Na gode da ziyartar Nature.com.Kuna amfani da sigar burauza tare da iyakancewar tallafin CSS.Don ƙwarewa mafi kyau, muna ba da shawarar ku yi amfani da sabuntar burauza (ko kuma musaki Yanayin dacewa a cikin Internet Explorer).Bugu da ƙari, don tabbatar da goyon baya mai gudana, muna nuna shafin ba tare da salo da JavaScript ba.
Yana nuna carousel na nunin faifai uku lokaci guda.Yi amfani da maɓallan da suka gabata da na gaba don matsawa ta cikin nunin faifai guda uku a lokaci ɗaya, ko amfani da maɓallan maɓalli a ƙarshen don matsawa ta cikin nunin faifai uku a lokaci ɗaya.
A cikin ƴan shekarun da suka gabata, an sami saurin haɓaka na'urorin ƙarfe na ruwa don ƙirƙira nano-/meso-sized porous da sifofi masu haɗaka tare da manyan musaya don abubuwa daban-daban.Koyaya, wannan hanyar a halin yanzu tana da iyakoki masu mahimmanci guda biyu.Na farko, yana haifar da sifofi masu ci gaba tare da babban tsari na topology don iyakataccen kewayon abubuwan haɗin gwal.Abu na biyu, tsarin yana da girman girman mai ɗaure saboda girman girman girma yayin rabuwar zafi mai zafi.Anan, muna nuna ƙididdigewa da gwaji cewa waɗannan iyakoki za a iya shawo kan su ta hanyar ƙara wani abu zuwa narkewar ƙarfe wanda ke haɓaka babban tsari na topology ta hanyar iyakance ɗigon abubuwan da ba su da kyau yayin yankewa.Bayan haka, muna yin bayanin wannan binciken ta hanyar nuna cewa yawan watsawar abubuwan da ba za a iya mantawa da su ba a cikin ruwa narke yana da tasiri mai ƙarfi ga haɓakar juzu'in juzu'i da topology na tsarin a lokacin flaking.Sakamakon ya bayyana bambance-bambancen bambance-bambance tsakanin karafa na ruwa da kau da ƙazanta na electrochemical, da kuma kafa wata sabuwar hanya don samun tsari daga karafa na ruwa tare da girma da kuma topology.
Tawagar ta samo asali a cikin fasaha mai ƙarfi da ƙwarewa don ƙirƙira nano-/ meso-sized bude pores da tsarin hade tare da ultra-high interfacial surface ga daban-daban ayyuka da tsarin kayan kamar catalysts1,2, man fetur cell3,4, electrolytic capacitors5, 6, kayan resistant zuwa radiation lalacewa 7, high-ikon baturi kayan tare da ƙãra inji kwanciyar hankali 8, 9 ko composite kayan da kyau kwarai inji Properties 10, 11. A daban-daban siffofin, tawagar ya ƙunshi zaži narkar da wani kashi na farko unstructured "precursor" gami” a cikin yanayi na waje, wanda ke haifar da sake tsara abubuwan da ba a narkar da su ba tare da wani abu maras muhimmanci, wanda ya bambanta da topology na asali na allo., Haɗin sinadaran.Ko da yake wakilan electrochemical na al'ada (ECD) ta yin amfani da electrolytes kamar yadda muhalli ya fi nazari har zuwa yau, wannan hanya ta iyakance tsarin wakilai (kamar Ag-Au ko Ni-Pt) zuwa waɗanda ke dauke da abubuwa masu daraja (Au, Pt) kuma suna da isasshe babban bambanci a rage yuwuwar samar da porosity.Wani muhimmin mataki don shawo kan wannan ƙayyadaddun shine sake gano kwanan nan na hanyar haɗakar da ƙarfe na ruwa na 13,14 (LMD), wanda ke amfani da gami na karafa na ruwa (misali, Cu, Ni, Bi, Mg, da sauransu) tare da wasu abubuwa a cikin muhalli. .(misali TaTi, NbTi, FeCrNi, SiMg, da sauransu)6,8,10,11,14,15,16,17,18,19.LMD da bambance-bambancensa na cire kayan haɗin ƙarfe (SMD) suna aiki a ƙananan yanayin zafi lokacin da ƙarfen tushe ya yi tauri20,21 yana haifar da haɗaɗɗen nau'i biyu ko fiye da ke shiga tsakani bayan etching sinadarai na lokaci ɗaya.Waɗannan matakan za su iya rikidewa zuwa buɗe pores.Tsarin.An ƙara inganta hanyoyin wakilai ta hanyar gabatarwar kwanan nan na wakilan lokaci na tururi (VPD), wanda ke yin amfani da bambance-bambance a cikin matsa lamba na abubuwa masu ƙarfi don samar da buɗaɗɗen sifofin nanoporous ta hanyar zaɓen fitar da sinadari guda22,23.
A matakin inganci, duk waɗannan hanyoyin kawar da ƙazanta suna raba mahimman fasalulluka guda biyu na tsarin kawar da ƙazantar da kanta.Da fari dai, wannan shine zaɓin narkar da abubuwan haɗaɗɗun abubuwan da aka ambata (kamar B a cikin mafi sauƙi gami AXB1-X) a cikin yanayin waje.Na biyu, wanda aka fara lura da shi a cikin gwaji na farko da nazarce-nazarce akan ECD24, shine yaɗuwar nau'in da ba a narkar da shi A tare da haɗin gwiwa tsakanin gami da muhalli yayin kawar da ƙazanta.Yadawa yana iya samar da yankuna masu arzikin atomic ta hanyar tsari mai kama da lalatawar spinodal a cikin manyan allurai, albeit iyakance ta hanyar sadarwa.Duk da wannan kamanceceniya, hanyoyin kawar da gami daban-daban na iya haifar da nau'ikan halittu daban-daban saboda dalilai marasa tushe18.Duk da yake ECD na iya samar da babban tsari mai alaƙa da topologically don ɓangarorin atomic (X) na abubuwan da ba a narkar da su ba (kamar Au a cikin AgAu) ƙasa da 5% 25, ​​ƙididdigar ƙididdiga da gwaji na LMD sun nuna cewa wannan hanyar da alama makamanciyar ita ce kawai ke haifar da sifofi masu alaƙa da topologically. .Misali, don mafi girma X, tsarin da ke da alaƙa guda biyu yana da kusan 20% a cikin yanayin TaTi gami da Cu melts (duba siffa 2 a cikin ref. 18 don kwatancen gefe-gefe tare da nau'ikan ECD da LMD iri-iri na X. ).Wannan bambance-bambancen an bayyana shi a ka'ida ta hanyar tsarin haɓaka-haɗe-haɗe da ya bambanta da bazuwar spinodal na tsaka-tsakin fuska kuma yana kama da eutectic-coupled growth26.A cikin yanayin kawar da ƙazanta, haɓaka-haɗe-haɗe-haɗe yana ba da damar filaments mai-arziki (ko flakes a cikin 2D) da tashoshi masu wadatar ruwa na B don haɓaka ta hanyar haɓakawa yayin cire ƙazanta15.Haɓaka nau'i-nau'i yana haifar da tsarin da ba a daɗe ba a cikin tsakiyar ɓangaren X kuma an danne shi a cikin ƙananan ɓangaren X, inda tsibiran da ba a daɗe ba kawai masu wadata a lokaci A zasu iya samuwa.A mafi girma X, haɓakar haɗin gwiwa ya zama mara ƙarfi, yana fifita samuwar ingantattun sifofin 3D waɗanda ke kiyaye mutuncin tsarin koda bayan etching lokaci-lokaci.Abin sha'awa, an lura da tsarin daidaitawa da LMD17 ko SMD20 (Fe80Cr20) XNi1-X alloys suka samar a gwaji don X har zuwa 0.5, yana ba da shawarar cewa haɓakar haɓaka-haɗe-haɗe hanya ce ta ko'ina ga LMD da SMD maimakon yawancin ECD da ke haifar da porous ba. suna da tsarin daidaitawa da aka fi so.
Don bayyana dalilin wannan bambance-bambance tsakanin ECD da NMD ilimin halittar jiki, mun yi wasan kwaikwayo na filin lokaci da kuma nazarin gwaji na NMD na TaXTi1-X alloys, wanda aka gyara narkar da kinetics ta hanyar ƙara abubuwa masu narkewa zuwa jan karfe na ruwa.Mun kammala cewa ko da yake duka ECD da LMD ana kayyade su ta hanyar rarrabuwar kawuna da rarrabawar fuska, waɗannan hanyoyin guda biyu kuma suna da bambance-bambance masu mahimmanci waɗanda zasu iya haifar da bambance-bambancen ilimin halittar jiki18.Na farko, kwasfa kinetics a cikin ECD ana sarrafa shi ta hanyar dubawa tare da ci gaba da saurin kwasfa na gaba V12 a matsayin aikin ƙarfin lantarki da aka yi amfani da shi.Wannan gaskiya ne ko da lokacin da aka ƙara ƙaramin juzu'i na ɓangarori na refractory (misali Pt a cikin Ag-Au) zuwa gariyar iyaye, wanda ke jinkirta ruwa mai tsaka-tsaki, yana tsaftacewa da daidaita abubuwan da ba a haɗa su ba, amma in ba haka ba yana riƙe da ilimin halittar jiki guda 27.Ana samun sifofi da aka haɗe da juna kawai a ƙananan X a ƙananan V, kuma riƙewar abubuwa masu ɓarna 25 yana da girma don kula da ƙaƙƙarfan juzu'i mai girma don hana ɓarna tsarin.Wannan yana nuna cewa adadin rushewa game da yadawar fuska na iya taka muhimmiyar rawa wajen zaɓin yanayin halitta.Sabanin haka, abin da ake cire alloy a cikin LMD ana sarrafa yaduwa15,16 kuma ƙimar tana raguwa da sauri tare da lokaci \(V \ sim \sqrt {{D}_{l}/t}\), inda Dl shine ɓangaren rashin kuskure. don ma'aunin yaduwar ruwa..
Na biyu, a lokacin ECD, solubility na immiscible abubuwa a cikin electrolyte ne musamman low, don haka ba za su iya kawai yaduwa tare da alloy-electrolyte interface.Sabanin haka, a cikin LMD, abubuwan "marasa iyawa" (A) na AXB1-X alloys precursor yawanci suna da kaɗan, ko da yake iyakancewa, narke solubility.Ana iya fahimtar wannan ɗan ƙaramin ƙarfi daga nazarin zane na ternary tsari na tsarin ternary na CuTaTi wanda aka nuna a Ƙarin Hoto 1. Za a iya ƙididdige mai narkewa ta hanyar tsara layin ruwa tare da ma'auni na Ta da Ti a gefen ruwa na mahaɗin (\( {c}_{ {{{{{\rm{Ta))))))}}} ^{l}\ ) da \({c}_{{{({\rm{Ti}}) }}}} }^ {l}\), bi da bi, a yawan zafin jiki na wakilai (Ƙarin Hoto na 1b) m-ruwa interface Ana kiyaye ma'auni na ma'aunin thermodynamic na gida yayin haɗawa, }}}}}} ^ {l} \) kusan akai-akai kuma ƙimarsa tana da alaƙa da X. Ƙarin Hoto na 1b yana nuna cewa \({c}_{{{{{{{\rm{Ta}}}}}})))}^{l}\) ya faɗi cikin kewayon 10 -3 - 10 ^ {l} \) daidai yake da 15.16.Wannan "leakage" na abubuwa masu banƙyama a cikin gami na iya rinjayar duka samuwar tsarin haɗin gwiwa a gaban delamination, a cikin bi da bi, wanda zai iya ba da gudummawa ga rushewa da haɓaka tsarin saboda yaduwar girma.
Domin tantance gudunmawar daban-daban na (i) raguwar adadin cire alluran alloy V da (ii) rage yawan kutsawa na abubuwan da ba su da tushe cikin narke, mun ci gaba a matakai biyu.Na farko, godiya ga \(V \ sim \sqrt{{D}_{l}/t}\)\), ta hanyar nazarin juyin halitta na tsarin daure gaba, ya yiwu a yi nazarin tasirin rage V sosai.babban lokaci.Sabili da haka, mun bincika wannan tasirin ta hanyar gudanar da wasan kwaikwayo na filin lokaci na tsawon lokaci fiye da binciken da ya gabata, wanda ya bayyana kasancewar tsarin daidaitawa na topologically wanda ba a haɗa shi da haɓakar haɓakar haɓakar matsakaicin X15.Na biyu, don bincika tasirin abubuwan da ba su da kyau a kan rage yawan zubar da ruwa, mun ƙara Ti da Ag zuwa narkewar jan ƙarfe don haɓakawa da rage yawan zubar da jini, bi da bi, kuma mun yi nazarin ilimin halittar jiki da ya haifar, rarrabuwar kawuna, da rarraba hankali a cikin narke.wakilan Cu narke ta hanyar lissafi da gwaje-gwaje a cikin tsarin gami.Mun ƙara Ti kari daga 10% zuwa 30% zuwa kafofin watsa labarai don cire narke Cu.Bugu da ƙari na Ti yana ƙara ƙaddamarwar Ti a gefen Layer ɗin da aka wakilta, wanda ke rage ƙaddamarwar Ti a cikin wannan Layer kuma yana rage yawan rushewar.Hakanan yana ƙara yawan ɗigowar Ta ta hanyar haɓaka \({c}_{{{({\rm{Ti}}}}}}}}}^{l}\), don haka \({c}_{{{{{ {\rm{Ta}}}}}}}^{l}\) (Ƙarin adadi na 1b). da solubility na alloying abubuwa a cikin narke, mun yi samfurin CuAgTaTi quaternary tsarin a matsayin ingantaccen tsarin (CuAg) TaTi ternary tsarin wanda solubility na Ti da Ta dogara da maida hankali na Ag a cikin CuAg narke (duba bayanin kula) 2 da Ƙari Hotuna 2-4).Bugu da ƙari na Ag baya ƙara ƙaddamar da Ti a gefen tsarin da aka wakilta.Duk da haka, tun da mai narkewar Ti a cikin Ag ya yi ƙasa da na Cu, wannan yana rage \({c}_{{{{{\rm{Ta}}}}}}}}}}^{l}\) (Ƙarin Fig. 1) 4b) da yawan zubar da ciki Ta.
Sakamako na siminti na filin lokaci ya nuna cewa haɓakar haɗe-haɗe suna zama mara karko cikin isassun lokaci mai tsawo don haɓaka samuwar sifofi da aka haɗa tare a gaban ruɓe.Mun gwada gwadawa tabbatar da wannan ƙarshe ta hanyar nuna cewa madaidaicin Layer na alloy Ta15T85, wanda ke samuwa a kusa da gaban delamination a wani mataki na delamination na gaba, ya kasance da alaƙa da yanayin yanayin bayan etching na lokaci mai arzikin jan ƙarfe.Sakamakonmu kuma yana ba da shawarar cewa yawan ɗigon ruwa yana da babban tasiri akan juyin halitta saboda yawan jigilar abubuwan da ba a taɓa gani ba a cikin ruwa narke.An nuna a nan cewa wannan tasirin, wanda ba ya nan a cikin ECD, yana tasiri sosai ga bayanan tattara bayanai na abubuwa daban-daban a cikin daftarin da aka wakilta, juzu'in lokaci mai ƙarfi, da topology na tsarin LMD.
A cikin wannan sashe, mun fara gabatar da sakamakon bincikenmu ta hanyar simintin filin lokaci na tasirin ƙara Ti ko Ag zuwa Cu narke wanda ya haifar da nau'i daban-daban.A kan fig.Hoto na 1 yana gabatar da sakamakon ƙirar ƙira mai girma uku na filin lokaci na TaXTi1-X alloys da aka samu daga Cu70Ti30, Cu70Ag30 da jan ƙarfe mai tsafta yana narkewa tare da ƙaramin atomic abun ciki na abubuwan da ba a taɓa gani ba daga 5 zuwa 15%.Layukan farko guda biyu sun nuna cewa ƙari na duka Ti da Ag yana haɓaka samuwar tsarin haɗin kai idan aka kwatanta da tsarin da ba a ɗaure ba na tsantsar Cu (jere na uku).Koyaya, ƙari na Ti, kamar yadda ake tsammani, yana ƙaruwa ta ɗigon Ta, don haka yana hana lalata ƙananan alluran X (Ta5Ti95 da Ta10Ti90) da haifar da ɗimbin narkar da ɓangarorin ɓarna mai ɓarna yayin delamination Ta15Ti85.Akasin haka, ƙari na Ag (jere na biyu) yana ba da gudummawa ga samuwar tsarin da ke da alaƙa da duk abubuwan haɗin ginin tushe tare da ɗan rushewar Layer ɗin da aka wakilta.Samuwar tsari mai ci gaba kuma an kwatanta shi a cikin Figs.1b, wanda ke nuna hotunan tsarin da aka wakilta tare da haɓaka zurfin delamination daga hagu zuwa dama da kuma hoton madaidaicin ruwa mai ƙarfi a zurfin zurfin (hoton dama mai nisa).
Simulation filin lokaci na 3D (128 × 128 × 128 nm3) yana nuna tasiri mai ban mamaki na ƙara soluti zuwa narkewar ruwa akan tsarin halittar ƙarshe na alloy ɗin da aka wakilta.Alamar babba tana nuna abun da ke tattare da haɗin gwal na iyaye (TaXti1-X) kuma alamar tsaye tana nuna narke abun da ke cikin matsakaicin laushi na tushen Cu.Wuraren da ke da babban taro na Ta a cikin tsari ba tare da ƙazanta ba ana nuna su cikin launin ruwan kasa, kuma ana nuna alamar ruwa mai ƙarfi a cikin shuɗi.b Simulation mai girma uku na filin zamani na Ta15Ti85 precursor alloy wanda ba a kwance ba a cikin Cu70Ag30 narke (190 × 190 × 190 nm3).Firam guda 3 na farko suna nuna ƙaƙƙarfan yanki na tsarin da aka wakilta a zurfin wakilai daban-daban, kuma firam na ƙarshe yana nuna kawai ƙaƙƙarfan keɓancewar ruwa a matsakaicin zurfin.Fim ɗin da ya yi daidai da (b) ana nuna shi a Ƙarin Fim na 1.
An ci gaba da bincika tasirin ƙari na solute tare da simintin filin wasan 2D, wanda ya ba da ƙarin bayani game da samuwar yanayin tsaka-tsaki a gaban delamination kuma ya ba da damar isa ga tsayi da ma'auni na lokaci fiye da simintin 3D don ƙididdige kinetics na delamination.A kan fig.Hoto na 2 yana nuna hotunan kwaikwaiyo na cire Ta15Ti85 precursor alloy ta hanyar Cu70Ti30 da Cu70Ag30 narke.A cikin duka biyun, haɓakar haɓaka-haɗe-haɗe ba shi da kwanciyar hankali.Maimakon shiga a tsaye a cikin gami, tukwici na tashoshi na ruwa suna motsawa cikin rudani hagu da dama a cikin rikitattun yanayi yayin tsarin haɓakar barga wanda ke haɓaka tsarin da aka daidaita wanda ke haɓaka samuwar tsarin da ke da alaƙa a cikin sararin 3D (Fig. 1).Duk da haka, akwai muhimmin bambanci tsakanin Ti da Ag additives.Don narkewar Cu70Ti30 (Fig. 2a), karo na tashoshi na ruwa guda biyu yana haifar da haɗuwa da ƙayyadaddun ƙayyadaddun ruwa mai ƙarfi, wanda ke haifar da extrusion na daskararrun masu ɗaure da tashoshi biyu suka kama daga tsarin kuma, a ƙarshe, zuwa rushewa. .Akasin haka, don narkewar Cu70Ag30 (Fig. 2b), Ta haɓakawa a tsaka-tsakin tsaka-tsakin ƙarfi da ruwa yana hana haɗin gwiwa saboda raguwar Ta yadudduka a cikin narke.A sakamakon haka, an danne matsi na haɗin gwiwa a gaban delamination, don haka inganta samuwar tsarin haɗin kai.Abin sha'awa shine, motsin motsi na oscillatory mai rudani na tashar ruwa yana haifar da tsari mai nau'i biyu tare da wani nau'i na daidaitawa lokacin da aka dakatar da yanke (Fig. 2b).Duk da haka, wannan jeri ba shine sakamakon ingantaccen haɓakar haɗin gwiwa ba.A cikin 3D, shigarwa mara ƙarfi yana haifar da tsarin da ba a haɗa shi ba tare da coaxial (Fig. 1b).
Hotunan hotunan filin wasan kwaikwayo na zamani na 2D na Cu70Ti30 (a) da Cu70Ag30 (b) sun narke zuwa Ta15Ti85 gami da ke nuna haɓakar haɓakar haɓakar da ba ta da ƙarfi.Hotunan da ke nuna zurfin cire ƙazanta daban-daban waɗanda aka auna daga wurin farko na lebur mai ƙarfi/ruwa.Abubuwan da aka shigar suna nuna tsarin mulki daban-daban na karo na tashar ruwa, wanda ke haifar da rarrabuwar kawuna masu ƙarfi da adana Cu70Ti30 da Cu70Ag30 narke, bi da bi.Faɗin yanki na Cu70Ti30 shine 1024 nm, Cu70Ag30 shine 384 nm.Ƙaƙwalwar launi tana nuna ƙaddamarwar Ta, kuma launuka daban-daban suna bambanta tsakanin yankin ruwa (duhu mai duhu), gunkin tushe (shuɗi mai haske), da tsarin da ba a haɗa shi ba (kusan ja).Fina-finan waɗannan simintin an nuna su a Ƙarin Fina-Finai na 2 da 3, waɗanda ke haskaka hadaddun hanyoyin da ke ratsa tashoshi na ruwa yayin haɓakar haɓakar yaɗuwar da ba ta da kyau.
Sauran sakamakon 2D lokaci siminulation filin ana nuna a cikin Fig.3.Hotunan zurfin delamination tare da lokaci ( gangare daidai da V) a cikin fig.3a yana nuna cewa ƙari na Ti ko Ag zuwa Cu narke yana rage jinkirin rabuwa, kamar yadda aka sa ran.A kan fig.3b yana nuna cewa wannan jinkirin yana faruwa ne ta hanyar raguwar raguwar tattarawar Ti a cikin ruwa a cikin rukunin da aka wakilta.Hakanan yana nuna cewa ƙari na Ti (Ag) yana ƙaruwa (raguwa) ƙaddamarwar Ti a gefen ruwa na mahaɗin (\({c}_{{{{{{\rm{Ti))))))) ))) ^{l \) ), wanda ke haifar da zubar da Ta, wanda aka auna ta hanyar juzu'in Ta narkar da shi a matsayin aikin lokaci (Fig. 3c), wanda ya karu (raguwa) tare da ƙarin Ti (Ag). ).Hoto na 3d yana nuna cewa duka biyun solutes, ƙarar juzu'i na daskararrun ya kasance sama da maƙasudin samuwar sifofi masu alaƙa da juna28,29,30.Yayin da ƙara Ti zuwa narkewa yana ƙara ɗigowar Ta, yana kuma ƙara riƙe Ti a cikin ɗauri mai ƙarfi saboda daidaiton lokaci, don haka ƙara juzu'in ƙara don kiyaye haɗin tsarin ba tare da ƙazanta ba.Ƙididdigar mu gabaɗaya sun yarda da ma'aunin gwaji na juzu'in juzu'i na gaba.
Simulation filin wasan lokaci na alloy na Ta15Ti85 yana ƙididdige tasirin daban-daban na ƙari na Ti da Ag zuwa Cu narke akan abubuwan cirewar gami da aka auna daga zurfin cire alloy azaman aikin lokaci (a), bayanin martabar Ti a cikin ruwa a wani lokaci. zurfin cire alloy na 400 nm (zurfin mara kyau yana faɗaɗa cikin narkewa a waje da tsarin gami (gaban allo a hagu) b Ta leakage tare da lokaci (c) da ƙaƙƙarfan juzu'i a cikin tsarin da ba a haɗa shi ba tare da abun da ke narkewa (d) Tattaunawar ƙarin abubuwa. a cikin narke an ƙulla tare da abscissa (d). (Ti - layin kore, Ag - layin purple da gwaji).
Tun da saurin gaban delamination yana raguwa tare da lokaci, juyin halitta na ilimin halittar jiki yayin ƙaddamarwa yana nuna tasirin rage saurin lalata.A cikin binciken filin da ya gabata, mun lura da haɓakar eutectic-kamar haɗe-haɗe wanda ya haifar da daidaitattun tsarin da ba a ɗaure ba yayin cire Ta15Ti85 precursor gami da tsantsar jan ƙarfe mai narkewa15.Koyaya, tsayin gudu na simintin filin lokaci ɗaya yana nuna (duba Ƙarin Fim na 4) cewa lokacin da bazuwar gaba ya zama ƙanƙanta, haɓakar haɗe-haɗe ya zama mara ƙarfi.Rashin kwanciyar hankali yana bayyana kansa a cikin ruɗaɗɗen gefe na flakes, wanda ya hana daidaitawar su kuma, don haka, yana inganta samuwar tsarin haɗin kai.Canji daga ci gaban dauri mai tsayi zuwa girma mai girgiza mara karko yana faruwa kusa da xi = 250 nm akan ƙimar 4.7 mm/s.Akasin haka, madaidaicin zurfin delamination xi na Cu70Ti30 narke shine kusan 40 nm a daidai wannan ƙimar.Saboda haka, ba za mu iya lura da irin wannan canji ba lokacin cire gami da narkewar Cu70Ti30 (duba Ƙarin Fim na 3), saboda ƙara 30% Ti zuwa narkewa yana rage haɓakar haɓakar gami.A ƙarshe, kodayake haɓakar haɓaka-haɗe-haɗe ba shi da kwanciyar hankali saboda jinkirin motsin motsin motsi, nisan λ0 na igiyoyi masu ƙarfi a gaban delamination yana yin biyayya da dokar ({\lambda }_{0}^{2}V=C\) na tsaye. girma15,31 inda C ne akai.
Don gwada tsinkayar simintin filin lokaci, an yi gwaje-gwajen cire alloy tare da samfurori mafi girma da lokutan cire gami da tsayi.Hoto 4a zane ne na tsari wanda ke nuna mahimman sigogin tsarin da aka wakilta.Jimlar zurfin delamination daidai yake da xi, nisa daga farkon iyakar ƙaƙƙarfan matakan ruwa da ruwa zuwa gaban delamination.hL shine nisa daga farkon ma'aunin ruwa mai ƙarfi zuwa ƙarshen tsarin da aka wakilta kafin etching.Babban hL yana nuna ƙarfi Ta yayyo.Daga hoton SEM na samfurin wakilci, za mu iya auna girman HDD na tsarin da aka wakilta kafin etching.Duk da haka, tun da narke kuma yana ƙarfafawa a zafin jiki, yana yiwuwa a riƙe tsarin da aka wakilta ba tare da shaidu ba.Sabili da haka, mun ƙaddamar da narke (lokacin mai arziki na jan karfe) don samun tsarin canji kuma mun yi amfani da hC don ƙididdige kauri na tsarin canji.
zane mai tsari na juyin halittar halittar jiki yayin kawar da ƙazanta da ƙayyadaddun sigogi na geometric: ƙyalli kauri Ta hL, kauri na tsarin da aka lalata, kauri na tsarin haɗin hC.(b), (c) Gwajin ingantattun sakamako na simintin filin lokaci wanda ya kwatanta sassan giciye na SEM da 3D etched ilimin halittar jiki na Ta15Ti85 alloy wanda aka shirya daga tsantsar Cu (b) da Cu70Ag30 yana narkewa, yana ba da haɗin kai na topological tare da tsarin girman haɗin kai (c), mashaya sikelin. 10 µm ku.
Sassan giciye na tsarin da aka wakilta da aka nuna a fig.4b,c tabbatar da babban tasirin da aka annabta na ƙara Ti da Ag zuwa Cu narke akan ilimin halittar jiki da motsin abubuwan da aka wakilta.A kan fig.Hoto 4b yana nuna ƙananan yanki na yanke SEM (a hagu) na Ta15T85 alloy ta hanyar nutsewa a cikin tagulla mai tsabta don 10 s zuwa zurfin xi ~ 270 μm.A kan ma'aunin gwaji da za'a iya aunawa, wanda shine umarni da yawa na girma fiye da na wasan kwaikwayo na filin lokaci, saurin juyewar gaban gaba yana ƙasa da saurin ƙofa da aka ambata na 4.7 mm/s, a ƙasa wanda ingantaccen haɗin haɗin eutectic ya zama mara ƙarfi.Sabili da haka, ana sa ran tsarin da ke sama da gaban kwasfa zai kasance da cikakken haɗin kai.Kafin etching, wani bakin ciki Layer na tushen gami da aka narkar da gaba daya (hL = 20 μm), wanda aka hade da Ta leakage (Table 1).Bayan etching sinadarai na lokaci mai arzikin jan ƙarfe (dama), ƙaramin ƙaramin allo na wakilai (hC = 42 µm) ne kawai ya rage, yana nuna cewa yawancin tsarin da aka wakilta ya ɓace amincin tsarin yayin etching kuma ba, kamar yadda ake tsammani, topologically bonded ( Hoto 1 a)., hoton da ya dace a jere na uku).A kan fig.4c yana nuna cikakken sashin giciye na SEM da hotunan 3D na etching na alloy Ta15Ti85 wanda aka cire ta nutsewa a cikin Cu70Ag30 narke don 10 s zuwa zurfin kusan 200 µm.Tun da zurfin kwasfa ana hasashen zai ƙaru tare da \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\) sarrafa motsin motsin motsi (duba Karin Bayani na 4) 15 16, Tare da ƙari na 30% Ag zuwa Cu narke, raguwa a cikin zurfin rabuwa daga 270 μm zuwa 220 μm ya dace da raguwa a cikin lambar Peclet p ta hanyar 1.5.Bayan etching sinadarai na lokaci mai albarka na Cu/A (dama), duk tsarin da aka wakilta yana riƙe da mutuncin tsari (hC = 200 µm), yana nuna cewa ainihin tsari ne mai haɗaɗɗiyar yanayin yanayi (Hoto 1, mafi kyawun hoto) jere na biyu da gaba ɗaya. layin kasa).Dukkan ma'auni na abin da aka wakilta ta alloy Ta15T85 a cikin narkewa daban-daban an taƙaita su a cikin Tebur.1. Har ila yau, muna gabatar da sakamako don unalloyed Ta10Ti90 tushe gami a cikin daban-daban narkewa, tabbatar da mu ƙarshe.Ma'aunai na kauri mai ƙyalƙyali Ta nuna cewa tsarin da aka narkar a cikin Cu70Ag30 narke (hL = 0 μm) ya fi wannan a cikin tsantsar Cu narke (hL = 20 μm).Akasin haka, ƙari na Ti zuwa narkewa yana narkar da sifofi marasa ƙarfi (hL = 190 μm).Ragewar rushewar tsarin da aka wakilta tsakanin tsantsar Cu narke (hL = 250 μm) da narkewar Cu70Ag30 (hL = 150 μm) ya fi fitowa fili a cikin abubuwan da aka wakilta bisa Ta10Ti90.
Don fahimtar tasirin narkewa daban-daban, mun yi ƙarin bincike na ƙididdiga na sakamakon gwaji a cikin siffa 5 (duba kuma Ƙarin Bayanai 1).A kan fig.Figures 5a-b suna nuna ma'auni na rarraba abubuwa daban-daban tare da jagorancin exfoliation a cikin gwaje-gwajen exfoliation a cikin tsabta Cu narke (Fig. 5a) da Cu70Ag30 narke (Fig. 5b).An tsara ƙididdiga na abubuwa daban-daban akan nisa d daga gaban delamination zuwa gefen Layer delamination a cikin ɗauri mai ƙarfi da kuma lokacin da yake ruwa (wadata cikin Cu ko CuAg) a lokacin ƙaddamarwa.Ba kamar ECD ba, inda aka ƙaddara riƙe abubuwan da ba daidai ba ta hanyar adadin rabuwa, a cikin LMD, ƙaddamarwa a cikin ɗaure mai ƙarfi yana ƙaddara ta hanyar ma'auni na thermodynamic na gida tsakanin matakai masu ƙarfi da ruwa kuma, don haka, kaddarorin haɗin kai na m. matakan ruwa.Alamar Jahar Alloy.Saboda narkar da Ti daga tushe gami, Ti maida hankali rage tare da kara d daga delamination gaba zuwa gefen delamination Layer.A sakamakon haka, ƙaddamarwar Ta ya karu tare da ƙara d tare da damfara, wanda ya dace da simintin filin lokaci (Ƙarin Hoton 5).Matsakaicin Ti a cikin narkewar Cu70Ag30 ya faɗi ƙasa kaɗan fiye da narken Cu mai tsafta, wanda ya yi daidai da ƙimar cire gami a hankali.Ƙididdigar ƙididdiga masu yawa a cikin Fig.5b kuma ya nuna cewa rabo daga cikin taro na Ag da Cu a cikin ruwa ba daidai ba ne tare da Layer na wakilta gami, yayin da a cikin simulation na lokaci filin wannan rabo da aka zaci zama akai a cikin kwaikwaiyo na narkewa kamar yadda. Cu70Ag30.Duk da wannan bambance-bambancen ƙididdiga, ƙirar filin lokaci yana ɗaukar babban tasiri na ƙara Ag akan murkushe Ta.Cikakken ƙididdige ƙididdige ƙirar ƙira na duk abubuwan abubuwa guda huɗu a cikin ƙwararrun masu ɗaure da ruwaye suna buƙatar ingantaccen tsari mai sassa huɗu na zane-zane na TaTiCuAg, wanda ya wuce iyakar wannan aikin.
Ma'auni bayanan martaba dangane da nisa d daga delamination gaban Ta15Ti85 gami a (a) tsantsar Cu narke da (b) Cu70Ag30 narke.Kwatanta ma'auni juzu'in juzu'i na daskararru ρ(d) na tsarin da aka wakilta (layi mai ƙarfi) tare da tsinkayar ka'idar da ta dace da ma'auni ba tare da zubewar Ta (layin dage).(1) (c) Hasashen haɓakar ƙima.(1) Daidaita daidaito a gaban delamination.(2) Wato Ta leakage ana la'akari.Auna matsakaicin faɗin haɗin λw da nisa λs (d).Kuskuren sanduna suna wakiltar daidaitaccen karkatacciyar hanya.
A kan fig.5c yana kwatanta ƙayyadaddun juzu'in juzu'i na daskararru ρ (d) (layi mai ƙarfi) don tsantsar tsarin Cu da Cu70Ag30 waɗanda aka wakilta daga narke tare da tsinkayar ka'idar (layin dage) da aka samu daga kiyaye yawan jama'a ta amfani da auna ma'aunin Ta a cikin ingantaccen ɗaure \({ c }_ {Ta}^{s}(d)\) (Fig. 5a,b) da kuma watsi da yoyon Ta da safarar Ta tsakanin igiyoyi da zurfin rarrabuwa daban-daban.Idan Ta ya canza daga ƙaƙƙarfan zuwa ruwa, duk Ta da ke ƙunshe a cikin gariyar tushe dole ne a sake rarraba shi zuwa madaidaicin ɗaure.Don haka, a cikin kowane Layer na tsarin nesa wanda yake daidai da alkiblar cire gawa, kiyaye yawan jama'a yana nufin cewa \({c}_{Ta}^{s}(d){S}_{s}(d) )={c}_ {Ta}^{0}(d){S}_{t}\), inda \({c}_{Ta}^{s}(d)\) da \({c) }_{Ta }^ {0}\) sune abubuwan Ta a matsayi d a cikin abin ɗaure da matrix alloy, bi da bi, kuma Ss (d) da St sune wuraren giciye na mai ɗaure mai wuya da duk yanki mai nisa, bi da bi.Wannan yana tsinkayar girman juzu'in daskararru a cikin Layer mai nisa.
Ana iya amfani da wannan cikin sauƙi ga tsarin da aka wakilta pure Cu da Cu70Ag30 narke ta amfani da madaidaicin \({c}_{Ta}^{s}(d)\) masu lanƙwasa daidai da layin shuɗi.Waɗannan tsinkaya an fi ƙarfinsu akan siffa 5c suna nuna cewa yin watsi da zubar Ta shine rashin hangen nesa na rarraba juzu'i.Kiyaye yawan jama'a ba tare da yatsa ba yana annabta raguwar monotonic a cikin juzu'in juzu'i tare da ƙara d, wanda aka lura da shi a cikin tsantsar Cu narke, amma ba a cikin Cu70Ag30 narke ba, inda ρ(d) ke da ƙaranci.Bugu da ƙari, wannan yana haifar da ƙima mai mahimmanci na ƙananan juzu'i a gaban rabuwa don duka narke.Don mafi ƙarancin ma'auni d ≈ 10 µm, ƙimar ρ da aka annabta don duka narke sun wuce 0.5, yayin da ma'aunin ρ na Cu da Cu70Ag30 narke sun ɗan fi 0.3 da 0.4, bi da bi.
Don jaddada babban aikin leakage Ta, sai mu nuna cewa bambance-bambancen ƙididdiga tsakanin ma'auni da ƙididdiga na ρ da ke kusa da gaban lalata za a iya kawar da su ta hanyar tsaftace tsinkayen tsinkayenmu don haɗawa da wannan leka.Don wannan, bari mu ƙididdige adadin adadin Ta atom ɗin da ke gudana daga ƙaƙƙarfan ruwa zuwa ruwa lokacin da ruɓewar gaba ta motsa a nesa Δxi = vΔt a cikin tazarar lokaci Δt Δxi = vΔt, inda \(v={\dot{x) )) _{i }( t ) \) - ƙididdige ƙima, zurfin da lokaci ana iya samo su daga dangantakar da aka sani \({x}_{i} (t)=\sqrt{4p{D}_{l}t } \) rashin hankali.Doka ta gida na kiyaye taro a gaban rabuwa (d ≈ 0) shine irin wannan ΔN = DlglΔtSl/va, inda gl shine matakin maida hankali na Ta atom a cikin ruwa, va shine adadin atomic wanda yayi daidai da maida hankali da aka ayyana azaman juzu'in atomic, da Sl = St - Ss shine yanki na yanki na tashar ruwa a gaban delamination.Ana iya ƙididdige ma'aunin maida hankali gl ta hanyar ɗauka cewa tattarawar Ta atoms yana da ƙima mai ɗorewa \({c}_{Ta}^{l}\) a mahaɗar kuma yana da ƙanƙanta a cikin narkewar waje na exfoliated Layer, wanda yana bada \( {g}_ {l}={c}_{Ta}^{l}/{x}_{i}\) So, \({{\Delta}}N=({{\Delta} {x}_{i} {S}_{l}/{v}_{a}){c}_{Ta}^{l}/(2p)\).Lokacin da gaba ya matsa zuwa nesa Δxi, ƙaƙƙarfan juzu'in yana daidai da jimlar adadin Ta atom da aka cire daga gunkin alloy, \({{\Delta}}{x}_{i}{S}_{t} { c }_{Ta}^ {0}/{v}_{a}\), zuwa jimlar adadin Ta atom da ke zubowa cikin ruwa, ΔN, kuma an haɗa su a cikin maɗaurin ƙarfi\({{ \Delta}) } {x}_{i}{S}_{s }{c}_{Ta}^{s}/{v}_{a}\).Wannan ma'auni, tare da bayanin da ke sama don ΔN da dangantakar St = Ss + Sl da matakai a gaban delamination.
A cikin iyakar sifili mai narkewa na Ta atoms, wanda ke ragewa zuwa farkon hasashen rashin leaks, \(\rho ={c}_{Ta}^{0}/{c}_{Ta}^{s} \) ruwa ( \({c }_{Ta}^{l}=0\)).Yin amfani da ma'auni \ ({c}_{Ta}^{l} \ game da 0.03 \) daga ma'auni na gwaji (ba a nuna su a cikin Fig. 5a, b) da lambobin Peclet p ≈ 0.26 da p ≈ 0.17 da daskararrun ma'auni \ ( {c}_{Ta}^{s} kusan 0.3 \) da \({c}_{Ta}^{s}\kimanin 0.25 \) don Cu da Cu70Ag30 sun narke, bi da bi , mun sami ƙimar annabta na Narke, ρ ≈ 0.38 da ρ ≈ 0.39.Waɗannan tsinkaya suna da ƙima cikin ingantacciyar yarjejeniya tare da ma'auni.Sauran bambance-bambance (an annabta 0.38 vs. auna 0.32 don tsantsar Cu narke da 0.39 annabta vs. auna 0.43 don Cu70Ag30 narkewa) ana iya bayyana shi ta mafi girman rashin tabbas ga ƙarancin Ta a cikin ruwaye (\({c}_{Ta) }^ {l}\kimanin 0.03\)), wanda ake tsammanin zai zama ɗan girma a cikin tsantsar narkar da tagulla.
Kodayake gwaje-gwajen da aka yi a yanzu an yi su ne a kan ƙayyadaddun abubuwan haɗin ginin da narke, muna sa ran cewa sakamakon binciken waɗannan gwaje-gwajen zai taimaka wajen samo ma'auni.(2) Faɗin zartarwa ga sauran tsarin LMD doping da sauran hanyoyin da ke da alaƙa kamar Solid State Impurity Removal (SSD).Har ya zuwa yanzu, an yi watsi da tasirin kwararar abubuwan da ba za a iya kwatanta su ba akan tsarin LMD gaba ɗaya.Wannan ya faru ne saboda gaskiyar cewa wannan tasirin ba shi da mahimmanci a cikin ECDD, kuma ya zuwa yanzu an yi tunanin cewa NMD yana kama da REC.Duk da haka, babban bambanci tsakanin ECD da LMD shine cewa a cikin LMD ƙwaƙƙwarar abubuwan da ba za a iya kwatanta su ba a cikin ruwaye suna karuwa sosai saboda yawan abubuwan da ba su da kyau a gefen ruwa na mahaɗin ({c}_{Ti} ^{ l}\)), wanda hakan yana ƙara yawan abubuwan da ba za a iya kwatanta su ba (\({c}_{Ta}^{l}\)) a gefen ruwa na mahaɗar kuma yana rage juzu'in juzu'in da aka annabta ta madaidaicin yanayi. .(2) Wannan haɓakawa ya faru ne saboda gaskiyar cewa ƙaƙƙarfan ƙirar ruwa a lokacin LMD yana cikin ma'auni na thermodynamic na gida, don haka babban \({c}_{Ti}^{l}\) yana taimakawa wajen haɓaka \({c} _) {Ta} ^{l}\ Hakazalika, babban \({c}_{Ti}^{s}\) yana ba da damar shigar da Cu cikin masu ɗaure masu wuya, kuma ƙaddamarwar Cu a cikin waɗannan ɗauren ya bambanta daga kusan 10% a hankali. ragewa zuwa dabi'u ne negligible a gefen kananan delegated Layer (Karin siffa. 6) .A bambanci, da electrochemical cire Ag daga AgAu gami da ECD ne mara daidaito dauki da cewa ba ya ƙara solubility na Au a cikin da electrolyte. Baya ga LMD, muna kuma fatan cewa sakamakonmu ya dace da ƙwararrun ƙwararrun jihohi, inda ake sa ran iyakar iyaka don kula da ma'aunin thermodynamic na gida yayin cirewar gami. An lura da daskararru a cikin rukunin da aka wakilta na tsarin SSD, yana nuna I, cewa a lokacin tawagar akwai narkar da ƙaƙƙarfan ligament, wanda ke da alaƙa da zubar da abubuwan da ba su da kyau.
Kuma ma'auni.(2) Don yin hasashen raguwar raguwar ƙaƙƙarfan juzu'i a gaban cirewar alloy saboda yatsaniyar Ta, Hakanan ya zama dole a la'akari da jigilar Ta a cikin yankin kawar da gami don fahimtar ƙaƙƙarfan rarraba juzu'i a cikin duka. alloy cire Layer, wanda yayi daidai da tagulla mai tsabta da Cu70Ag30 narke.Don narkewar Cu70Ag30 (layin ja a cikin siffa 5c), ρ(d) yana da ƙarancin kusan rabin abin da aka wakilta.Wannan mafi ƙarancin shi ne saboda gaskiyar cewa jimlar adadin Ta da ke ƙunshe a cikin ɗaurin wuyar kusa da gefen layin da aka wakilta ya fi girma fiye da a cikin haɗin ginin.Wato na d ≈ 230 μm \({S}_{s}(d){c}_{Ta}^{s}(d)\, > \,{S}_{t}{c} _ {Ta}^{0}\), ko kuma yayi daidai, ma'aunin ρ(d) = Ss(d)/St ≈ 0.35 ya fi girma fiye da yadda aka annabta.(1) Babu yabo\({c}_{Ta}^{0}/{c}_{Ta}^{s}(d)\kimanin 0.2\).Wannan yana nufin cewa wani ɓangare na tserewa Ta ana ɗaukar shi daga gaban rabuwa zuwa wani yanki mai nisa daga wannan gaba, yana yaduwa a cikin ruwa da kuma tare da ingantaccen ruwa mai ƙarfi, inda aka sake dawo da shi.
Wannan sake fasalin yana da akasin tasirin Ta don wadatar da masu ɗaure masu wuyar Ta, kuma za a iya bayyana rabe-raben ƙwaƙƙwaran ƙwaƙƙwara a matsayin ma'auni na zubar Ta da sake fasalin.Don narkewar Cu70Ag30, ƙaddamarwar Ag a cikin ruwa yana ƙaruwa tare da ƙara d (layin dige mai launin ruwan kasa a cikin siffa 5b) don rage raguwar Ta ta hanyar rage Ta solubility, wanda ke haifar da karuwa a cikin ρ (d) tare da ƙara d bayan ya kai ƙarami. .Wannan yana kiyaye ƙaƙƙarfan yanki mai girma wanda zai hana rarrabuwa saboda rarrabuwar kawuna, wanda ke bayanin dalilin da yasa tsarin da aka wakilta a cikin Cu70Ag30 narke yana riƙe amincin tsarin bayan etching.Sabanin haka, don tsantsar jan ƙarfe na narkewa, yoyo da redeposition sun kusan soke juna, wanda ke haifar da raguwar daskararrun da ke ƙasa da maƙasudin rarrabuwar kawuna ga mafi yawan maƙallan da aka wakilta, yana barin ƙaramin bakin ciki ne kawai wanda ke riƙe amincin tsarin kusa da kan iyakar. wakilta Layer.(Hoto na 4b, Table 1).
Ya zuwa yanzu, bincikenmu ya fi mayar da hankali kan yin bayanin tasirin tasirin ɗigon abubuwa masu ɓarna a cikin matsakaita mai tarwatsewa akan ƙaƙƙarfan juzu'i da yanayin tsarin da aka wakilta.Yanzu bari mu juya zuwa ga tasirin wannan ɗigon ruwa akan murƙushe tsarin bicontinuum a cikin rukunin da aka wakilta, wanda yawanci ke faruwa yayin LMD saboda yanayin yanayin aiki mai girma.Wannan ya bambanta da ECD inda coarsening kusan babu shi yayin cire gami, amma ana iya lalacewa ta hanyar annealing a yanayin zafi mafi girma bayan cire gami.Ya zuwa yanzu, an ƙirƙiri ƙira yayin LMD a ƙarƙashin zaton yana faruwa ne saboda yaɗuwar abubuwan da ba za a iya kwatanta su ba tare da ƙaƙƙarfan mu'amalar ruwa, mai kama da rarrabuwar-tsakiyar tsaka-tsakin saman na sifofin ECD na nanoporous.Don haka, an ƙirƙira girman haɗin haɗin ta amfani da daidaitattun dokokin ƙa'idar haɓaka ƙarfin ƙarfi.
inda tc shine lokacin haɓakawa, wanda aka ayyana azaman lokacin da ya wuce bayan wucewar gaba ta gaba a zurfin xi a cikin Layer na delamination (inda λ yana da ƙimar farko na λ00) har zuwa ƙarshen gwajin delamination, da ma'aunin sikelin n = 4 yana watsa saman.Ya kamata a yi amfani da Eq tare da taka tsantsan.(3) Fassara ma'auni na λ da nisa d don tsari na ƙarshe ba tare da ƙazanta ba a ƙarshen gwajin.Wannan shi ne saboda gaskiyar cewa yankin da ke kusa da gefen ɓangaren da aka wakilta yana ɗaukar tsawon lokaci don girma fiye da yankin da ke kusa da gaba.Ana iya yin wannan tare da ƙarin ma'auni.(3) Sadarwa tare da tc da d.Ana iya samun wannan alaƙa cikin sauƙi ta hanyar tsinkayar zurfin cire gami a matsayin aikin lokaci, \({x}_{i}(t)=\sqrt{4p{D}_{l}t}\), wanda ke bada tc( d ) = te − tf(d), inda te shine tsawon lokacin gwajin gaba dayansa, \({t}_{f}(d)={(\sqrt{4p{D}_{l} {t}_{ e } }-d)}^{2}/(4p{D}_{l})\) shine lokacin da za'a iya kaiwa ga zurfafa daidai da zurfin delamination na ƙarshe a debe d.Toshe wannan magana don tc(d) cikin lissafin.(3) Yi tsinkaya λ(d) (duba ƙarin bayanin kula 5).
Don gwada wannan hasashe, mun yi ma'auni na faɗi da nisa tsakanin dam ɗin akan cikakkun sassan giciye na tsarin da aka wakilta da aka nuna a Ƙarin Hoto 9 don tsantsar Cu da Cu70Ag30 narke.Daga sikanin layi daidai gwargwado zuwa jagorar delamination a nisa daban-daban d daga gaban delamination, mun sami matsakaicin faɗin λw (d) na Ta-rich bundles da matsakaicin nisa λs(d) tsakanin daure.Ana nuna waɗannan ma'auni a cikin fig.5d kuma idan aka kwatanta da hasashen ma'auni.(3) a Ƙarin Hoto 10 don ƙima daban-daban na n.Kwatankwacin ya nuna cewa fihirisar yaɗuwar ƙasa na n = 4 yana ba da tsinkaya mara kyau.Wannan tsinkayar ba ta inganta sosai ta zaɓin n = 3 don haɓakar ɗimbin yawa-matsakaici na capillary coarsening, wanda mutum zai iya sa ran zai samar da ingantacciyar dacewa saboda zubar Ta cikin ruwa.
Wannan bambance-bambancen adadi tsakanin ka'idar da gwaji ba abin mamaki bane, tun da Eq.(3) ya bayyana coarsening capillary a akai-akai juzu'i juzu'i ρ, yayin da a LMD da daskararru juzu'i ρ ba akai.ρ yana canzawa a sarari a cikin Layer da aka cire a ƙarshen cirewar gami, kamar yadda aka nuna a cikin fig.5c ku.ρ kuma yana canzawa tare da lokaci yayin cire ƙazanta a ƙayyadaddun zurfin cirewa, daga ƙimar gaban cirewa (wanda yake kusan tsayin lokaci kuma don haka mai zaman kansa daga tf da d) zuwa ƙimar ƙimar ρ (d) da aka nuna a cikin siffa. 5c daidai da lokacin ƙarshe.Daga fig.3d, ana iya ƙididdige cewa ƙimar gaban lalacewa ta kusan 0.4 da 0.35 don AgCu da tsabta Cu narke, bi da bi, wanda a duk lokuta ya fi ƙimar ƙarshe na ρ a lokacin te.Yana da mahimmanci a lura cewa raguwa a cikin ρ tare da lokaci a ƙayyadaddun d shine sakamakon kai tsaye na kasancewar ma'auni mai mahimmanci na ɓangaren miscible (Ti) a cikin ruwa.Tun da maida hankali na Ti a cikin ruwaye yana raguwa tare da ƙara d, ma'auni na ma'auni na Ti a cikin daskararru shima aikin ragewa ne na d, wanda ke haifar da rushewar Ti daga masu ɗaure mai ƙarfi da raguwar ƙaƙƙarfan juzu'i na tsawon lokaci.Canjin na ɗan lokaci a cikin ρ shima yana shafar yoyo da sake fasalin Ta.Don haka, saboda ƙarin tasirin rushewa da maimaitawa, muna sa ran cewa haɓakawa yayin LMD zai kasance, a matsayin mai mulkin, zai faru a cikin juzu'in juzu'i marasa daidaituwa, wanda zai haifar da juyin halittar tsarin ban da haɓakawar capillary, amma kuma saboda yaduwa a ciki. ruwa kuma ba kawai tare da iyaka m-ruwa.
Bayanan daidaito.(3) Nisa da ma'aunin tazara na 3 ≤ n ≤ 4 ba a ƙididdige su ba (Ƙarin Hoton 10), yana ba da shawarar cewa rushewa da sake fasalin ba saboda raguwar dubawa suna taka muhimmiyar rawa a cikin gwaji na yanzu.Don coarsening capillary, λw da λs ana tsammanin samun dogaro iri ɗaya akan d, yayin da Fig. 5d ya nuna cewa λs yana ƙaruwa da d da sauri fiye da λw don tsantsar Cu da Cu70Ag30 narke.Yayin da ka'idar da ke yin la'akari da rushewa da sake fasalin dole ne a yi la'akari da ita don bayyana waɗannan ma'auni a adadi mai yawa, ana sa ran wannan bambanci da inganci, tun da cikakken rushewar ƙananan shaidu yana ba da gudummawa ga karuwa a cikin nisa tsakanin shaidu.Bugu da ƙari, λs na Cu70Ag30 narke ya kai matsakaicin darajarsa a gefen Layer ba tare da alloy ba, amma gaskiyar cewa λs na narke mai tsabta na jan karfe yana ci gaba da haɓaka monotonically za'a iya bayyana shi ta hanyar karuwa a cikin taro na Ag a cikin ruwa, inda d ana amfani da shi don bayyana ρ(d) a cikin siffa 5c halin da ba a taɓa gani ba.Ƙara haɓakar Ag tare da ƙara d yana hana zubar Ta da rushewar ɗaure, wanda ke haifar da raguwa a cikin λs bayan kai matsakaicin darajar.
A ƙarshe, lura cewa nazarin kwamfuta na coarsening capillary a akai-akai juzu'i juzu'i ya nuna cewa lokacin da juzu'in juzu'i fado kasa da kofa na kamar 0.329.30, tsarin gutsure a lokacin coarsening.A aikace, wannan bakin kofa na iya zama ɗan ƙasa kaɗan saboda rarrabuwa da raguwar jinsi ɗaya na faruwa akan sikelin lokaci mai kwatankwacin ko mafi girma fiye da jimlar lokacin cire gami a cikin wannan gwaji.Kasancewar tsarin da aka wakilta a cikin Cu70Ag30 narke yana riƙe amincin tsarin su duk da cewa ρ (d) ya ɗan yi ƙasa da 0.3 a matsakaicin kewayon d yana nuna cewa rarrabuwa, idan akwai, yana faruwa ne kawai a wani yanki.Matsakaicin juzu'in ƙarar don rarrabuwa na iya dogara da rushewa da maimaitawa.
Wannan binciken ya zana manyan abubuwa guda biyu.Na farko, kuma a aikace, ana iya sarrafa yanayin tsarin da aka wakilta ta LMD ta zaɓin narke.Ta hanyar zabar narkewa don rage narkewar abubuwan da ba za a iya kwatanta su ba A na AXB1-X base alloy a cikin narke, kodayake iyakance, ana iya ƙirƙirar tsarin da aka wakilta wanda ke riƙe da haɗin kai har ma da ƙarancin ƙima na rukunin bene X da daidaiton tsari. .A baya an san cewa wannan yana yiwuwa ga ECD25, amma ba ga LMD ba.Ƙarshe na biyu, wanda ya fi mahimmanci, shine dalilin da ya sa a cikin LMD za'a iya kiyaye mutuncin tsarin ta hanyar gyaggyarawa matsakaicin wakilci, wanda yake da ban sha'awa a cikin kansa kuma zai iya bayyana abubuwan da muke gani na TaTi alloy a cikin tsabta Cu da CuAg suna narkewa a cikin , amma kuma a ciki. gabaɗaya don fayyace mahimmanci, bambance-bambancen da ba a ƙima ba a baya tsakanin ECD da LMD.
A cikin ECD, ana kiyaye haɗin kai na tsarin ta hanyar kiyaye ƙarancin ƙazanta a ƙaramin matakin X, wanda ke dawwama akan lokaci don ƙayyadaddun ƙarfin tuƙi, ƙarami isa don kiyaye isassun abubuwan ɓarna B a cikin ɗauri mai ƙarfi yayin cire ƙazanta don kiyayewa. daskararrun girma.juzu'in ρ yana da girma sosai don hana ɓarna25.A cikin LMD, ƙimar cire alloy \(d{x}_{i}(t)/dt=\sqrt{p{D}_{l}/t}\) yana raguwa da lokaci saboda iyakantaccen motsin motsi.Don haka, ba tare da la'akari da nau'in abun da ke narke ba wanda ke shafar kawai lambar Peclet p, ƙimar delamination da sauri ta kai darajar ƙaramin isa don riƙe isasshen adadin B a cikin ɗauri mai ƙarfi, wanda ke nunawa kai tsaye a cikin gaskiyar cewa ρ a delamination gaba ya kasance kusan m tare da lokaci.Gaskiya kuma sama da ƙofofin rarrabuwa.Kamar yadda aka nuna ta hanyar simintin filin lokaci, ƙimar kwasfa shima da sauri ya kai ƙima kaɗan kaɗan don lalata haɓakar haɗin gwiwar eutectic, ta haka yana sauƙaƙe samuwar sifofi masu alaƙa saboda motsin motsin lamellae.Don haka, babban babban bambanci tsakanin ECD da LMD ya ta'allaka ne a cikin juyin halitta na gaba ta hanyar tsarin ciki na Layer bayan tsagawa da ρ, maimakon ƙimar delamination.
A cikin ECD, ρ da haɗin kai sun kasance masu tsayi a cikin layin nesa.A cikin LMD, akasin haka, dukansu sun bambanta a cikin wani Layer, wanda aka nuna a fili a cikin wannan binciken, wanda ke yin taswirar atomic taro da rarraba ρ cikin zurfin tsarin da aka ba da izini wanda LMD ya ƙirƙira.Akwai dalilai guda biyu na wannan canjin.Na farko, ko da a sifili mai solubility iyaka A, maida hankali gradient B a cikin ruwa, wanda ba ya nan a cikin DZE, haifar da maida hankali gradient A a cikin m daure, wanda yake a cikin sinadaran ma'auni da ruwa.A gradient A, bi da bi, yana haifar da gradient ρ a cikin Layer ba tare da datti ba.Na biyu, zub da jini na A cikin ruwa saboda rashin narkewar sifili yana ƙara daidaita bambance-bambancen sararin samaniya na ρ a cikin wannan Layer, tare da raguwar solubility yana taimakawa wajen ci gaba da ρ mafi girma kuma mafi daidaituwa ta sarari don kiyaye haɗin kai.
A ƙarshe, juyin halittar girman haɗin gwiwa da haɗin kai a cikin layin da aka wakilta a lokacin LMD ya fi rikitarwa fiye da yanayin yaduwa-iyakantaccen capillary coarsening a madaidaicin juzu'i mai tsayi, kamar yadda aka yi tunani a baya ta kwatanci tare da haɓakar sifofin nanoporous ECD.Kamar yadda aka nuna a nan, ƙwanƙwasa a cikin LMD yana faruwa a cikin ɗan gajeren lokaci mai ban sha'awa mai ƙarfi kuma yawanci yana tasiri ta hanyar watsawar A da B a cikin yanayin ruwa daga ɓangarorin gaba zuwa ƙarshen rabe-raben.Dokokin sikeli don ƙayyadaddun ƙayyadaddun ƙayyadaddun sararin samaniya ko yaɗuwar girma ba za su iya ƙididdige canje-canje a cikin nisa da nisa tsakanin dam ɗin da ke cikin rukunin da aka wakilta ba, suna ɗauka cewa jigilar A da B masu alaƙa da matakan tattara ruwa suna taka rawa daidai ko iri ɗaya.Mahimmanci fiye da rage yanki na dubawa.Haɓaka ka'idar da ke yin la'akari da waɗannan tasiri daban-daban shine muhimmiyar bege na gaba.
Titanium-tantalum binary alloys an siyi su ne daga Arcast, Inc (Oxford, Maine) ta hanyar amfani da wutar lantarki mai karfin 45kW Ambrell Ekoheat ES da crucible tagulla mai sanyaya ruwa.Bayan da yawa zafi, kowane gami da aka annealed ga 8 hours a zazzabi a cikin 200 ° C. na narkewa batu don cimma homogenization da hatsi girma.Samfuran da aka yanke daga wannan ingot na master an haɗa su da tabo zuwa wayoyin Ta kuma an dakatar da su daga hannun mutum-mutumi.An shirya baho na ƙarfe ta hanyar dumama cakuda 40 g Cu (McMaster Carr, 99.99%) tare da Ag (Kurt J. Lesker, 99.95%) ko Ti barbashi a babban iko ta amfani da 4 kW Ameritherm Easyheat dumama tsarin dumama har sai da cikakken rushewa.wanka.cikakken mai zafi narke.Rage wuta kuma bari wanka ya motsa kuma yayi daidai da rabin sa'a a zazzabi na 1240 ° C.Sa'an nan kuma an saukar da hannun mutum-mutumi, ana nutsar da samfurin a cikin wanka don ƙayyadadden lokaci kuma an cire shi don sanyaya.An gudanar da duk dumama billet ɗin gami da LMD a cikin yanayi na tsaftar argon (99.999%).Bayan cire alluran, sassan giciye na samfuran an goge su kuma an bincika su ta amfani da microscopy na gani da na'urar daukar hoto (SEM, JEOL JSM-6700F).An gudanar da nazarin abubuwan da aka yi amfani da su ta hanyar tarwatsawar X-ray spectroscopy (EDS) a cikin SEM.Microstructure mai girma uku na samfuran da aka wakilta an lura da shi ta hanyar narkar da ingantaccen lokaci mai arzikin jan ƙarfe a cikin maganin nitric acid 35% (majin nazari, Fluka).
An gudanar da simintin ta hanyar amfani da samfurin da aka ƙera a baya na filin yanki na ƙaddamarwa na ternary alloy15.Samfurin yana da alaƙa da juyin halitta na filin lokaci ϕ, wanda ke bambanta tsakanin matakan ƙarfi da ruwa, zuwa filin taro ci na abubuwan haɗaka.An bayyana jimlar kuzarin kyauta na tsarin azaman
inda f (φ) shine yuwuwar shamaki biyu tare da minima a φ = 1 da φ = 0 daidai da daskararru da ruwaye, bi da bi, kuma fc (φ, c1, c2, c3) shine gudummawar sinadarai zuwa ƙarar ƴancin da ke kwatanta ƙarfin kuzari. na thermodynamic Properties gami.Don yin kwatankwacin remelting na tsantsar Cu ko CuTi narke cikin TaTi gami, muna amfani da nau'i iri ɗaya fc (φ, c1, c2, c3) da sigogi kamar yadda yake cikin tunani.15. Don cire TaTi alloys tare da CuAg melts, mun sauƙaƙa tsarin quaternary (CuAg) TaTi zuwa tsarin ternary mai tasiri tare da sigogi daban-daban dangane da ƙaddamarwar Ag, kamar yadda aka bayyana a Ƙarin Bayanin 2. Ƙididdigar juyin halitta don filin lokaci da kuma An samo filin maida hankali a cikin nau'i daban-daban a cikin nau'i
Inda \({M}_{ij}={M}_{l}(1-\phi){c}_{i}\hagu({\delta}_{ij}-{c}_{j} \ dama)\) shine matrix motsi na atomic, kuma Lϕ ne ke sarrafa motsin abubuwan da aka makala atomic a madaidaicin ruwa mai ƙarfi.
Ana iya samun bayanan gwaji masu goyan bayan sakamakon wannan binciken a cikin ƙarin fayil ɗin bayanai.Ana ba da sigogin kwaikwaiyo a ƙarin bayanin.Hakanan ana samun duk bayanan daga marubuta daban-daban akan buƙata.
Wittstock A., Zelasek W., Biner J., Aboki SM da Baumer M. Nanoporous zinariya masu kara kuzari don ƙananan zafin zaɓin zaɓin gas-lokacin oxidative na methanol.Kimiyya 327, 319-322 (2010).
Zugic, B. et al.Haɗuwa mai ƙarfi yana ƙayyadaddun ayyukan ƙara kuzari na masu kara kuzarin gwal-azurfa na nanoporous.Almajiri na kasa.16, 558 (2017).
Zeis, R., Mathur, A., Fritz, G., Lee, J. 和 Erlebacher, J. Platinum mai rufi na nanoporous zinariya: ingantaccen ƙananan pt loading electrocatalyst don ƙwayoyin man fetur na PEM.Jaridar #165, 65-72 (2007).
Snyder, J., Fujita, T., Chen, MW da Erlebacher, J. Oxygen raguwa a cikin nanoporous karfe-ion ruwa hada electrocatalysts.Almajiri na kasa.9, 904 (2010).
Lang, X., Hirata, A., Fujita, T. da Chen, M. Nanoporous matasan karfe/oxide lantarki ga electrochemical supercapacitors.Nanotechnology na kasa.6, 232 (2011).
Kim, JW et al.Haɓaka haɗakar niobium tare da narke ƙarfe don ƙirƙirar sifofi masu ƙarfi don masu ƙarfin lantarki.Jarida.84, 497-505 (2015).
Bringa, EM da sauransu. Shin kayan nanoporous suna da juriya ga radiation?Nanolet.12, 3351-3355 (2011).