3,4, electrolytic capacitors5, 6, izinto ezimelana nokulimala kwemisebe 7, izinto zebhethri ezinomthamo omkhulu ezinokuzinza kwemishini okukhuphukile 8, 9 noma izinto eziyinhlanganisela ezinezakhiwo ezinhle kakhulu zemishini. ingxubevange” endaweni engaphandle, okuholela ekuhlelweni kabusha kwezinto ezingancibilikisiwe eziyingxubevange ezine-topology engasho lutho, ehlukile ku-topology yengxubevange yokuqala., Ukwakheka kwezithako.Nakuba ukuthunyelwa okujwayelekile kwe-electrochemical (ECD) kusetshenziswa ama-electrolyte njengoba imvelo kuyikhona okufundwe kakhulu kuze kube manje, le ndlela ikhawulela izinhlelo zokudlulisela amandla (ezifana ne-Ag-Au noma i-Ni-Pt) kulabo abaqukethe izakhi ezinhle kakhulu (Au, Pt) futhi umehluko omkhulu ngokwanele emandleni okunciphisa ukunikeza i-porosity.Isinyathelo esibalulekile ekunqobeni lo mkhawulo kube ukutholwa kabusha kwakamuva kwe-liquid metal alloying method13,14 (LMD), esebenzisa ingxubevange yezinsimbi eziwuketshezi (isb., Cu, Ni, Bi, Mg, njll.) nezinye izakhi endaweni ezungezile. .(isb. TaTi, NbTi, FeCrNi, SiMg, njll.)6,8,10,11,14,15,16,17,18,19.I-LMD kanye nokwahluka kwayo kwe-hard metal alloy remove (SMD) kusebenza emazingeni okushisa aphansi lapho isisekelo sensimbi siqinile20,21 okuholela ekuhlanganiseni kwezigaba ezimbili noma ngaphezulu ezingene phakathi ngemva kokushumeka kwamakhemikhali kwesigaba esisodwa.Lezi zigaba zingashintsha zibe izimbotshana ezivulekile.izakhiwo.Izindlela zokudlulisela ziye zathuthukiswa nakakhulu ngokwethulwa kwakamuva kwe-vapor phase delegation (VPD), esebenzisa umehluko wokucindezelwa komhwamuko wezinto eziqinile ukuze zakhe izakhiwo ezivulekile ze-nanoporous ngokusebenzisa ukuhwamuka okukhethiwe kwesici esisodwa22,23.
Ezingeni lekhwalithi, zonke lezi zindlela zokususa ukungcola zabelana ngezici ezimbili ezibalulekile ezivamile zenqubo yokususwa kokungcola okuzihlelele.Okokuqala, lokhu ukuhlakazwa okukhethekile kwezakhi ze-alloying ezishiwo ngenhla (ezifana no-B ku-alloy elula kakhulu i-AXB1-X) endaweni yangaphandle.Okwesibili, okokuqala okuphawulwe ocwaningweni oluhamba phambili lokuhlola kanye nethiyori ku-ECD24, ukusakazeka kwesici esingancibilikisiwe A eduze kwesixhumi esibonakalayo phakathi kwengxubevange nemvelo ngesikhathi sokususwa kokungcola.I-Diffusion iyakwazi ukwakha izifunda ezicebile nge-athomu ngenqubo efana nokubola kwe-spinodal kuma-alloys amaningi, nakuba kunqunyelwe isixhumi esibonakalayo.Naphezu kwalokhu kufana, izindlela ezihlukene zokususa ingxubevange zingase zikhiqize ama-morphologies ahlukene ngezizathu ezingacacile18.Nakuba i-ECD ingakwazi ukukhiqiza izakhiwo zokuhleleka okuphezulu okuhlobene ne-topologically zezingxenye ze-athomu (X) zezinto ezingancibilikisiwe (ezifana ne-Au in AgAu) eziphansi zibe ngu-5%25, ucwaningo lwekhompiyutha nokuhlola lwe-LMD lubonisa ukuthi le ndlela ebonakala ifana ikhiqiza kuphela izakhiwo ezihlobene ne-topologically. .Isibonelo, ngo-X omkhulu kakhulu, ukwakheka okuhambisanayo okuhambisanayo kucishe kube ngu-20% esimweni sengxubevange ye-TaTi ehlanganiswe yi-Cu iyancibilika (bona u-Fig. 2 ku-ref. 18 ukuze uthole ukuqhathanisa okuhlangene ne-ECD ehlukahlukene kanye nefomu le-LMD X. ).Lokhu kwehluka kuchazwa ngokwethiyori indlela yokukhula ehlanganiswe nokusabalalisa ehlukile ekuboleni kwe-spinodal ehlangene ebusweni futhi efana kakhulu nokukhula okuhlanganisiwe kwe-eutectic26.Endaweni yokususa ukungcola, ukukhula okuhlanganiswe nokusabalalisa kuvumela ama-A-rich rich filaments (noma ama-flakes ku-2D) kanye namashaneli aketshezi acebile B ukuthi akhule ngokubambisana ngokusakazwa ngesikhathi sokususwa kokungcola15.Ukukhula ngakubili kuholela esakhiweni esingabophekile esihambisana ne-topologically engxenyeni emaphakathi ka-X futhi icindezelwe engxenyeni engezansi ka-X, lapho kungakheka khona iziqhingi ezingaboshiwe ezicebile ngesigaba A.Ku-X enkulu, ukukhula okuhlanganisiwe kuba nokungazinzi, kuvumela ukwakheka kwezakhiwo ze-3D eziboshwe ngokuphelele ezigcina ubuqotho besakhiwo ngisho nangemva kokubhala kwesigaba esisodwa.Kuyathakazelisa ukuthi ukwakheka kwe-orientation okukhiqizwe yi-LMD17 noma i-SMD20 (Fe80Cr20) XNi1-X alloys iye yabonwa ngokuhlolwa kwe-X kufika ku-0.5, okuphakamisa ukuthi ukukhula okuhlanganiswe nokusabalalisa kuyindlela etholakala yonke indawo ye-LMD ne-SMD kunokuba i-ECD evame ukuphumela ngaphandle ayikwenzi. ube nesakhiwo sokuqondanisa esincanyelwayo.
Ukuze sicacise isizathu salo mehluko phakathi kwe-ECD ne-NMD morphology, senze ukulingisa kwenkundla yesigaba kanye nezifundo zokuhlola ze-NMD ye-TaXTi1-X alloys, lapho i-kinetics yokuhlakazeka yashintshwa ngokungeza izakhi ezincibilikisiwe kuthusi oluwuketshezi.Siphethe ngokuthi nakuba kokubili i-ECD ne-LMD kulawulwa ukuhlakazeka okukhethiwe kanye nokusabalalisa kobuso, lezi zinqubo ezimbili zibuye zibe nomehluko obalulekile ongaholela ekuhlukeni kwe-morphological18.Okokuqala, i-peel kinetics ku-ECD ilawulwa yi-interface ene-peel velocity yangaphambili ye-V12 engaguquki njengomsebenzi we-voltage esetshenzisiwe.Lokhu kuyiqiniso ngisho nalapho ingxenye encane yezinhlayiya eziphikisayo (isb. I-Pt ku-Ag-Au) yengezwa ku-alloy engumzali, ebambezela uketshezi oluphakathi kobuso, ihlanza futhi izinze izinto ezingaxutshiwe, kodwa ngaphandle kwalokho igcina i-morphology efanayo 27.Izakhiwo ezihlanganiswe nge-topologically zitholakala kuphela ku-X ephansi ku-V ephansi, futhi ukugcinwa kwezinto ezixubene 25 kukhulu ukuze kugcinwe ingxenyenamba yevolumu eqinile enkulu ngokwanele ukuvimbela ukuhlukana kwesakhiwo.Lokhu kusikisela ukuthi izinga lokuqedwa ngokuphathelene nokuhlukana phakathi kobuso lingase libe nendima ebalulekile ekukhethweni kwe-morphological.Ngokuphambene, i-kinetics yokususa i-alloy ku-LMD ilawulwa ngokusakazwa15,16 futhi izinga liyancipha ngokushesha uma kuqhathaniswa nesikhathi \(V \sim \sqrt{{D}_{l}/t}\), lapho i-Dl iyingxenye ye-miscibility. nge-coefficient yokusabalalisa uketshezi..
Okwesibili, ngesikhathi se-ECD, ukunyibilika kwezinto ezingenakulinganiswa ku-electrolyte kuphansi kakhulu, ngakho-ke zingasabalalisa kuphela ku-interface yealloy-electrolyte.Ngokuphambene, ku-LMD, izakhi "ezingabonakali" (A) ze-AXB1-X zama-alloys angaphambili ngokuvamile zinokuncibilika okuncane, nakuba kulinganiselwe.Lokhu kuncibilika okuncane kungathathwa ekuhlaziyweni komdwebo wesigaba se-ternary wesistimu ye-CuTaTi ternary ekhonjiswe Emfanekisweni Owengeziwe 1. Ukuncibilika kungalinganiswa ngokuhlela umugqa we-liquidius ngokumelene nokugxila kokulingana kuka-Ta no-Ti ohlangothini oluwuketshezi lwesixhumi esibonakalayo (\( {c}_{ {{{{{\rm{Ta)))))))}}}} ^{l}\ ) kanye \({c}_{{{{({\rm{Ti}}} }}}} }^ {l}\), ngokulandelana, ezingeni lokushisa lokuthumela (I-Fig. 1b) isixhumi esibonakalayo esiqinile-uketshezi Ukulingana kwe-thermodynamic kwasendaweni kuyagcinwa phakathi ne-alloying, }}}}}}^{l}\) cishe engaguquki futhi inani layo lihlobene no-X. Umfanekiso Owengeziwe 1b ubonisa ukuthi \({c}_{{{{{{{\rm{Ta}}}}}}} ))}^{l}\) iwela kububanzi 10 -3 − 10 ^{l}\) zilingana no-15.16.Lokhu "kuvuza" kwezakhi ezingenakulinganiswa ku-alloy kungathinta kokubili ukwakheka kwesakhiwo sobuso obuhlangene ngaphambili kwe-delamination, ngokushintshana kwakho, okungaba nomthelela ekuhlakazweni nasekuqineni kwesakhiwo ngenxa yokusabalalisa ivolumu.
Ukuze sihlaziye ngokuhlukana umnikelo (i) wezinga elincishisiwe lokukhishwa kwengxubevange engu-V kanye (ii) nenani elincishisiwe lokungena kwezinto ezingahlangani ekuncibilikeni, siqhubeke ngezinyathelo ezimbili.Okokuqala, sibonga \(V \sim \sqrt{{D}_{l}/t}\), ngokutadisha inguquko ye-morphological yesakhiwo se-bundle front, kwakungenzeka ukutadisha umphumela wokunciphisa V ngokwanele.isikhathi esikhulu.Ngakho-ke, siphenye lo mphumela ngokusebenzisa izifaniso zenkundla yesigaba esikhathini eside kunezifundo zangaphambilini, eziveze ukuba khona kwezakhiwo zokuqondanisa ze-topologically ezingahlanganisiwe ezakhiwe ukukhula okuhlanganisiwe kokusabalalisa kwe-X15 emaphakathi.Okwesibili, ukuze kuphenywe umthelela wezinto ezingaqondakali ekwehliseni izinga lokuvuza, sengeze i-Ti ne-Ag ekuncibilikeni kwethusi ukuze sikhulise futhi sinciphise izinga lokuvuza, ngokulandelana, futhi safunda i-morphology ewumphumela, i-kinetics yokuhlukanisa, kanye nokusatshalaliswa kokugxilisa ingqondo. ncibilika.Okuthunyelwe kwe-Cu kuncibilika ngezibalo nokuhlola ngaphakathi kwesakhiwo sengxubevange.Sengeze izengezo ze-Ti ezisuka ku-10% ziye ku-30% kwabezindaba ukuze sisuse i-Cu melt.Ukwengezwa kwe-Ti kukhulisa ukugxila kuka-Ti emaphethelweni esendlalelo esiphathisiwe, okunciphisa i-gradient ye-Ti ngaphakathi kwalesi sendlalelo futhi kunciphisa izinga lokuhlakazeka.Iphinde inyuse izinga lokuvuza kwe-Ta ngokunyusa \({c}_{{{({\rm{Ti}}}}}}}}^{l}\), ngakho \({c}_{{{{{ {\rm{Ta}}}}}}}^{l}\) (Inani lesiliva esilingezayo liyahlukahluka kusuka ku-10% kuya ku-30%. ukuncibilika kwezakhi ze-alloying ekuncibilikeni, senze imodeli yesistimu ye-quaternary ye-CuAgTaTi njengesistimu ye-ternary esebenzayo (CuAg)TaTi lapho ukuncibilika kwe-Ti ne-Ta kuncike ekugxilweni kwe-Ag ku-CuAg encibilikayo (bona Inothi) 2 kanye Nokwengeza. Amakhiwane 2-4).Ukwengezwa kwe-Ag akukhulisi ukugxila kwe-Ti emaphethelweni esakhiwo esiphathisiwe.Nokho, njengoba ukunyibilika kwe-Ti ku-Ag kungaphansi kwalokho kwe-Cu, lokhu kunciphisa \({c}_{{{{{\rm{Ta}}}}}}}}^{l}\) (I-Supplementary Fig . 1 ) 4b) nezinga lokuvuza Ta.
Imiphumela yokulingisa kwenkundla yesigaba ibonisa ukuthi ukukhula okuhlanganisiwe kuba nokungazinzi esikhathini eside ngokwanele ukuze kuthuthukiswe ukwakheka kwezakhiwo ezihambisana ne-topologically ngaphambili kokubola.Siqinisekisa ngokuhlolwa lesi siphetho ngokubonisa ukuthi ungqimba olungaphansi lwengxubevange ye-Ta15T85, olwakheka eduze nendawo engaphambili ye-delamination esikhathini sakamuva se-delamination, luhlala luboshelwe ngokomthetho ngemva kokusikwa kwesigaba esinothe ngethusi.Imiphumela yethu iphinda iphakamise ukuthi izinga lokuvuza linomthelela omkhulu ekuziphendukeleni kwemvelo ngenxa yokuthuthwa kwenqwaba yezinto ezingahlangani ekuncibilikeni koketshezi.Kuboniswa lapha ukuthi lo mphumela, ongekho ku-ECD, uthinta kakhulu amaphrofayili okugxiliswa kwezakhi ezihlukahlukene kungqimba oluthunyelwe, ingxenyena yesigaba esiqinile, kanye ne-topology yesakhiwo se-LMD.
Kulesi sigaba, siqala ukwethula imiphumela yocwaningo lwethu ngokulingisa inkambu yesigaba yomphumela wokwengeza i-Ti noma i-Ag ku-Cu iyancibilika okuholela ku-morphology ehlukene.Emkhiwaneni.Umfanekiso 1 wethula imiphumela yokumodela okunezinhlangothi ezintathu zenkambu yesigaba se-TaXTi1-X alloys etholwe ku-Cu70Ti30, Cu70Ag30 kanye nokuncibilika kwethusi elimsulwa ngokuqukethwe okuphansi kwe-athomu yezinto ezingaqondakali kusuka ku-5 kuya ku-15%.Imigqa emibili yokuqala ibonisa ukuthi ukungezwa kwakho kokubili i-Ti ne-Ag kukhuthaza ukwakheka kwezakhiwo eziboshwe nge-topologically uma kuqhathaniswa nesakhiwo esingaboshiwe se-Cu ehlanzekile (umugqa wesithathu).Kodwa-ke, ukungezwa kwe-Ti, njengoba bekulindelekile, kukhuphule ukuvuza kwe-Ta, ngaleyo ndlela kuvimbele ukubola kwama-alloy angu-X aphansi (i-Ta5Ti95 ne-Ta10Ti90) futhi kubangele ukuhlakazeka okukhulu kongqimba olumbotshana olukhishiwe phakathi ne-Ta15Ti85 delamination.Ngokuphambene nalokho, ukungezwa kwe-Ag (umugqa wesibili) kunomthelela ekwakhekeni kwesakhiwo esihlobene ne-topologically sazo zonke izingxenye ze-alloy eyisisekelo ngokuhlakazeka okuncane kongqimba oluthunyelwe.Ukwakhiwa kwesakhiwo esiqhubekayo kuboniswa futhi ku-Fig.1b, ebonisa izithombe zesakhiwo esiphathisiwe esinokujula okwandayo kokuhlukana ukusuka kwesokunxele kuye kwesokudla kanye nesithombe sokusebenzelana okuqinile koketshezi ekujuleni okuphezulu (isithombe esikude kwesokudla).
Ukulingiswa kwenkundla yesigaba se-3D (128 × 128 × 128 nm3) okubonisa umthelela omkhulu wokwengeza i-solute ekuncibilikeni koketshezi ku-morphology yokugcina ye-alloy ethunyelwe.Uphawu olungaphezulu lubonisa ukwakheka kwengxubevange engumzali (i-TaXTi1-X) futhi uphawu oluqondile lubonisa ukwakheka kokuncibilika kwe-Cu-based softening medium.Izindawo ezinokugxiliswa kwe-Ta okuphezulu esakhiweni esingenakho ukungcola ziboniswa ngombala onsundu, futhi isixhumi esibonakalayo esinoketshezi oluqinile siboniswa ngoluhlaza okwesibhakabhaka.b Ukulingiswa kwezinhlangothi ezintathu kwenkambu yesigaba sengxubevange ye-Ta15Ti85 engavuliwe ku-Cu70Ag30 melt (190 × 190 × 190 nm3).Ozimele bokuqala abangu-3 babonisa isifunda esiqinile sesakhiwo esithunyelwe ekujuleni okuhlukile kokuthunyelwa, futhi uhlaka lokugcina lubonisa kuphela isixhumi esibonakalayo soketshezi oluqinile ekujuleni okuphezulu.Imuvi ehambisana no-(b) iboniswa ku-Supplementary Movie 1.
Umthelela wokwengezwa kwe-solute wabuye wahlolwa ngokulingiswa kwenkundla yesigaba se-2D, okunikeze ulwazi olwengeziwe ekwakhekeni kwemodi yokuhlangana kobuso ngaphambili kwe-delamination futhi kwavumela ukufinyelela kubude obukhulu nezikali zesikhathi kunezifaniso ze-3D ukuze kulinganise i-delamination kinetics.Emkhiwaneni.Umfanekiso 2 ubonisa izithombe zokulingiswa kokukhishwa kwe-alloy ye-Ta15Ti85 eyandulelayo ngokusebenzisa i-Cu70Ti30 kanye ne-Cu70Ag30 encibilikayo.Kuzo zombili izimo, ukukhula okuhlanganisiwe kokusabalalisa akuzinzile kakhulu.Esikhundleni sokungena ngokuma ku-alloy, amathiphu eziteshi eziwuketshezi ahamba ngesiphithiphithi kwesokunxele nakwesokudla emigwaqweni eyinkimbinkimbi kakhulu phakathi nenqubo yokukhula ezinzile ekhuthaza izakhiwo eziqondile ezikhuthaza ukwakheka kwezakhiwo ezihlobene ne-topologically endaweni ye-3D (Fig. 1).Kodwa-ke, kunomehluko obalulekile phakathi kwezithasiselo ze-Ti ne-Ag.Ukuze kuncibilike i-Cu70Ti30 (Fig. 2a), ukungqubuzana kwamashaneli amabili oketshezi kuholela ekuhlanganisweni kwesixhumi esibonakalayo soketshezi oluqinile, okuholela ekukhishweni kwezibophelelo eziqinile ezithathwe iziteshi ezimbili kusukela esakhiweni futhi, ekugcineni, ekuhlakazweni. .Ngokuphambene, ku-Cu70Ag30 melt (Fig. 2b), ukucebisa kwe-Ta kusixhumi esibonakalayo phakathi kwezigaba eziqinile neziwuketshezi kuvimbela ukuhlangana ngenxa yokuncipha kokuvuza kwe-Ta ekuncibilikeni.Ngenxa yalokho, ukucindezelwa kwebhondi ngaphambili kwe-delamination kuyacindezelwa, ngaleyo ndlela kuthuthukiswe ukwakheka kwezakhiwo ezixhumeneyo.Kuyathakazelisa ukuthi ukunyakaza kwe-oscillatory ye-chaotic yesiteshi se-liquid kudala isakhiwo esinezinhlangothi ezimbili ezinezinga elithile lokuqondanisa lapho i-cutoff icindezelwa (Fig. 2b).Nokho, lokhu kuqondaniswa akuwona umphumela wokukhula okuzinzile kwesibopho.Ku-3D, ukungena okungazinzile kudala ukwakheka kwe-bicontinuous non-coaxial exhunywe (Fig. 1b).
Izifinyezo zokulingiswa kwenkundla yesigaba se-2D se-Cu70Ti30 (a) kanye ne-Cu70Ag30 (b) encibilikayo ku-Ta15Ti85 ingxubevange ebonisa ukukhula okungazinzile okuhlanganiswe nokusabalalisa.Izithombe ezibonisa ukujula okuhlukile kokususwa kokungcola kukalwa ukusuka endaweni yokuqala yesixhumi esibonakalayo esiyisicaba esiqinile/uketshezi.Amasetha abonisa izimiso ezihlukene zokushayisana kwesiteshi esiwuketshezi, okuholela ekuhlanganisweni kwezibophezelo eziqinile kanye nokulondolozwa kokuncibilika kwe-Cu70Ti30 ne-Cu70Ag30, ngokulandelana.Ububanzi besizinda be-Cu70Ti30 bungu-1024 nm, i-Cu70Ag30 ingu-384 nm.Ibhendi enombala ikhombisa ukugxila kuka-Ta, futhi imibala ehlukene ihlukanisa phakathi kwendawo ewuketshezi (okuluhlaza okwesibhakabhaka), ingxubevange (okuluhlaza okwesibhakabhaka okukhanyayo), kanye nesakhiwo esingaxutshiwe (cishe sibebomvu).Ama-movie alokhu kulingisa afakwe ku-Supplemental Movie 2 no-3, agqamisa izindlela eziyinkimbinkimbi ezingena eziteshini eziwuketshezi ngesikhathi sokukhula okuhlanganisiwe kokusabalalisa okungazinzile.
Eminye imiphumela yokulingiswa kwenkundla yesigaba se-2D iboniswa ku-Fig.3.Igrafu yokujula kwe-delamination iqhathaniswa nesikhathi (umthambeka olingana no-V) kufig.I-3a ibonisa ukuthi ukungezwa kwe-Ti noma i-Ag ku-Cu kuncibilika kunciphisa i-kinetics yokuhlukanisa, njengoba kulindelekile.Emkhiwaneni.I-3b ibonisa ukuthi lokhu kuhamba kancane kubangelwa ukwehla kwegradient ye-Ti oketshezini olungaphakathi kwesendlalelo esithunyelwe.Kuphinde kubonise ukuthi ukungezwa kwe-Ti(Ag) kukhulisa (kunciphisa) ukugxila kwe-Ti ohlangothini oluwuketshezi lwesixhumi esibonakalayo (\({c}_{{{{{{{\rm{Ti))))))))) ))) ^{l \) ), okuholela ekuvuzeni kwe-Ta, kukalwa ngengxenye ka-Ta encibilike ekuncibilikeni njengomsebenzi wesikhathi (Fig. 3c), okwandisa (ukuncipha) ngokwengezwa kwe-Ti(Ag ).Umfanekiso we-3d ubonisa ukuthi kuzo zombili izincibilikisi, ingxenye yevolumu yezinto eziqinile ihlala ingaphezulu komkhawulo wokwakhiwa kwezakhiwo ezihlobene ne-bicontinuous topologically28,29,30.Ngenkathi ukungeza i-Ti ekuncibilikeni kukhulisa ukuvuza kwe-Ta, kuphinde kwenyuse nokugcinwa kwe-Ti kusibophezelo esiqinile ngenxa yokulingana kwesigaba, ngaleyo ndlela kukhulisa ingxenyenamba yevolumu ukuze kugcinwe ukuhlangana kwesakhiwo ngaphandle kokungcola.Izibalo zethu ngokuvamile zivumelana nezilinganiso zokuhlola zengxenye yevolumu ye-delamination front.
Ukulingiswa kwenkambu yesigaba sengxubevange ye-Ta15Ti85 kulinganisa imiphumela ehlukene yezengezo ze-Ti ne-Ag ku-Cu melt ku-kinetics yokukhipha ingxubevange elinganiswa ukusuka ekujuleni kokukhishwa kwe-alloy njengomsebenzi wesikhathi (a), iphrofayela yokugxilisa ye-Ti oketshezini Ukujula kokususwa kwengxubevange okungu-400 nm (ukushona okunegethivu kunwebeka kuncibilike ngaphandle kwesakhiwo sengxubevange (ingxubevange ngaphambili kwesokunxele) b Ukuvuza kuqhathaniswa nesikhathi (c) kanye nengxenye eqinile esakhiweni esingaxutshiwe uma kuqhathaniswa nokuncibilika (d) Ukuhlangana kwezakhi ezengeziwe ekuncibilikeni kuhlelwe eduze kwe-abscissa (d) (Ti - umugqa oluhlaza, u-Ag - umugqa onsomi kanye nokuhlola).
Njengoba ijubane langaphambili le-delamination lincipha ngokuhamba kwesikhathi, ukuvela kwe-morphology ngesikhathi se-delamination kukhombisa umphumela wokunciphisa isivinini se-delamination.Ocwaningweni lwensimu yesigaba sangaphambilini, sibone ukukhula okuhambisanayo okufana ne-eutectic okuholela ekwakhiweni okungahlanganisiwe kwe-topologically ngesikhathi sokususwa kwe-alloy precursor ye-Ta15Ti85 ngokuncibilika kwethusi okumsulwa.Kodwa-ke, ukugijima okude komdlalo wokulingisa wenkundla yesigaba esifanayo (bona i-Supplementary Movie 4) lapho isivinini sangaphambili sokubola siba sincane ngokwanele, ukukhula okuhlanganisiwe kuba nokungazinzi.Ukungazinzi kubonakala ekunyakazeni kwe-lateral kwama-flakes, okuvimbela ukuqondanisa kwawo futhi, ngaleyo ndlela, kukhuthaze ukwakheka kwezakhiwo ezixhumene ne-topologically.Ushintsho olusuka ekukhuleni okuzinzile luye ekukhuleni okungazinzile lwenzeka eduze kuka-xi = 250 nm ngesilinganiso esingu-4.7 mm/s.Ngokuphambene nalokho, ukujula okuhambisanayo kwe-delamination xi kwe-Cu70Ti30 melt cishe ku-40 nm ngesilinganiso esifanayo.Ngakho-ke, asikwazanga ukubona ukuguqulwa okunjalo lapho sisusa i-alloy nge-Cu70Ti30 melt (bheka i-Supplementary Movie 3), ngoba ukwengeza u-30% Ti ekuncibilikeni kunciphisa kakhulu i-kinetics yokususa i-alloy.Ekugcineni, nakuba ukukhula okuhlanganisiwe kokusabalalisa kungazinzi ngenxa ye-delamination kinetics ehamba kancane, ibanga elingu-λ0 lamabhondi aqinile ngaphambili lithobela cishe umthetho \({\lambda }_{0}^{2}V=C\) wokumisa ukukhula15,31 lapho u-C ehlala njalo.
Ukuhlola ukuqagela kokulingisa kwenkundla yesigaba, ukuhlolwa kokukhipha ingxubevange kwenziwa ngamasampula amakhulu kanye nezikhathi ezinde zokususa ingxubevange.Umfanekiso 4a uwumdwebo wohlelo obonisa amapharamitha angukhiye wesakhiwo esiphathisiwe.Ingqikithi yokujula kwe-delamination ilingana no-xi, ibanga ukusuka emngceleni wokuqala wezigaba eziqinile neziwuketshezi ukuya endaweni engaphambili ye-delamination.I-hL ibanga ukusuka kusixhumi esibonakalayo esiqinile-soketshezi lokuqala ukuya emaphethelweni esakhiwo esithunyelwe ngaphambi kokusijwa.I-hL enkulu ikhombisa ukuvuza okuqinile kwe-Ta.Kusukela kusithombe se-SEM sesampula esithunyelwe, singakala usayizi we-hD wesakhiwo esithunyelwe ngaphambi kokuqoshwa.Kodwa-ke, njengoba ukuncibilika kuqinisa futhi ekushiseni kwekamelo, kungenzeka ukugcina isakhiwo esiphathisiwe ngaphandle kwezibopho.Ngakho-ke, simise ukuncibilika (isigaba esicebile ngethusi) ukuze sithole isakhiwo soshintsho futhi sasebenzisa i-hC ukuze silinganise ubukhulu besakhiwo soguquko.
umdwebo weSchematic wokuziphendukela kwemvelo kwe-morphology ngesikhathi sokususwa kokungcola kanye nokunqunywa kwemingcele yejometri: ukujiya kongqimba bokuvuza i-Ta hL, ukujiya kwesakhiwo se-delaminated hD, ukujiya kwesakhiwo sokuxhuma i-hC.(b), (c) Ukuqinisekiswa kokuhlolwa kwemiphumela yokulingisa yenkundla yesigaba eqhathanisa izigaba eziphambanayo ze-SEM kanye ne-3D emisiwe morphology ye-Ta15Ti85 ingxubevange elungiswe kusukela ekuncibilikeni okumsulwa kwe-Cu(b) ne-Cu70Ag30, okunikeza amabhondi e-topological anosayizi webhondi efanayo Isakhiwo (c), ibha yesikali 10µm.
Izingxenye eziphambanayo zezakhiwo eziphathisiwe eziboniswe emkhiwaneni.I-4b,c iqinisekisa imiphumela ebikezelwe eyinhloko yokwengeza i-Ti ne-Ag ku-Cu iyancibilika ku-morphology kanye ne-kinetics ye-alloy ethunyelwe.Emkhiwaneni.Umfanekiso 4b ubonisa indawo engezansi yokusikwa kwe-SEM (ngakwesokunxele) yengxubevange ye-Ta15T85 ehlanganiswe ngokucwiliswa kukhopha elihlanzekile amasekhondi ayi-10 ukuya ekujuleni kuka-xi ~ 270 μm.Esilinganisweni sesikhathi sokuhlola esilinganisekayo, esingama-oda amaningana obukhulu kunezifaniso zenkundla yesigaba, isivinini esingaphambili sokuhlukanisa singaphansi kakhulu kwesivinini esishiwo ngenhla esingu-4.7 mm/s, okungaphansi kwalokho ukukhula kwebhondi ye-eutectic ezinzile kuba nokungazinzi.Ngakho-ke, isakhiwo esingenhla kwekhasi langaphambili kulindeleke ukuthi sixhumeke ngokugcwele ngokwe-topologically.Ngaphambi kokucwiliswa, ungqimba oluncane lwe-alloy yesisekelo luhlakazwe ngokuphelele (hL = 20 μm), olwaluhlotshaniswa nokuvuza kwe-Ta (Ithebula 1).Ngemva kokunamathiselwa kwamakhemikhali esigaba esinothe ngethusi (kwesokudla), kusele ungqimba oluncane lwengxubevange ephathisiwe (hC = 42 µm) esele, okubonisa ukuthi ingxenye enkulu yesakhiwo esiphathisiwe yalahlekelwa ubuqotho besakhiwo ngesikhathi sokunamathisela futhi yayingaboshiwe, njengoba bekulindelekile, Umfanekiso 1a)., isithombe esingakwesokudla kumugqa wesithathu).Emkhiwaneni.I-4c ibonisa ingxenye egcwele ye-SEM enqamulayo kanye nezithombe ze-3D zokushumeka kwengxubevange ye-Ta15Ti85 ekhishwe ngokucwiliswa ku-Cu70Ag30 melt amasekhondi angu-10 ukuya ekujuleni okungaba ngu-200 µm.Njengoba ukujula kwekhasi kubikezelwa ngokomcabango ukuthi kuzokwanda \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\) nge-kinetics elawulwayo yokusabalalisa (bona I-Supplementary Note 4) 15 16, Ngokungezwa kwe-30% Ag kuya ku-Cu melt, ukuncipha kokujula kokuhlukana kusuka ku-270 μm kuya ku-220 μm kuhambisana nokuncipha kwenombolo ye-Peclet p nge-factory ye-1.5.Ngemva kokuhlotshaniswa kwamakhemikhali kwesigaba esicebile se-Cu/Ag (kwesokudla), sonke isakhiwo esithunyelwe sigcina ubuqotho besakhiwo (hC = 200 µm), okubonisa ukuthi ngokuyisisekelo siyisakhiwo esibikezelwe se-topologically esihlanganiswe ngokuqhubekayo okubili (Umfanekiso 1, isithombe esingakwesokudla) umugqa wesibili futhi uphelele. umugqa ongezansi).Zonke izilinganiso ze-alloy yesisekelo esiphathisiwe i-Ta15T85 ekuncibilikeni okuhlukahlukene kufinyezwa kuThebula.1. Sethula futhi imiphumela ye-Ta10Ti90 base alloys engahlanganisiwe ekuncibilikeni okuhlukahlukene, eqinisekisa iziphetho zethu.Izilinganiso zogqinsi lwesendlalelo sokuvuza i-Ta ibonise ukuthi isakhiwo esincibilikisiwe ku-Cu70Ag30 melt (hL = 0 μm) sincane kunaleso ekuncibilikeni okuhlanzekile kwe-Cu (hL = 20 μm).Ngokuphambene nalokho, ukungezwa kwe-Ti ekuncibilikeni kuncibilikisa izakhiwo ezihlanganisiwe ezibuthakathaka (hL = 190 μm).Ukuncipha kokuhlakazwa kwesakhiwo esithunyelwe phakathi kwe-Cu melt emsulwa (hL = 250 μm) kanye ne-Cu70Ag30 melt (hL = 150 μm) kugqama kakhulu kuma-alloys athunyelwe asekelwe ku-Ta10Ti90.
Ukuze uqonde umthelela wokuncibilika okuhlukile, senze ukuhlaziya komthamo okwengeziwe kwemiphumela yokuhlola ku-Fig. 5 (bona futhi Idatha Eyengeziwe 1).Emkhiwaneni.Amanani 5a–b abonisa ukusatshalaliswa kokugxilisa okulinganiselwe kwama-elementi ahlukene ngakundlela yokukhipha inkomba ekuhlolweni kwe-exfoliation ku-Cu melt emsulwa (Fig. 5a) kanye ne-Cu70Ag30 melt (Fig. 5b).Ukugxiliswa kwezakhi ezihlukahlukene kuhlelwa ngokumelene nebanga elingu-d ukusuka ngaphambili kwe-delamination ukuya onqenqemeni lwesendlalelo se-delamination kusibophezelo esiqinile kanye nesigaba esasiwuketshezi (esinothiswe nge-Cu noma i-CuAg) ngesikhathi se-delamination.Ngokungafani ne-ECD, lapho ukugcinwa kwezinto ezixubene kunqunywa izinga lokuhlukana, ku-LMD, ukugxiliswa kusibophezelo esiqinile kunqunywa ukulingana kwe-thermodynamic yendawo phakathi kwezigaba eziqinile neziwuketshezi futhi, ngaleyo ndlela, izakhiwo zokuhlalisana kokuqinile nokuqinile. izigaba eziwuketshezi.Imidwebo ye-Alloy State.Ngenxa yokuhlakazeka kwe-Ti kusuka ku-alloy eyisisekelo, ukugxiliswa kwe-Ti kuncipha ngokukhuphuka kuka-d ukusuka phambili okudelelekile kuya emaphethelweni ongqimba lwe-delamination.Ngenxa yalokho, ukugxilisa ingqondo kwe-Ta kwanda ngokukhula kuka-d eduze kwenqwaba, okwakuhambisana nokulingiswa kwensimu yesigaba (I-Supplementary Fig. 5).Ukugxiliswa kwe-Ti ku-Cu70Ag30 melt yehla kancane kakhulu kune-Cure melt ehlanzekile, ehambisana nezinga elihamba kancane lokususwa kwe-alloy.Amaphrofayili okugxilisa alinganisiwe ku-Fig.I-5b iphinde ibonise ukuthi isilinganiso sokugxiliswa kwe-Ag ne-Cu oketshezini asihambisani ncamashi nongqimba lwengxubevange ephathisiwe, kuyilapho ekulingiseni inkambu yesigaba lesi silinganiso sathathwa njengesingaguquki ekulingiseni ukuncibilika njenge i-pseudo-element Cu70Ag30.Ngaphandle kwalo mehluko wobuningi, imodeli yensimu yesigaba ithwebula umthelela wekhwalithi ovelele wokwengeza i-Ag ekucindezeleni ukuvuza kwe-Ta.Ukumodela okugcwele komthamo wama-gradients okugxilisa ingqondo yazo zonke izici ezine kuzibophezelo eziqinile noketshezi kudinga imodeli enemba kakhudlwana yezingxenye ezine zomdwebo wesigaba se-TaTiCuAg, ongaphezu kobubanzi balo msebenzi.
Amaphrofayili okugxilisa alinganisiwe kuye ngebanga elingu-d ukusuka ku-delamination phambi kwengxubevange ye-Ta15Ti85 ku-(a) Cu encibilikayo ehlanzekile kanye (b) ne-Cu70Ag30 encibilikayo.Ukuqhathaniswa kwengxenye yevolumu elinganisiwe yezinto eziqinile ρ(d) zesakhiwo esithunyelwe (umugqa oqinile) nesibikezelo sethiyori esihambisana nesibalo ngaphandle kokuvuza u-Ta (umugqa odeshi).(1) (c) Gcwalisa isibikezelo sezibalo.(1) Izibalo zilungisiwe ngaphambili kwe-delamination.(2) Okusho ukuthi, ukuvuza kwe-Ta kuyabhekwa.Linganisa ububanzi bobubanzi bebhondi engu-λw nebanga elingu-λs (d).Amabha wephutha amele ukuchezuka okujwayelekile.
Emkhiwaneni.I-5c iqhathanisa ingxenye yevolumu elinganisiwe yezinto eziqinile ρ(d) (umugqa oqinile) wezakhiwo ezithunyiwe ezimsulwa ze-Cu kanye ne-Cu70Ag30 kusukela ekuncibilikeni nokuqagela kwethiyori (umugqa odeshi) otholwe ekulondolozweni kwesisindo kusetshenziswa ukugxiliswa kuka-Ta kukalwa kusibophezelo esiqinile \({{{ c }_ {Ta}^{s}(d)\) (Fig. 5a,b) futhi uzibe ukuvuza kwe-Ta kanye nokuthuthwa kuka-Ta phakathi kwamabhondi anobunzulu obuhlukene bokuhlukana.Uma i-Ta ishintsha isuka kokuqinile iye oketshezini, yonke i-Ta equkethwe ku-alloy eyisisekelo kufanele isatshalaliswe kabusha ibe isibopho esiqinile.Ngakho-ke, kunoma yisiphi isendlalelo sesakhiwo esikude esincike ekuqondeni kokususwa kwe-alloy, ukulondolozwa kwesisindo kusho ukuthi \({c}_{Ta}^{s}(d){S}_{s}(d) )={c}_ {Ta}^{0}(d){S}_{t}\), lapho \({c}_{Ta}^{s}(d)\) kanye \({c) }_{Ta }^ {0}\) ukugxilisa kuka-Ta endaweni d ku-binder ne-matrix alloy, ngokulandelanayo, futhi i-Ss(d) ne-St yizindawo ezihlukene ze-hard binder kanye nesifunda sonke esikude, ngokulandelana.Lokhu kubikezela ingxenye yevolumu yezinto eziqinile kusendlalelo esikude.
Lokhu kungasetshenziswa kalula esakhiweni se-Pure ekhethiwe ephathisiwe kanye ne-Cu70Ag30 encibilikayo kusetshenziswa amajika \({c}_{Ta}^{s}(d)\) ahambisanayo" ahambisana nomugqa oluhlaza okwesibhakabhaka.Lezi zibikezelo zibekwe phezulu ku-Fig. 5c okubonisa ukuthi ukuziba ukuvuza kwe-Ta kuwukubikezela okungalungile kokusatshalaliswa kwengxenye yevolumu.Ukulondolozwa kwesisindo esingavuzisi kubikezela ukwehla kwe-monotonic kwingxenye yevolumu ngokukhuphuka kuka-d, okubonakala ngekhwalithi ekuncibilikeni okumsulwa kwe-Cu, kodwa hhayi ku-Cu70Ag30 encibilikayo, lapho u-ρ(d) enobuncane.Ngaphezu kwalokho, lokhu kuholela ekulinganisweni okweqile okuphawulekayo kwezingxenye zevolumu ngaphambili kokuhlukana kwakho kokubili okuncibilikayo.Ku-d ≈ 10 µm encane kakhulu elinganisekayo, amanani abikezelwe ρ kukho kokubili ukuncibilika adlula u-0.5, kuyilapho amanani alinganiselwe ka-ρ we-Cu kanye ne-Cu70Ag30 encibilikayo ephakeme kancane kuno-0.3 no-0.4, ngokulandelana.
Ukuze sigcizelele indima eyinhloko yokuvuza kwe-Ta, sibe sesikhombisa ukuthi umehluko wenani phakathi kwamanani ka-ρ akaliwe futhi abikezelwe eduze nendawo yokubola angaqedwa ngokucwengisiswa kwezibikezelo zethu zethiyori ukuze kufakwe lokhu kuvuza.Kulokhu, ake sibale isamba senani lama-athomu e-Ta agelezayo asuka kokuqinile abe oketshezini lapho ukubola okungaphambili kuhamba ibanga elide Δxi = vΔt esikhawulweni sesikhathi Δt Δxi = vΔt, lapho \(v={\dot{x) )) _{i }( t )\) - izinga lokunciphisa, ukujula kanye nesikhathi kungatholakala ebudlelwaneni obaziwayo \({x}_{i}(t)=\sqrt{4p{D}_{l}t } \) ukudakwa.Umthetho wendawo wokongiwa kwesisindo endaweni engaphambili yokuhlukanisa (d ≈ 0) uthi ΔN = DlglΔtSl/va, lapho i-gl iyi-gradient yokugxilisa ama-athomu e-Ta oketshezini, i-va iyivolumu ye-athomu ehambisana nokugxilisa ingqondo okuchazwa ngokuthi ingxenyenamba ye-athomu, kanye ne-Sl = St − Ss iyindawo enqamula ingxenye yesiteshi esiwuketshezi ngaphambili kwe-delamination.I-concentration gradient gl ingabalwa ngokucabangela ukuthi ukuhlangana kwama-athomu e-Ta kunenani elingaguquki \({c}_{Ta}^{l}\) kusixhumi esibonakalayo futhi kuncane kakhulu ekuncibilikeni ngaphandle kwesendlalelo esikhishwe, okuyinto inikeza \( {g}_ {l}={c}_{Ta}^{l}/{x}_{i}\) Ngakho, \({{\Delta}}}N=({{\ Delta} {x}_{i} {S}_{l}/{v}_{a}){c}_{Ta}^{l}/(2p)\).Uma ingaphambili liya ebangeni elingu-Δxi, ingxenyenamba eqinile ilingana nenani eliphelele lama-athomu e-Ta akhishwe ku-alloy yesisekelo, \({{\Delta}}{x}_{i}{S}_{t} { c }_{Ta}^ { 0}/{v}_{a}\), ukuya esibalweni senani lama-athomu e-Ta avuzela oketshezini, ΔN, futhi afakwe kusibophezelo esiqinile\({{\Delta} } {x}_{i}{S}_{s {c}_{Ta}^{s}/{v}_{a}\).Le zibalo, kanye nenkulumo engenhla ye-ΔN kanye nobudlelwano St = Ss + Sl kanye nezigaba ngaphambili kwe-delamination.
Emkhawulweni wokuncibilika kukaziro we-athomu ye-Ta, okwehlisela ekuqageleni kwangaphambili kokungabikho kokuvuza, \(\rho ={c}_{Ta}^{0}/{c}_{Ta}^{s} \)uketshezi ( \({c }_{Ta}^{l}=0\)).Kusetshenziswa amanani \({c}_{Ta}^{l}\cishe 0.03\) kusuka kuzilinganiso zokuhlola (akuboniswe ku-Fig. 5a, b) kanye nezinombolo ze-Peclet p ≈ 0.26 kanye no-p ≈ 0.17 kanye nokugxiliswa kwezinto eziqinile \ ( {c}_{Ta}^{s}\ cishe u-0.3\) kanye \({c}_{Ta}^{s}\ cishe u-0.25\) we-Cu kanye ne-Cu70Ag30 iyancibilika, ngokulandelana , sithola inani elibikezelwe ukuncibilika, ρ ≈ 0.38 kanye ρ ≈ 0.39.Lezi zibikezelo ngobuningi zivumelana kahle nezilinganiso.Omunye umehluko (okubikezelwe u-0.38 vs. okukalwe okungu-0.32 kokuncibilika okumsulwa kwe-Cu kanye no-0.39 okubikezelwe uma kuqhathaniswa no-0.43 we-Cu70Ag30 melt) kungachazwa ukungaqiniseki okukhulu kwesilinganiso sokugxila kwe-Ta okuphansi kakhulu oketshezini (\( {c }_{Ta }^ {l}\ cishe 0.03\)), okulindeleke ukuthi ibe kukhudlwana ekuncibilikeni kwethusi okumsulwa.
Nakuba ukuhlolwa kwamanje kwenziwe kuma-alloys athile ayisisekelo nezinto ezincibilikayo, silindele ukuthi imiphumela yokuhlaziywa kwalokhu kuhlolwa izosiza ekutholeni izibalo.(2) Ukusebenza okubanzi kwezinye izinhlelo zokudotshwa kwezidakamizwa ze-LMD nezinye izindlela ezihlobene ezifana Nokususwa Kokungcola Kwesifunda Esiqinile (SSD).Kuze kube manje, umthelela wokuvuza kwezinto ezingahlangani esakhiweni se-LMD azinakwa ngokuphelele.Lokhu kubangelwa ikakhulukazi ukuthi lo mphumela awubalulekile ku-ECDD, futhi kuze kube manje sekucatshangwe ngokungenangqondo ukuthi i-NMD ifana ne-REC.Kodwa-ke, umehluko oyinhloko phakathi kwe-ECD ne-LMD ukuthi ku-LMD ukunyibilika kwezinto ezingahlangani oketshezini kukhuphuka kakhulu ngenxa yokugcwala okuphezulu kwezinto ezixubene ohlangothini oluwuketshezi lwesixhumi esibonakalayo (\({c}_{Ti} ^{ l}\)), okubuye kwenyuse ukuhlangana kwezinto ezingaqondakali (\({c}_{Ta}^{l}\)) kuhlangothi oluwuketshezi lwesixhumi esibonakalayo futhi yehlise ingxenye yevolumu ebikezelwe isibalo sesimo esiqinile. .(2) Lokhu kuthuthukiswa kungenxa yokuthi i-solid-liquid interface phakathi ne-LMD iku-equilibrium yasendaweni ye-thermodynamic, ephakeme kakhulu \({c}_{Ti}^{l}\) isiza ukuthuthukisa \({c} _ {Ta} ^{l}\ Ngokufanayo, okuphezulu \({c}_{Ti}^{s}\) kuvumela i-Cu ukuthi ifakwe kuma-hard binder, futhi ukugxiliswa kwe-Cu eqinile kulezi zibophezelo kuyahlukahluka kusuka cishe ku-10% kancane kancane. ukwehla ukuya kumanani akunakwa emaphethelweni ongqimba oluncane oluthunyelwe (I-Supplementary Fig. 6). Ngokuphambene, ukukhishwa kwe-electrochemical kwe-Ag ku-AgAu alloys nge-ECD kuwukusabela okungalingani okungakukhulisi ukunyibilika kwe-Au in. i-electrolyte.Ngaphezu kwe-LMD, sithemba futhi ukuthi imiphumela yethu iyasebenza kumadrayivu wesimo esiqinile, lapho umngcele oqinile kulindeleke ukuthi ugcine ukulingana kwe-thermodynamic yendawo ngesikhathi sokususwa kwe-alloy.Lokhu okulindelekile kusekelwa iqiniso lokuthi ushintsho kungxenyana yevolumu kokuqinile kungqimba oluphathisiwe lwesakhiwo se-SSD kwaqashelwa, okusho mina, ukuthi phakathi nokuthunyelwa kuba khona ukuhlakazeka komsipha oqinile, okuhambisana nokuvuza kwezinto ezingahlangani.
Futhi i-equation.(2) Ukuze ubikezele ukwehla okuphawulekayo kwengxenye eqinile ngaphambili kokususwa kwe-alloy ngenxa yokuvuza kwe-Ta, kuyadingeka futhi ukucabangela ukuthutha kwe-Ta endaweni yokukhipha ingxubevange ukuze kuqondwe ukusatshalaliswa kwengxenye eqinile kulo lonke. isendlalelo sokususa i-alloy, esihambisana nethusi elimsulwa kanye ne-Cu70Ag30 encibilikayo.Okokuncibilika kwe-Cu70Ag30 (umugqa obomvu ku-Fig. 5c), u-ρ(d) unobuncane obungaba ingxenye yesendlalelo esithunyelwe.Lobu buncane bubangelwa iqiniso lokuthi inani eliphelele lika-Ta eliqukethwe kusibophezelo esiqinile eduze komkhawulo wesendlalelo esithunyelwe likhulu kune-alloy eyisisekelo.Okungukuthi, ku-d ≈ 230 μm \({S}_{s}(d){c}_{Ta}^{s}(d)\, > \,{S}_{t}{c} _ { Ta}^{0}\), noma okulingana ngokuphelele, isilinganiso ρ(d) = Ss(d)/St ≈ 0.35 sikhulu kakhulu kunesibikezelo sezibalo.(1) Akukho ukuvuza\({c}_{Ta}^{0}/{c}_{Ta}^{s}(d)\approx. 0.2\).Lokhu kusho ukuthi ingxenye ye-Ta ephunyukayo ithuthwa isuka endaweni engaphambili yokwehlukana iyiswe endaweni eqhelile kusuka kule ngaphambili, isakazeke oketshezini kanye nesixhumi esibonakalayo esiwuketshezi oluqinile, lapho iphinde ifakwe khona.
Lokhu kubekwa kabusha kunomphumela ophambene wokuvuza kwe-Ta ukuze kucebise ama-Ta hard binder, futhi ukusatshalaliswa kwengxenyana eqinile kungachazwa ngokwekhwalithi njengebhalansi yokuvuza kwe-Ta kanye nokuphinda kubekwe kabusha.Ngokuncibilika kwe-Cu70Ag30, ukugxiliswa kwe-Ag oketshezini kukhuphuka ngokukhula kuka-d (umugqa onamachashazi ansundu ku-Fig. 5b) ukuze kuncishiswe ukuvuza kwe-Ta ngokunciphisa ukunyibilika kwe-Ta, okuholela ekwenyukeni ku-ρ(d) ngokukhuphuka kuka-d ngemuva kokufinyelela ubuncane. .Lokhu kugcina ingxenye eqinile enkulu ngokwanele ukuvimbela ukuhlukana ngenxa yokuhlukaniswa kwebhondi eqinile, okuchaza ukuthi kungani izakhiwo ezidluliselwe ku-Cu70Ag30 zincibilika zigcina ubuqotho besakhiwo ngemva kokunamathiselwa.Ngokuphambene, ekuncibilikeni kwethusi elimsulwa, ukuvuza kanye nokwakheka kabusha kucishe kucishe kuphume okunye, okuholela ekuncipheni kancane kwezinto eziqinile ngaphansi komkhawulo wokuhlukana kweningi lesendlalelo esithunyelwe, okushiya kuphela ungqimba oluncane kakhulu olugcina ubuqotho besakhiwo eduze komngcele ungqimba oluthunyelwe.(Umdwebo 4b, Ithebula 1).
Kuze kube manje, ukuhlaziya kwethu kugxile kakhulu ekuchazeni umthelela oqinile wokuvuza kwezinto ezixubekile endaweni ehlukanisayo engxenyeni eqinile kanye ne-topology yezakhiwo eziphathisiwe.Manje ake sibheke umphumela walokhu kuvuza ekubhidlikeni kwesakhiwo se-bicontinuum ngaphakathi kwesendlalelo esiphathisiwe, okuvame ukwenzeka phakathi ne-LMD ngenxa yokushisa okuphezulu kokucubungula.Lokhu kuhlukile kune-ECD lapho ukugwaza kucishe kungabi khona ngesikhathi sokukhishwa kwengxubevange, kodwa kungabangelwa ukugoqa emazingeni okushisa aphakeme ngemva kokususwa kwengxubevange.Kuze kube manje, ukukhohlakala ngesikhathi se-LMD kumodelwe ngaphansi kokucatshangwa ukuthi kwenzeka ngenxa yokusatshalaliswa kwezinto ezingaxubeki eduze nesixhumi esibonakalayo esiwuketshezi oluqinile, okufana nokunwebeka okuphakathi kokusabalalisa okuphakathi kwezakhiwo ze-ECD ezihlanganisiwe.Ngakho-ke, usayizi webhondi ulinganiswe kusetshenziswa imithetho yokukala ejwayelekile yokukhulisa i-capillary.
lapho i-tc iyisikhathi sokuqina, esichazwa ngokuthi isikhathi esidlulile ngemva kokudlula kwe-delamination front ekujuleni xi ngaphakathi kongqimba lwe-delamination (lapho u-λ enenani lokuqala elingu-λ00) kuze kube sekupheleni kokuhlolwa kwe-delamination, kanye nenkomba yokukala n = 4 isabalalisa ubuso.I-Eq kufanele isetshenziswe ngokuqapha.(3) Humusha izilinganiso zika-λ nebanga d zesakhiwo sokugcina ngaphandle kokungcola ekupheleni kokuhlolwa.Lokhu kungenxa yokuthi isifunda esiseduze nomkhawulo wesendlalelo esithunyelwe sithatha isikhathi eside ukunwetshwa kunesifunda esiseduze nangaphambili.Lokhu kungenziwa ngezibalo ezengeziwe.(3) Ukuxhumana no-tc kanye no-d.Lokhu kuhlobana kungatholwa kalula ngokubikezela ukujula kokususwa kwengxubevange njengomsebenzi wesikhathi, \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\), okunikeza tc( d ) = te − tf(d), lapho te kuwubude besikhathi saso sonke isilingo, \({t}_{f}(d)={(\sqrt{4p{D}_{l}) {t}_{ e } }-d)}^{2}/(4p{D}_{l})\) isikhathi sokuthi i-delamination front ifinyelele ukujula okulingana nokujula kokugcina kokususa u-d.Xhuma lesi sisho se-tc(d) kusibalo.(3) Qagela u-λ(d) (bona inothi eyengeziwe 5).
Ukuze sihlole lesi sibikezelo, senze izilinganiso zobubanzi nebanga phakathi kwezinqwaba ezigabeni ezigcwele eziphambanayo zezakhiwo eziphathisiwe eziboniswe Kumfanekiso Owengeziwe 9 wokuncibilika okumsulwa kwe-Cu ne-Cu70Ag30.Kusukela ekuhloleni kolayini okuqondile kuya ekuqondeni kwe-delamination kumabanga ahlukene d ukusuka ngaphambili kwe-delamination, sithole ububanzi obuyisilinganiso esingu-λw(d) benqwaba ye-Ta-rich kanye nebanga elimaphakathi λs(d) phakathi kwamanqwaba.Lezi zilinganiso ziboniswa ku-fig.5d futhi uma kuqhathaniswa nezibikezelo zezibalo.(3) ku-Supplementary Fig. 10 ngamavelu ahlukene we-n.Ukuqhathanisa kukhombisa ukuthi inkomba yokusabalalisa kwendawo ye-n = 4 inikeza izibikezelo ezimbi.Lesi sibikezelo asithuthukisiwe kakhulu ngokukhetha okuthi n = 3 ngobuningi be-capillary coarsening-mediated coarsening, umuntu angase alindele ngokungazi ukuhlinzeka ngokulingana okungcono ngenxa yokuvuza kwe-Ta oketshezini.
Lo mehluko wobuningi phakathi kwethiyori nokuhlola akumangazi, njengoba u-Eq.(3) ichaza i-capillary coarsening engxenyeni yevolumu engashintshi engu-ρ, kuyilapho ku-LMD ingxenyenamba eqinile engu-ρ ayishintshile.ρ ishintsha ngokwendawo ngaphakathi kwesendlalelo esisusiwe ekugcineni kokukhishwa kwengxubevange, njengoba kuboniswe kumfanekiso.5c.ρ futhi ishintsha nesikhathi phakathi nokukhishwa kokungcola ekujuleni okungaguquki kokukhipha, ukusuka enanini lendawo engaphambili yokukhipha (elicishe lilingane ngesikhathi futhi ngaleyo ndlela linganciki ku-tf no-d) liye kunani elilinganiselwe lika-ρ(d) eliboniswe ku-Fig. 5c ehambisana nesikhathi sokugcina.Kusukela emkhiwaneni.3d, kungalinganiselwa ukuthi amanani angaphambili okubola angaba ngu-0.4 kanye no-0.35 ku-AgCu kanye ne-Cu ecwebile iyancibilika, ngokulandelana, okuthi kuzo zonke izimo iphakame kunenani lokugcina lika-ρ ngesikhathi te.Kubalulekile ukuqaphela ukuthi ukwehla ku-ρ ngesikhathi ku-d emisiwe kuwumphumela oqondile wokuba khona kwegradiyenti yokugxilisa ingqondo yento ehlanganisiwe (Ti) oketshezini.Njengoba ukugcwala kwe-Ti oketshezini kuncipha ngokukhula kuka-d, ukugxiliswa kokulingana kwe-Ti kokuqinile nakho kuwukwehla komsebenzi ka-d, okuholela ekuhlakazweni kwe-Ti ezibopheni eziqinile kanye nokuncipha kwengxenyana eqinile ngokuhamba kwesikhathi.Ushintsho lwesikhashana ku-ρ nalo luthintwa ukuvuza nokuhlelwa kabusha kwe-Ta.Ngakho-ke, ngenxa yemiphumela eyengeziwe yokuqedwa nokubuyiswa kabusha, silindele ukuthi ukukhuphuka ngesikhathi se-LMD, njengomthetho, kuzokwenzeka kuma-fractions wevolumu angashintshi, okuzoholela ekuguquguqukeni kwesakhiwo ngaphezu kwe-capillary coarsening, kodwa futhi ngenxa yokusabalalisa uketshezi hhayi kuphela eduze komngcele okuqinile-uketshezi.
Amaqiniso ezibalo.(3) Ububanzi bebhondi nezilinganiso zesikhala ze-3 ≤ n ≤ 4 azibalwa (I-Supplementary Fig. 10), iphakamisa ukuthi ukuhlakazwa nokuhlelwa kabusha okungabangelwa ukuncishiswa kwesixhumi esibonakalayo kudlala indima enkulu ekuhlolweni kwamanje.Ekubambiseni kwama-capillary, u-λw kanye no-λs kulindeleke ukuthi ancike okufanayo ku-d, kuyilapho u-Fig. 5d ubonisa ukuthi u-λs ukhuphuka ngo-d ngokushesha kakhulu kuno-λw ku-Cu kanye ne-Cu70Ag30 encibilikayo.Nakuba ithiyori eqinile ecabangela ukuhlakazeka kanye nokuhlelwa kabusha kufanele kucatshangelwe ukuchaza lezi zilinganiso ngokwesilinganiso, lo mehluko ulindeleke ngokwekhwalithi, njengoba ukuqedwa okuphelele kwamabhondi amancane kunomthelela ekwenyukeni kwebanga phakathi kwamabhondi.Ngaphezu kwalokho, ama-λs we-Cu70Ag30 ancibilika afinyelela inani lawo eliphakeme emaphethelweni ongqimba ngaphandle kwe-alloy, kodwa iqiniso lokuthi i-λs ye-copper ecwebile encibilika iyaqhubeka nokukhula nge-monotonically ingachazwa ngokwanda kokuhlushwa kwe-Ag oketshezini, lapho. u-d usetshenziselwa ukuchaza u-ρ(d) ku-Fig. 5c ukuziphatha okungahambisani ne-nonmonotonic.Ukwandisa ukugxila kwe-Ag ngokukhuphuka kwe-d kucindezela ukuvuza kwe-Ta kanye nokuhlakazeka kwe-binder, okuholela ekwehleni kwama-λs ngemuva kokufinyelela inani eliphakeme.
Okokugcina, qaphela ukuthi izifundo zekhompiyutha ze-capillary coarsening ngengxenye yevolumu engaguquki zibonisa ukuthi uma ingxenyenamba yevolumu iwela ngaphansi komkhawulo ocishe ube ngu-0.329.30, izingcezu zesakhiwo ngesikhathi sokuqhafaza.Empeleni, lo mkhawulo ungase ube ngaphansi kancane ngenxa yokuthi ukuhlukana nokwehliswa kohlobo okuhambisanayo kwenzeka esikalini sesikhathi esiqhathanisekayo noma esikhulu kunesamba sesikhathi sokususwa kwe-alloy kulokhu kuhlolwa.Iqiniso lokuthi izakhiwo eziphathisiwe ku-Cu70Ag30 ziyancibilika zigcina ubuqotho bazo besakhiwo nakuba u-ρ(d) engaphansi kancane kuka-0.3 ebangeni elimaphakathi lika-d libonisa ukuthi ukuhlukana, uma kukhona, kwenzeka kancane.Umkhawulo wengxenye yevolumu yokuhlukaniswa ungase uncike ekuhlakazweni nasekukhuphukeni kabusha.
Lolu cwaningo ludonsa iziphetho ezimbili ezibalulekile.Okokuqala, nangaphezulu, i-topology yezinhlaka eziphathisiwe ezikhiqizwe i-LMD ingalawulwa ngokukhetha ukuncibilika.Ngokukhetha ukuncibilika ukuze kuncishiswe ukuncibilika kwento engaqondakali A ye-AXB1-X eyisisekelo ye-alloy ekuncibilikeni, nakuba ilinganiselwe, kungadalwa isakhiwo esithunywe kakhulu esigcina ukuhlangana kwaso ngisho nasezindaweni eziphansi zokugxila kwe-elementi X kanye nobuqotho besakhiwo. .Ngaphambilini kwakwaziwa ukuthi lokhu kungenzeka ku-ECD25, kodwa hhayi nge-LMD.Isiphetho sesibili, esibaluleke kakhulu, ukuthi kungani ku-LMD ubuqotho besakhiwo bungalondolozwa ngokushintsha indlela yokuthumela, ethakazelisa ngokwayo futhi engachaza ukubonwa kwengxube yethu ye-TaTi ku-Cu ne-CuAg ehlanzekile in , kodwa futhi ngokujwayelekile ukuze kucaciswe umehluko obalulekile, obekade ubukelwe phansi phakathi kwe-ECD ne-LMD.
Ku-ECD, ukubumbana kwesakhiwo kugcinwa ngokugcina izinga lokususwa kokungcola ezingeni eliphansi X, elihlala lingaguquki ngokuhamba kwesikhathi ukuze amandla okushayela angaguquki, amancane ngokwanele ukugcina i-miscible element B eyanele kusibophezelo esiqinile ngesikhathi sokususwa kokungcola ukuze sigcinwe. ivolumu eqinile.ingxenye ρ inkulu ngokwanele ukuvimbela ukuhlukana25.Ku-LMD, izinga lokususwa kwe-alloy \(d{x}_{i}(t)/dt=\sqrt{p{D}_{l}/t}\) liyehla ngokuhamba kwesikhathi ngenxa ye-diffusion limited kinetics.Ngakho-ke, kungakhathaliseki ukuthi hlobo luni lokuncibilika okuthinta kuphela inombolo ye-Peclet p, izinga le-delamination ngokushesha lifinyelela inani elincane ngokwanele ukuze kugcinwe inani elanele lika-B ku-binder eqinile, elibonakala ngokuqondile eqinisweni lokuthi ρ at the delamination. ingaphambili lihlala lilingana nesikhathi.Iqiniso nangaphezulu komkhawulo wokuhlukaniswa.Njengoba kuboniswa ukulingiswa kwenkundla yesigaba, izinga le-peel liphinde lifinyelele ngokushesha inani elincane ngokwanele ukuze liphazamise ukukhula kwesibopho se-eutectic, ngaleyo ndlela kube lula ukwakheka kwezakhiwo eziboshwe nge-topologically ngenxa yokunyakaza kwe-lateral rocking ye-lamellae.Ngakho-ke, umehluko omkhulu oyisisekelo phakathi kwe-ECD ne-LMD usekuguqukeni kwengaphambili le-delamination ngokusebenzisa isakhiwo sangaphakathi songqimba ngemva kokuhlukana kanye no-ρ, kunezinga le-delamination.
Ku-ECD, ρ kanye nokuxhumana kuhlala kungashintshi kulo lonke ungqimba olukude.Ku-LMD, ngokuphambene, kokubili kuyahlukahluka ngaphakathi kwesendlalelo, esiboniswa ngokucacile kulolu cwaningo, esibonisa ukugxiliswa kwe-athomu nokusabalalisa kuka-ρ kukho konke ukujula kwezakhiwo eziphathisiwe ezidalwe i-LMD.Kunezizathu ezimbili zalolu shintsho.Okokuqala, ngisho nasemkhawulweni onguziro wokuncibilika A, igradient B oketshezini, engekho ku-DZE, ingenisa i-concentration gradient A kusibophezelo esiqinile, esisekulinganisweni kwamakhemikhali noketshezi.Igradient A, yona, ingenisa i-gradient ρ ngaphakathi kwesendlalelo ngaphandle kokungcola.Okwesibili, ukuvuza kuka-A oketshezini ngenxa yokungancibiliki okungenaziro kuqhubekela phambili kulungisa ukuhluka kwendawo ka-ρ ngaphakathi kwalolu ungqimba, ngokuncibilika okuncishisiwe kusiza ukugcina u-ρ uphakeme futhi ufana nendawo ukuze kugcinwe ukuxhumana.
Okokugcina, ukuvela kosayizi webhondi kanye nokuxhumana phakathi kwesendlalelo esiphathisiwe ngesikhathi se-LMD kuyinkimbinkimbi kakhulu kune-surface diffusion-limited capillary coarsening engxenyeni yevolumu engashintshi, njengoba kwakucatshangwa ngaphambili ngesifaniso nokuqiniswa kwezakhiwo ze-ECD ezinanoporous.Njengoba kubonisiwe lapha, ukuqina ku-LMD kwenzeka engxenyeni eqinile eshintshashintshayo ngokwe-spatiotemporally futhi kuthonywa ukudluliswa okuhlukene kuka-A no-B kusimo soketshezi kusukela ngaphambili kwe-delamination ukuya ekugcineni kongqimba oluhlukene.Imithetho yokukala ye-capillary coarsening ekhawulelwe ngokusabalaliswa kwendawo noma ngobuningi ayikwazi ukulinganisa izinguquko kububanzi nebanga phakathi kwenqwaba ngaphakathi kwesendlalelo esithunyelwe, kucatshangwa ukuthi ezokuthutha zika-A no-B ezihlotshaniswa nama-gradients ahlanganisa uketshezi zidlala izindima ezilinganayo noma ezifanayo.Okubaluleke kakhulu kunokunciphisa indawo yesixhumi esibonakalayo.Ukuthuthukiswa kwethiyori ecabangela la mathonya ahlukahlukene kuyithemba elibalulekile lekusasa.
Ama-alloys kanambambili e-Titanium-tantalum athengwe kwa-Arcast, Inc (Oxford, Maine) kusetshenziswa ugesi wokungenisa i-Ambrell Ekoheat ES ongu-45 kW kanye ne-crucible yethusi epholiswe ngamanzi.Ngemva kokushisa okuningana, ingxubevange ngayinye yafakwa amahora angu-8 ekushiseni okungaphakathi kuka-200° C. wendawo yokuncibilika ukuze kuzuzwe i-homogenization kanye nokukhula okusanhlamvu.Amasampula asikwe kusukela kule ingot eyinhloko ayeshiselwe amabala ezintambo ze-Ta futhi amiswa engalweni yerobhothi.Amabhavu ensimbi alungiswa ngokushisisa ingxube engu-40 g Cu (McMaster Carr, 99.99%) nge-Ag (Kurt J. Lesker, 99.95%) noma izinhlayiya ze-Ti ngamandla amakhulu kusetshenziswa isistimu yokushisisa engu-4 kW Ameritherm Easyheat kuze kube yilapho iqedwa ngokuphelele.okugeza.ncibilika ngokuphelele.Nciphisa amandla bese uvumela ukugeza kunyakaze futhi kulingane isigamu sehora ekushiseni okusabelayo okungu-1240°C.Khona-ke ingalo yerobhothi iyehliswa, isampula icwiliswa kubhavu isikhathi esinqunyiwe futhi ikhishwe ukuze ipholiswe.Konke ukufudumeza kwe-alloy billet kanye ne-LMD kwenziwa endaweni yokuhlanzeka okuphezulu kwe-argon (99.999%).Ngemva kokukhipha ingxubevange, izingxenye eziphambanayo zamasampuli zapholishwa futhi zahlolwa kusetshenziswa i-optical microscopy kanye ne-scan electron microscopy (SEM, JEOL JSM-6700F).Ukuhlaziywa kwe-elemental kwenziwa yi-energy dispersive X-ray spectroscopy (EDS) ku-SEM.Isakhiwo esincane esinezinhlangothi ezintathu samasampuli athunyelwe sibonwe ngokuhlakaza isigaba esinothe ngethusi eliqinile kusixazululo se-nitric acid esingu-35% (ibanga lokuhlaziya, i-Fluka).
Ukulingisa kwenziwa kusetshenziswa imodeli ethuthukisiwe yenkambu yesigaba sokuqaqa se-ternary alloy15.Imodeli ihlobanisa ukuvela kwenkambu yesigaba ϕ, ehlukanisa phakathi kwezigaba eziqinile neziwuketshezi, nenkambu yokuhlushwa ci yezakhi ze-alloying.Isamba samandla wamahhala wesistimu avezwa njenge
lapho i-f(φ) inamandla okuvimba kabili nge-minima kokuthi φ = 1 kanye no-φ = 0 ehambisana nezinto eziqinile neziwuketshezi, ngokulandelana, kanye ne-fc(φ, c1, c2, c3) igalelo lamakhemikhali enkululekweni yevolumu echaza ukuminyana kwamandla I-alloy yezakhiwo ze-thermodynamic.Ukuze silingise ukuncibilika kabusha kwe-Cu noma i-CuTi emsulwa ibe ama-alloys e-TaTi, sisebenzisa ifomu elifanayo fc(φ, c1, c2, c3) namapharamitha njengakureferensi.15. Ukuze sisuse ama-alloys e-TaTi ane-CuAg encibilikayo, senze isistimu ye-quaternary (CuAg)TaTi ibe lula ohlelweni lwe-ternary olusebenzayo olunamapharamitha ahlukene kuye ngokugxila kwe-Ag, njengoba kuchazwe ku-Supplementary Note 2. Izibalo zokuvela kwenkundla yesigaba kanye inkambu yokuhlushwa itholwe ngendlela ehlukile efomini
Lapho \({M}_{ij}={M}_{l}(1-\phi){c}_{i}\left({\delta}_{ij}-{c}_{j} \kwesokudla)\) i-matrix yokuhamba kwe-athomu, futhi i-Lϕ ibusa i-kinetics yokunamathiselwe kwe-athomu kusixhumi esibonakalayo soketshezi oluqinile.
Idatha yokuhlola esekela imiphumela yalolu cwaningo ingatholakala kufayela ledatha elingeziwe.Amapharamitha wokulingisa anikezwa olwazini olwengeziwe.Yonke idatha iyatholakala futhi kubabhali abafanele uma uyicela.
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