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Cov biofilms yog ib qho tseem ceeb hauv kev txhim kho cov kab mob ntev, tshwj xeeb tshaj yog thaum nws los txog rau cov khoom siv kho mob. Qhov teeb meem no ua rau muaj kev cov nyom loj heev rau lub zej zog kho mob, vim tias cov tshuaj tua kab mob ib txwm muaj peev xwm rhuav tshem cov biofilms rau qee qhov tsawg heev. Kev tiv thaiv kev tsim cov biofilm tau ua rau muaj kev tsim ntau txoj hauv kev txheej thiab cov ntaub ntawv tshiab. Cov txheej txheem no tsom mus rau txheej cov nplaim hauv txoj kev uas tiv thaiv kev tsim cov biofilm. Cov hlau sib xyaw ua ke, tshwj xeeb tshaj yog cov uas muaj tooj liab thiab titanium hlau, tau dhau los ua cov tshuaj tiv thaiv kab mob zoo tagnrho. Tib lub sijhawm, kev siv cov thev naus laus zis txau txias tau nce ntxiv vim nws yog ib txoj hauv kev tsim nyog rau kev ua cov ntaub ntawv rhiab heev rau qhov kub. Ib feem ntawm lub hom phiaj ntawm kev tshawb fawb no yog los tsim cov iav tiv thaiv kab mob tshiab uas muaj Cu-Zr-Ni ternary siv cov txheej txheem sib xyaw ua ke. Cov hmoov kheej kheej uas ua rau cov khoom kawg yog siv ua cov khoom siv raw rau kev txau txias ntawm cov hlau tsis xeb ntawm qhov kub qis. Cov hlau iav coated substrates tau txo qis biofilm tsim los ntawm tsawg kawg 1 cav piv rau stainless hlau.
Thoob plaws hauv keeb kwm tib neeg, txhua lub zej zog tau muaj peev xwm tsim thiab txhawb nqa kev qhia txog cov ntaub ntawv tshiab los ua kom tau raws li nws cov kev xav tau tshwj xeeb, ua rau muaj kev tsim khoom ntau ntxiv thiab qeb duas hauv kev lag luam thoob ntiaj teb1. Nws ib txwm raug suav hais tias yog tib neeg muaj peev xwm tsim cov ntaub ntawv thiab cov khoom siv tsim khoom, nrog rau kev tsim qauv los tsim thiab piav qhia cov ntaub ntawv kom ua tiav kev noj qab haus huv, kev kawm, kev lag luam, kev lag luam, kab lis kev cai thiab lwm yam teb los ntawm ib lub tebchaws lossis thaj chaw mus rau lwm qhov. Kev nce qib raug ntsuas tsis hais lub tebchaws lossis thaj chaw2. Tau 60 xyoo, cov kws tshawb fawb txog cov ntaub ntawv tau siv sijhawm ntau rau ib txoj haujlwm tseem ceeb: kev tshawb nrhiav cov ntaub ntawv tshiab thiab siab heev. Kev tshawb fawb tsis ntev los no tau tsom mus rau kev txhim kho qhov zoo thiab kev ua tau zoo ntawm cov ntaub ntawv uas twb muaj lawm, nrog rau kev sib xyaw thiab tsim cov ntaub ntawv tshiab kiag li.
Kev ntxiv cov khoom sib xyaw ua ke, kev hloov kho ntawm cov qauv me me ntawm cov khoom siv thiab kev siv cov txheej txheem kho cua sov, tshuab lossis thermomechanical tau ua rau muaj kev txhim kho tseem ceeb hauv cov khoom siv tshuab, tshuaj lom neeg thiab lub cev ntawm ntau yam khoom siv. Tsis tas li ntawd, cov tshuaj tsis paub txog tam sim no tau ua tiav synthesized. Cov kev siv zog no tau ua rau muaj tsev neeg tshiab ntawm cov khoom siv tshiab hu ua Advanced Materials2. Nanocrystals, nanoparticles, nanotubes, quantum dots, xoom-dimensional, amorphous metallic glasses, thiab high-entropy alloys tsuas yog qee qhov piv txwv ntawm cov khoom siv siab heev uas tau tshwm sim hauv ntiaj teb txij li nruab nrab ntawm lub xyoo pua dhau los. Hauv kev tsim khoom thiab kev txhim kho cov alloys tshiab nrog cov khoom zoo dua, ob qho tib si hauv cov khoom kawg thiab hauv cov theem nruab nrab ntawm nws cov khoom tsim tawm, qhov teeb meem ntawm kev tsis sib npaug feem ntau ntxiv. Vim yog kev qhia txog cov txheej txheem tsim khoom tshiab uas tso cai rau kev hloov pauv tseem ceeb ntawm qhov sib npaug, ib chav kawm tshiab ntawm metastable alloys, hu ua metallic glasses, tau pom.
Nws txoj haujlwm ntawm Caltech xyoo 1960 tau hloov pauv lub tswv yim ntawm cov hlau sib xyaw thaum nws tsim Au-25 ntawm.% Si cov hlau sib xyaw iav los ntawm kev ua kom cov kua khov sai sai ntawm yuav luag ib lab degrees ib ob. 4 Xibfwb Paul Duves qhov kev tshawb pom tsis yog tsuas yog cim qhov pib ntawm keeb kwm hlau iav (MS), tab sis kuj ua rau muaj kev hloov pauv paradigm hauv tib neeg xav li cas txog cov hlau sib xyaw. Txij li thaum thawj qhov kev tshawb fawb thawj zaug hauv kev tsim cov hlau sib xyaw MS, yuav luag txhua lub iav hlau tau txais tag nrho siv ib qho ntawm cov hauv qab no: (i) khov sai ntawm cov yaj lossis pa, (ii) atomic lattice disorder, (iii) cov tshuaj tiv thaiv amorphization ntawm cov ntsiab lus hlau ntshiab thiab (iv) cov khoom hloov pauv ntawm cov theem metastable.
MGs yog qhov txawv los ntawm qhov tsis muaj kev txiav txim siab ntev ntawm atomic uas cuam tshuam nrog cov siv lead ua, uas yog ib qho cim qhia txog cov siv lead ua. Hauv lub ntiaj teb niaj hnub no, kev vam meej loj tau ua tiav hauv thaj chaw ntawm cov iav hlau. Cov no yog cov ntaub ntawv tshiab nrog cov khoom nthuav uas tsis yog rau cov khoom khov kho xwb, tab sis kuj rau metallurgy, chemistry nto, thev naus laus zis, biology, thiab ntau lwm qhov chaw. Hom khoom tshiab no muaj cov khoom uas txawv ntawm cov hlau tawv, ua rau nws yog tus neeg sib tw nthuav rau kev siv thev naus laus zis hauv ntau qhov chaw. Lawv muaj qee cov khoom tseem ceeb: (i) kev ua haujlwm siab thiab lub zog tso zis, (ii) kev sib nqus permeability siab, (iii) coercivity qis, (iv) kev tiv thaiv corrosion tsis zoo, (v) kev ywj pheej kub. Conductivity 6.7.
Kev sib xyaw ua ke ntawm cov khoom siv kho tshuab (MA)1,8 yog ib txoj kev tshiab, thawj zaug tau qhia tawm xyoo 19839 los ntawm Prof. KK Kok thiab nws cov npoj yaig. Lawv tsim cov hmoov Ni60Nb40 amorphous los ntawm kev sib tsoo cov khoom sib xyaw ntawm qhov kub thiab txias ze rau qhov kub thiab txias hauv chav. Feem ntau, qhov kev sib xyaw ua ke ntawm MA yog ua tiav ntawm kev sib txuas ntawm cov hmoov reactant hauv lub reactor, feem ntau yog ua los ntawm cov hlau tsis xeb, rau hauv lub tshuab zeb pob. 10 (Daim Duab 1a, b). Txij thaum ntawd los, txoj kev sib xyaw ua ke ntawm cov khoom siv kho tshuab no tau siv los npaj cov hmoov hlau iav amorphous / hlau tshiab siv cov tshuab pob qis (Daim Duab 1c) thiab lub zog siab thiab cov tshuab zeb pas nrig 11,12,13,14,15,16. Tshwj xeeb, txoj kev no tau siv los npaj cov kab ke tsis sib xyaw xws li Cu-Ta17 nrog rau cov hlau sib xyaw siab xws li Al-hloov pauv hlau (TM, Zr, Hf, Nb thiab Ta) 18,19 thiab Fe-W20. , uas tsis tuaj yeem tau txais los ntawm kev siv cov txheej txheem ua noj ua haus ib txwm muaj. Tsis tas li ntawd, MA yog suav hais tias yog ib qho ntawm cov cuab yeej nanotechnological muaj zog tshaj plaws rau kev tsim cov khoom siv nanocrystalline thiab nanocomposite hmoov ntawm cov hlau oxides, carbides, nitrides, hydrides, carbon nanotubes, nanodiamonds, nrog rau kev ruaj khov dav dav siv txoj hauv kev saum toj-rau-hauv qab. 1 thiab theem metastable.
Daim duab qhia txog txoj kev tsim khoom siv los npaj Cu50 (Zr50-xNix) / SUS 304 xim hlau iav txheej hauv txoj kev tshawb fawb no. (a) Kev npaj cov hmoov hlau MC nrog ntau yam kev sib xyaw ntawm Ni x (x; 10, 20, 30, thiab 40 at.%) siv txoj kev sib tsoo pob qis zog. (a) Cov khoom pib raug thauj mus rau hauv lub tog raj kheej cuab yeej nrog rau cov pob hlau cuab yeej thiab (b) kaw rau hauv lub thawv hnab looj tes He huab cua. (c) Tus qauv pob tshab ntawm lub thawv sib tsoo qhia txog kev txav ntawm lub pob thaum sib tsoo. Cov khoom hmoov kawg tau txais tom qab 50 teev tau siv los tsuag txias rau SUS 304 substrate (d).
Thaum nws los txog rau cov khoom siv loj (substrates), kev tsim kho qhov chaw cuam tshuam nrog kev tsim thiab kev hloov kho ntawm qhov chaw (substrates) los muab qee yam khoom siv lub cev, tshuaj lom neeg, thiab kev siv tshuab uas tsis muaj nyob rau hauv cov khoom siv thawj. Qee yam khoom uas tuaj yeem txhim kho tau zoo los ntawm kev kho qhov chaw suav nrog kev sib txhuam, kev tiv thaiv oxidation thiab corrosion, coefficient ntawm kev sib txhuam, bioinertness, cov khoom hluav taws xob thiab thermal rwb thaiv tsev, tsuas yog hais ob peb yam xwb. Qhov zoo ntawm qhov chaw tuaj yeem txhim kho los ntawm cov txheej txheem metallurgical, mechanical lossis chemical. Raws li cov txheej txheem paub zoo, txheej txheem tsuas yog txhais tau tias yog ib lossis ntau txheej ntawm cov khoom siv dag siv rau ntawm qhov chaw ntawm cov khoom loj (substrate) ua los ntawm lwm cov khoom siv. Yog li, txheej txheem yog siv ib feem los ua tiav cov khoom siv lossis kho kom zoo nkauj, nrog rau kev tiv thaiv cov ntaub ntawv los ntawm kev sib cuam tshuam tshuaj lom neeg thiab lub cev nrog ib puag ncig23.
Muaj ntau txoj kev thiab cov txheej txheem siv tau los siv cov txheej tiv thaiv tsim nyog los ntawm ob peb micrometers (qis dua 10-20 micrometers) mus rau ntau dua 30 micrometers lossis txawm tias ob peb millimeters hauv tuab. Feem ntau, cov txheej txheem txheej txheej tuaj yeem muab faib ua ob pawg: (i) cov txheej txheem txheej txheej ntub, suav nrog electroplating, electroplating, thiab kub dip galvanizing, thiab (ii) cov txheej txheem txheej txheej qhuav, suav nrog soldering, hardfacing, lub cev vapor deposition (PVD). ), tshuaj vapor deposition (CVD), thermal spray techniques, thiab tsis ntev los no txias spray techniques 24 (Daim Duab 1d).
Cov biofilms yog txhais tias yog cov zej zog microbial uas txuas nrog cov nto thiab nyob ib puag ncig los ntawm cov polymers extracellular uas tsim tawm (EPS). Kev tsim cov biofilm uas loj hlob tuaj yeem ua rau muaj kev poob loj hauv ntau yam lag luam, suav nrog kev ua zaub mov, cov dej, thiab kev kho mob. Hauv tib neeg, nrog rau kev tsim cov biofilms, ntau dua 80% ntawm cov neeg mob microbial (suav nrog Enterobacteriaceae thiab Staphylococci) nyuaj rau kho. Tsis tas li ntawd, cov biofilms loj hlob tau tshaj tawm tias muaj zog dua 1000 npaug rau kev kho mob tshuaj tua kab mob piv rau cov hlwb planktonic, uas suav tias yog qhov kev sib tw loj hauv kev kho mob. Keeb kwm, cov khoom siv antimicrobial txheej saum npoo av uas tau los ntawm cov organic sib xyaw tau siv. Txawm hais tias cov ntaub ntawv no feem ntau muaj cov khoom lom uas ua rau tib neeg raug mob,25,26 qhov no tuaj yeem pab tiv thaiv kev kis kab mob thiab kev puas tsuaj ntawm cov khoom.
Kev tiv thaiv kab mob ntau yam rau kev kho mob tshuaj tua kab mob vim yog biofilm tsim tau ua rau muaj qhov xav tau los tsim ib qho chaw tiv thaiv kab mob zoo uas tuaj yeem siv tau zoo27. ​​Kev tsim cov chaw tiv thaiv kab mob lossis tshuaj uas cov kab mob tsis tuaj yeem khi thiab tsim cov biofilms vim yog kev nplaum yog thawj txoj hauv kev hauv cov txheej txheem no27. Cov thev naus laus zis thib ob yog tsim cov txheej txheem uas xa cov tshuaj tua kab mob raws nraim qhov twg lawv xav tau, hauv cov khoom siv ntau thiab ua raws li qhov ntau. Qhov no ua tiav los ntawm kev tsim cov ntaub ntawv txheej txheem tshwj xeeb xws li graphene / germanium28, pob zeb diamond dub29 thiab ZnO30-doped pob zeb diamond zoo li carbon uas tiv taus cov kab mob, ib qho thev naus laus zis uas ua rau muaj kev lom thiab kev tiv thaiv vim yog biofilm tsim. Tsis tas li ntawd, cov txheej txheem uas muaj cov tshuaj tua kab mob uas muab kev tiv thaiv mus sij hawm ntev tiv thaiv kev kis kab mob tau dhau los ua neeg nyiam. Txawm hais tias tag nrho peb txoj kev txheej txheem muaj peev xwm ua rau muaj kev ua haujlwm tiv thaiv kab mob ntawm cov chaw coated, txhua tus muaj nws cov kev txwv uas yuav tsum tau xav txog thaum tsim cov tswv yim thov.
Cov khoom lag luam tam sim no muaj nyob rau hauv kev ua lag luam raug cuam tshuam los ntawm qhov tsis muaj sijhawm los tshuaj xyuas thiab sim cov txheej tiv thaiv rau cov khoom xyaw biologically. Cov tuam txhab hais tias lawv cov khoom yuav muab cov neeg siv nrog cov yam ntxwv ua haujlwm xav tau, txawm li cas los xij, qhov no tau dhau los ua qhov teeb meem rau kev vam meej ntawm cov khoom lag luam tam sim no muaj nyob rau hauv kev ua lag luam. Cov tshuaj sib xyaw ua los ntawm nyiaj yog siv rau hauv feem ntau ntawm cov tshuaj tua kab mob tam sim no muaj rau cov neeg siv khoom. Cov khoom no yog tsim los tiv thaiv cov neeg siv los ntawm kev raug rau cov kab mob me me. Cov nyhuv antimicrobial qeeb thiab cov tshuaj lom ntawm cov tshuaj silver ua rau muaj kev nyuaj siab rau cov kws tshawb fawb los tsim lwm txoj hauv kev tsis muaj teeb meem tsawg dua 36,37. Kev tsim cov txheej tiv thaiv kab mob thoob ntiaj teb uas ua haujlwm sab hauv thiab sab nraud tseem yog qhov nyuaj. Qhov no los nrog kev pheej hmoo kev noj qab haus huv thiab kev nyab xeeb. Kev tshawb pom cov neeg sawv cev antimicrobial uas tsis muaj teeb meem rau tib neeg thiab xam seb yuav ua li cas koom nrog nws rau hauv cov txheej txheej nrog lub sijhawm ntev dua yog lub hom phiaj nrhiav tom qab 38. Cov ntaub ntawv antimicrobial thiab antibiofilm tshiab tshaj plaws yog tsim los tua cov kab mob ntawm qhov ze ze los ntawm kev sib cuag ncaj qha lossis tom qab tso tawm ntawm cov neeg sawv cev nquag. Lawv tuaj yeem ua qhov no los ntawm kev txwv tsis pub cov kab mob pib lo rau (xws li tiv thaiv kev tsim cov protein txheej ntawm qhov chaw) lossis los ntawm kev tua cov kab mob los ntawm kev cuam tshuam nrog phab ntsa cell.
Yeej, txheej txheej saum npoo yog txheej txheem ntawm kev siv lwm txheej rau saum npoo ntawm ib qho khoom kom txhim kho cov yam ntxwv ntawm saum npoo. Lub hom phiaj ntawm txheej txheej saum npoo yog hloov pauv qhov microstructure thiab/lossis cov khoom sib xyaw ntawm thaj chaw ze ntawm ib qho khoom39. Cov txheej txheem txheej txheej saum npoo tuaj yeem faib ua ntau txoj kev sib txawv, uas tau muab tso ua ke hauv daim duab 2a. Cov txheej txheej tuaj yeem faib ua pawg thermal, tshuaj lom neeg, lub cev thiab electrochemical nyob ntawm txoj kev siv los tsim cov txheej txheej.
(a) Ib daim duab ntxig qhia txog cov txheej txheem tsim kho qhov chaw tseem ceeb, thiab (b) cov txiaj ntsig thiab qhov tsis zoo ntawm txoj kev tsuag txias.
Cov txheej txheem txau txias muaj ntau yam zoo sib xws nrog cov txheej txheem txau thermal ib txwm muaj. Txawm li cas los xij, kuj tseem muaj qee yam khoom tseem ceeb uas ua rau cov txheej txheem txau txias thiab cov ntaub ntawv txau txias tshwj xeeb. Cov txheej txheem txau txias tseem nyob hauv nws thaum yau, tab sis nws muaj yav tom ntej zoo. Qee zaum, cov khoom tshwj xeeb ntawm kev txau txias muab cov txiaj ntsig zoo, kov yeej cov kev txwv ntawm cov txheej txheem txau thermal ib txwm muaj. Nws kov yeej cov kev txwv tseem ceeb ntawm cov txheej txheem txau thermal ib txwm muaj, uas cov hmoov yuav tsum tau yaj kom tso rau ntawm lub substrate. Nws pom tseeb, cov txheej txheem txheej txheem ib txwm muaj no tsis haum rau cov ntaub ntawv rhiab heev rau qhov kub xws li nanocrystals, nanoparticles, amorphous thiab cov iav hlau40, 41, 42. Tsis tas li ntawd, cov ntaub ntawv txau thermal ib txwm muaj qib siab ntawm porosity thiab oxides. Cov txheej txheem txau txias muaj ntau qhov zoo dua li cov txheej txheem txau thermal, xws li (i) qhov kub tsawg kawg nkaus rau lub substrate, (ii) kev ywj pheej hauv kev xaiv cov txheej txheem substrate, (iii) tsis muaj kev hloov pauv theem thiab kev loj hlob ntawm cov noob, (iv) lub zog nplaum siab1.39 (Daim duab 2b). Ntxiv rau, cov ntaub ntawv txheej txheem txau txias muaj kev tiv thaiv corrosion siab, lub zog siab thiab tawv, kev ua hluav taws xob siab thiab qhov ceev siab41. Txawm hais tias muaj qhov zoo ntawm cov txheej txheem txau txias, txoj kev no tseem muaj qee qhov tsis zoo, raws li pom hauv Daim Duab 2b. Thaum txheej cov hmoov ceramic ntshiab xws li Al2O3, TiO2, ZrO2, WC, thiab lwm yam, txoj kev txau txias tsis tuaj yeem siv. Ntawm qhov tod tes, cov hmoov ceramic / hlau sib xyaw tuaj yeem siv ua cov khoom siv raw rau cov txheej txheem. Tib yam mus rau lwm txoj kev txau thermal. Cov nto nyuaj thiab sab hauv cov yeeb nkab tseem nyuaj rau txau.
Xav txog tias cov haujlwm tam sim no yog tsom mus rau kev siv cov hmoov hlau vitreous ua cov khoom pib rau cov txheej txheem, nws yog qhov tseeb tias kev txau thermal ib txwm tsis tuaj yeem siv rau lub hom phiaj no. Qhov no yog vim qhov tseeb tias cov hmoov hlau vitreous crystallizes ntawm qhov kub siab1.
Feem ntau ntawm cov cuab yeej siv hauv kev kho mob thiab kev lag luam zaub mov yog ua los ntawm cov hlau tsis xeb austenitic (SUS316 thiab SUS304) nrog cov ntsiab lus chromium ntawm 12 txog 20 wt.% rau kev tsim cov cuab yeej phais. Feem ntau lees txais tias kev siv cov hlau chromium ua cov khoom sib xyaw hauv cov hlau sib xyaw tuaj yeem txhim kho qhov kev tiv thaiv corrosion ntawm cov hlau sib xyaw txheem. Cov hlau tsis xeb, txawm tias lawv qhov kev tiv thaiv corrosion siab, tsis muaj cov khoom tiv thaiv kab mob tseem ceeb 38,39. Qhov no sib txawv nrog lawv qhov kev tiv thaiv corrosion siab. Tom qab ntawd, nws muaj peev xwm kwv yees qhov kev loj hlob ntawm kev kis kab mob thiab o, uas feem ntau yog vim cov kab mob lo rau thiab kev loj hlob ntawm qhov chaw ntawm cov khoom siv hlau tsis xeb. Tej zaum yuav muaj teeb meem loj vim muaj teeb meem loj cuam tshuam nrog cov kab mob lo rau thiab cov txheej txheem tsim biofilm, uas tuaj yeem ua rau kev noj qab haus huv tsis zoo, uas tuaj yeem muaj ntau yam tshwm sim uas tuaj yeem cuam tshuam ncaj qha lossis tsis ncaj qha rau tib neeg kev noj qab haus huv.
Txoj kev tshawb fawb no yog thawj theem ntawm ib qhov project uas tau txais nyiaj los ntawm Kuwait Foundation for the Advancement of Science (KFAS), daim ntawv cog lus tsis muaj. 2010-550401, los tshawb nrhiav qhov ua tau ntawm kev tsim cov hmoov hlau glassy Cu-Zr-Ni ternary siv MA technology (rooj). 1) Rau kev tsim cov zaj duab xis tiv thaiv kab mob SUS304 / txheej txheej. Theem thib ob ntawm qhov project, uas yuav pib thaum Lub Ib Hlis 2023, yuav kawm txog cov yam ntxwv ntawm galvanic corrosion thiab cov khoom siv kho tshuab ntawm lub system. Kev ntsuam xyuas microbiological kom ntxaws rau ntau hom kab mob yuav raug ua.
Tsab xov xwm no tham txog qhov cuam tshuam ntawm Zr alloy cov ntsiab lus ntawm lub peev xwm ua iav (GFA) raws li cov yam ntxwv morphological thiab cov qauv. Tsis tas li ntawd, cov khoom tua kab mob ntawm cov hmoov coated hlau iav / SUS304 composite kuj tau tham txog. Tsis tas li ntawd, kev ua haujlwm txuas ntxiv tau ua tiav los tshawb nrhiav qhov ua tau ntawm kev hloov pauv ntawm cov qauv ntawm cov hmoov iav hlau tshwm sim thaum lub sijhawm txau txias hauv thaj chaw kua supercooled ntawm cov iav hlau tsim. Cu50Zr30Ni20 thiab Cu50Zr20Ni30 hlau iav alloys tau siv ua piv txwv sawv cev hauv txoj kev tshawb fawb no.
Tshooj no qhia txog kev hloov pauv morphological hauv cov hmoov ntawm cov khoom Cu, Zr thiab Ni thaum lub sijhawm sib tsoo pob uas tsis muaj zog. Ob lub tshuab sib txawv uas muaj Cu50Zr20Ni30 thiab Cu50Zr40Ni10 yuav raug siv ua piv txwv. Cov txheej txheem MA tuaj yeem faib ua peb theem sib cais, raws li pov thawj los ntawm cov yam ntxwv metallographic ntawm cov hmoov tau txais hauv theem sib tsoo (Daim duab 3).
Cov yam ntxwv ntawm cov hmoov ntawm cov khoom siv hlau (MA) tau txais tom qab ntau theem ntawm kev sib tsoo pob. Cov duab ntawm Field emission scanning electron microscopy (FE-SEM) ntawm MA thiab Cu50Zr40Ni10 hmoov tau txais tom qab kev sib tsoo pob zog tsawg rau 3, 12 thiab 50 teev tau qhia hauv (a), (c) thiab (e) rau Cu50Zr20Ni30 system, thaum nyob rau tib MA. Cov duab sib xws ntawm Cu50Zr40Ni10 system uas tau coj tom qab lub sijhawm tau qhia hauv (b), (d), thiab (f).
Thaum lub sijhawm milling pob, lub zog kinetic zoo uas tuaj yeem hloov mus rau cov hmoov hlau raug cuam tshuam los ntawm kev sib xyaw ua ke ntawm cov kev ntsuas, raws li pom hauv daim duab 1a. Qhov no suav nrog kev sib tsoo ntawm cov pob thiab cov hmoov, shear compression ntawm cov hmoov daig ntawm lossis ntawm cov khoom sib tsoo, kev cuam tshuam los ntawm cov pob poob, shear thiab hnav los ntawm cov hmoov rub ntawm cov cev txav ntawm lub tshuab zeb pob, thiab lub zog poob siab hla cov pob poob uas nthuav dav los ntawm cov kab lis kev cai thauj khoom (Daim duab 1a). 3. образованию крупных частиц порошка (> 1 мм в диаметре). Cov hmoov Cu, Zr, thiab Ni tau raug hloov pauv hnyav heev vim yog kev vuam txias thaum ntxov ntawm MA (3 teev), uas ua rau muaj cov hmoov loj (> 1 hli hauv txoj kab uas hla).Cov khoom me me loj no yog cov yam ntxwv los ntawm kev tsim cov txheej tuab ntawm cov khoom sib xyaw (Cu, Zr, Ni), raws li pom hauv daim duab 3a, b. Kev nce lub sijhawm MA mus rau 12 teev (theem nrab) ua rau lub zog kinetic ntawm lub pob zeb nce ntxiv, uas ua rau cov hmoov sib xyaw ua cov hmoov me me (tsawg dua 200 μm), raws li pom hauv daim duab 3c, lub nroog. Nyob rau theem no, lub zog shear siv ua rau kev tsim cov hlau tshiab nrog cov txheej nyias Cu, Zr, Ni, raws li pom hauv daim duab 3c, d. Vim yog kev sib tsoo ntawm cov txheej ntawm qhov sib tshuam ntawm cov flakes, cov tshuaj tiv thaiv theem khov kho tshwm sim nrog kev tsim cov theem tshiab.
Thaum kawg ntawm cov txheej txheem MA (tom qab 50 teev), flake metallography tsis tshua pom tseeb (Daim duab 3e, f), thiab daim iav metallography tau pom ntawm qhov chaw polished ntawm cov hmoov. Qhov no txhais tau tias cov txheej txheem MA tau ua tiav thiab ib theem tshuaj tiv thaiv tau tsim. Cov khoom sib xyaw ntawm cov cheeb tsam qhia hauv Figs. 3e (I, II, III), f, v, vi) tau txiav txim siab siv kev siv lub tshuab hluav taws xob scanning electron microscopy (FE-SEM) ua ke nrog lub zog dispersive X-ray spectroscopy (EDS). (IV).
Hauv lub rooj. 2 cov ntsiab lus ntawm cov ntsiab lus alloying tau qhia ua feem pua ​​​​​​ntawm tag nrho cov pawg ntawm txhua thaj tsam xaiv hauv daim duab 3e, f. Kev sib piv cov txiaj ntsig no nrog cov qauv nominal thawj zaug ntawm Cu50Zr20Ni30 thiab Cu50Zr40Ni10 muab rau hauv Rooj 1 qhia tau hais tias cov qauv ntawm ob yam khoom kawg no ze heev rau cov qauv nominal. Tsis tas li ntawd, cov nqi sib piv ntawm cov khoom rau thaj tsam teev nyob rau hauv Daim Duab 3e, f tsis qhia txog kev puas tsuaj loj lossis kev hloov pauv hauv cov qauv ntawm txhua tus qauv los ntawm ib cheeb tsam mus rau lwm qhov. Qhov no yog pov thawj los ntawm qhov tseeb tias tsis muaj kev hloov pauv hauv cov qauv los ntawm ib cheeb tsam mus rau lwm qhov. Qhov no qhia txog kev tsim cov hmoov hlau sib xws raws li tau pom hauv Rooj 2.
Cov duab FE-SEM micrographs ntawm cov hmoov khoom kawg Cu50 (Zr50-xNix) tau txais tom qab 50 MA lub sijhawm, raws li pom hauv daim duab 4a-d, qhov twg x yog 10, 20, 30 thiab 40 ntawm.%, feem. Tom qab cov kauj ruam sib tsoo no, cov hmoov sib sau ua ke vim yog qhov cuam tshuam ntawm van der Waals, uas ua rau muaj cov khoom sib sau ua ke loj uas muaj cov khoom me me nrog lub cheeb ntawm 73 txog 126 nm, raws li pom hauv daim duab 4.
Cov yam ntxwv morphological ntawm Cu50 (Zr50-xNix) hmoov tau txais tom qab 50-teev MA. Rau Cu50Zr40Ni10, Cu50Zr30Ni20, Cu50Zr20Ni30, Cu50Zr10Ni40 systems, cov duab FE-SEM ntawm cov hmoov tau txais tom qab 50 MA tau qhia hauv (a), (b), (c), thiab (d), raws li.
Ua ntej muab cov hmoov tso rau hauv lub tshuab txau txias, lawv tau sonicated ua ntej hauv analytical qib ethanol rau 15 feeb thiab tom qab ntawd qhuav ntawm 150 ° C rau 2 teev. Cov kauj ruam no yuav tsum tau ua kom tiav los tawm tsam agglomeration, uas feem ntau ua rau muaj ntau yam teeb meem loj hauv cov txheej txheem txheej. Tom qab ua tiav ntawm cov txheej txheem MA, kev tshawb fawb ntxiv tau ua los tshawb xyuas qhov sib xws ntawm cov hmoov hlau. Ntawm daim duab 5a-d qhia FE-SEM micrographs thiab cov duab EDS sib xws ntawm Cu, Zr thiab Ni alloying ntsiab lus ntawm Cu50Zr30Ni20 alloy coj tom qab 50 teev lub sijhawm M, feem. Nws yuav tsum tau sau tseg tias cov hmoov hlau tau txais tom qab cov kauj ruam no yog homogeneous, vim tias lawv tsis qhia txog kev hloov pauv ntawm cov khoom sib xyaw dhau ntawm qib sub-nanometer, raws li pom hauv Daim Duab 5.
Morphology thiab kev faib tawm hauv zos ntawm cov ntsiab lus hauv MG Cu50Zr30Ni20 hmoov tau txais tom qab 50 MA los ntawm FE-SEM / Zog Dispersive X-ray Spectroscopy (EDS). (a) SEM thiab X-ray EDS imaging ntawm (b) Cu-Kα, (c) Zr-Lα, thiab (d) Ni-Kα.
Cov qauv X-ray diffraction ntawm cov hmoov Cu50Zr40Ni10, Cu50Zr30Ni20, Cu50Zr20Ni30, thiab Cu50Zr20Ni30 uas tau txais tom qab 50-teev MA tau qhia nyob rau hauv daim duab 6a-d, raws li. Tom qab theem sib tsoo no, tag nrho cov qauv nrog cov Zr sib txawv muaj cov qauv amorphous nrog cov qauv halo diffusion qhia nyob rau hauv daim duab 6.
Cov qauv X-ray diffraction ntawm Cu50Zr40Ni10 (a), Cu50Zr30Ni20 (b), Cu50Zr20Ni30 (c), thiab Cu50Zr20Ni30 (d) hmoov tom qab MA rau 50 teev. Ib qho qauv halo-diffusion tau pom nyob rau hauv tag nrho cov qauv tsis muaj kev zam, qhia txog kev tsim ntawm ib theem amorphous.
Siv lub tshuab ntsuas hluav taws xob xa hluav taws xob siab (FE-HRTEM) los soj ntsuam cov kev hloov pauv ntawm cov qauv thiab nkag siab txog cov qauv hauv zos ntawm cov hmoov uas tshwm sim los ntawm kev sib tsoo pob ntawm lub sijhawm MA sib txawv. Cov duab ntawm cov hmoov tau txais los ntawm txoj kev FE-HRTEM tom qab theem thaum ntxov (6 teev) thiab theem nruab nrab (18 teev) ntawm kev sib tsoo Cu50Zr30Ni20 thiab Cu50Zr40Ni10 hmoov tau pom hauv daim duab 7a, raws li. Raws li daim duab ci ntsa iab (BFI) ntawm cov hmoov tau txais tom qab 6 teev ntawm MA, cov hmoov muaj cov noob loj nrog cov ciam teb meej ntawm cov ntsiab lus fcc-Cu, hcp-Zr, thiab fcc-Ni, thiab tsis muaj cim ntawm kev tsim ntawm theem tshuaj tiv thaiv, raws li tau pom hauv daim duab 7a. Tsis tas li ntawd, tus qauv diffraction cheeb tsam xaiv (SADP) coj los ntawm thaj chaw nruab nrab (a) tau qhia txog tus qauv diffraction ntse (Daim duab 7b) qhia txog qhov muaj cov crystallites loj thiab tsis muaj theem tshuaj tiv thaiv.
Cov yam ntxwv ntawm cov qauv hauv zos ntawm cov hmoov MA tau txais tom qab theem thaum ntxov (6 teev) thiab theem nruab nrab (18 teev). (a) High resolution field emission transmission electron microscopy (FE-HRTEM) thiab (b) cov duab diffractogram (SADP) ntawm Cu50Zr30Ni20 hmoov tom qab kho MA rau 6 teev. Daim duab FE-HRTEM ntawm Cu50Zr40Ni10 tau txais tom qab 18-teev MA tau qhia hauv (c).
Raws li pom hauv daim duab 7c, kev nce lub sijhawm ntawm MA mus rau 18 teev ua rau muaj qhov tsis zoo ntawm cov lattice ua ke nrog kev hloov pauv yas. Nyob rau theem nruab nrab ntawm cov txheej txheem MA no, ntau yam kev tsis zoo tshwm sim hauv cov hmoov, suav nrog cov kev ua yuam kev stacking, cov kev tsis zoo ntawm lattice, thiab cov kev tsis zoo ntawm cov ntsiab lus (Daim duab 7). Cov kev tsis zoo no ua rau cov noob loj tawg ua tej daim me dua 20 nm (Daim duab 7c).
Cov qauv hauv zos ntawm Cu50Z30Ni20 hmoov uas tau sib tsoo rau 36 teev MA yog tus cwj pwm los ntawm kev tsim cov nanograins zoo heev uas tau muab tso rau hauv lub matrix nyias amorphous, raws li pom hauv daim duab 8a. Kev tshuaj xyuas hauv zos ntawm EMF qhia tau hais tias cov nanoclusters uas pom hauv daim duab 8a yog txuam nrog cov hmoov hlau Cu, Zr thiab Ni uas tsis tau kho. Cov ntsiab lus ntawm Cu hauv lub matrix sib txawv ntawm ~ 32 ntawm.% (cheeb tsam tsis zoo) mus rau ~ 74 ntawm.% (cheeb tsam nplua nuj), uas qhia txog kev tsim cov khoom sib txawv. Tsis tas li ntawd, cov SADPs sib xws ntawm cov hmoov tau txais tom qab sib tsoo hauv kauj ruam no qhia txog thawj thiab thib ob halo-diffusion amorphous theem nplhaib sib tshooj nrog cov ntsiab lus ntse cuam tshuam nrog cov khoom sib xyaw tsis tau kho, raws li pom hauv daim duab 8b.
Nanoscale local structural features ntawm Beyond 36 h-Cu50Zr30Ni20 hmoov. (a) Bright field image (BFI) thiab sib xws (b) SADP ntawm Cu50Zr30Ni20 hmoov tau txais tom qab milling rau 36 h MA.
Nyob rau thaum kawg ntawm cov txheej txheem MA (50 h), Cu50 (Zr50-xNix), X, 10, 20, 30, thiab 40 at.% hmoov, tsis muaj kev zam, muaj lub labyrinthine morphology ntawm theem amorphous, raws li pom hauv daim duab. Tsis yog qhov taw tes diffraction lossis cov qauv annular ntse tuaj yeem pom hauv SADS sib xws ntawm txhua qhov sib xyaw. Qhov no qhia txog qhov tsis muaj hlau crystalline tsis kho, tab sis theej kev tsim ntawm cov hmoov hlau amorphous. Cov SADPs sib raug zoo no qhia txog cov qauv diffusion halo kuj tau siv ua pov thawj rau kev txhim kho ntawm cov theem amorphous hauv cov khoom kawg.
Cov qauv hauv zos ntawm cov khoom kawg ntawm Cu50 MS system (Zr50-xNix). FE-HRTEM thiab cov qauv nanobeam diffraction (NBDP) sib raug zoo ntawm (a) Cu50Zr40Ni10, (b) Cu50Zr30Ni20, (c) Cu50Zr20Ni30, thiab (d) Cu50Zr10Ni40 tau txais tom qab 50 teev ntawm MA.
Siv cov kev ntsuas calorimetry sib txawv, qhov ruaj khov ntawm qhov kub hloov pauv iav (Tg), thaj chaw kua txias heev (ΔTx) thiab qhov kub thiab txias crystallization (Tx) tau kawm nyob ntawm cov ntsiab lus ntawm Ni (x) hauv Cu50 (Zr50-xNix) amorphous system. (DSC) cov khoom hauv He gas flow. Cov kab DSC ntawm cov hmoov ntawm Cu50Zr40Ni10, Cu50Zr30Ni20, thiab Cu50Zr10Ni40 amorphous alloys tau txais tom qab MA rau 50 teev tau qhia hauv Figs. 10a, b, e, feem. Thaum cov kab DSC ntawm amorphous Cu50Zr20Ni30 tau qhia cais hauv Fig. xyoo pua 10th Lub caij no, cov qauv Cu50Zr30Ni20 raug cua sov rau ~ 700 ° C hauv DSC tau qhia hauv Fig. 10g.
Qhov ruaj khov thermal ntawm Cu50 (Zr50-xNix) MG hmoov tau tom qab MA rau 50 teev yog txiav txim siab los ntawm qhov kub hloov iav (Tg), qhov kub crystallization (Tx) thiab thaj chaw kua supercooled (ΔTx). Thermograms ntawm differential scanning calorimeter (DSC) hmoov ntawm Cu50Zr40Ni10 (a), Cu50Zr30Ni20 (b), Cu50Zr20Ni30 (c), thiab (e) Cu50Zr10Ni40 MG alloy hmoov tom qab MA rau 50 teev. Tus qauv X-ray diffraction (XRD) ntawm Cu50Zr30Ni20 qauv cua sov rau ~ 700 ° C hauv DSC yog qhia nyob rau hauv (d).
Raws li pom hauv Daim Duab 10, cov kab DSC rau txhua qhov sib xyaw nrog cov nickel sib txawv (x) qhia txog ob qho xwm txheej sib txawv, ib qho endothermic thiab lwm qhov exothermic. Qhov xwm txheej endothermic thawj zaug sib raug rau Tg, thiab qhov thib ob yog cuam tshuam nrog Tx. Thaj chaw kab rov tav uas muaj nyob nruab nrab ntawm Tg thiab Tx hu ua thaj chaw kua dej txias (ΔTx = Tx - Tg). Cov txiaj ntsig qhia tau tias Tg thiab Tx ntawm Cu50Zr40Ni10 qauv (Daim Duab 10a) tso rau ntawm 526 ° C thiab 612 ° C hloov cov ntsiab lus (x) mus txog 20 ntawm % mus rau sab kub qis ntawm 482 ° C thiab 563 ° C. ° C nrog kev nce ntxiv ntawm Ni cov ntsiab lus (x), raws li pom hauv Daim Duab 10b. Yog li ntawd, ΔTx Cu50Zr40Ni10 txo qis los ntawm 86°C (Daim Duab 10a) mus rau 81°C rau Cu50Zr30Ni20 (Daim Duab 10b). Rau MC Cu50Zr40Ni10 alloy, qhov txo qis ntawm cov nqi ntawm Tg, Tx, thiab ΔTx mus rau theem ntawm 447°C, 526°C, thiab 79°C kuj tau pom (Daim Duab 10b). Qhov no qhia tau hais tias kev nce ntxiv ntawm cov ntsiab lus Ni ua rau qhov txo qis ntawm qhov ruaj khov thermal ntawm MS alloy. Ntawm qhov tsis sib xws, tus nqi ntawm Tg (507°C) ntawm MC Cu50Zr20Ni30 alloy qis dua li ntawm MC Cu50Zr40Ni10 alloy; txawm li cas los xij, nws Tx qhia tus nqi sib piv rau nws (612°C). Yog li ntawd, ΔTx muaj tus nqi siab dua (87°C) raws li pom hauv daim duab 10th xyoo pua.
Lub Cu50 (Zr50-xNix) MC system, siv Cu50Zr20Ni30 MC alloy ua piv txwv, crystallizes los ntawm lub ncov exothermic ntse mus rau hauv fcc-ZrCu5, orthorhombic-Zr7Cu10, thiab orthorhombic-ZrNi crystalline theem (Daim Duab 10c). Qhov kev hloov pauv theem no los ntawm amorphous mus rau crystalline tau lees paub los ntawm X-ray diffraction tsom xam ntawm MG qauv (Daim Duab 10d) uas tau cua sov rau 700 ° C hauv DSC.
Hauv daim duab 11 qhia cov duab thaij thaum lub sijhawm ua haujlwm tam sim no. Hauv kev tshawb fawb no, cov hmoov hlau iav uas tau tsim tom qab MA rau 50 teev (siv Cu50Zr20Ni30 ua piv txwv) tau siv ua cov khoom siv tua kab mob, thiab lub phaj hlau tsis xeb (SUS304) tau pleev xim rau tshuaj tsuag txias. Txoj kev pleev xim txias tau xaiv rau kev pleev xim hauv cov koob tshuaj thermal spray vim nws yog txoj kev ua haujlwm zoo tshaj plaws hauv cov koob tshuaj thermal spray uas nws tuaj yeem siv rau cov khoom siv hlau uas rhiab heev rau cua sov xws li amorphous thiab nanocrystalline hmoov. Tsis raug rau theem. kev hloov pauv. Qhov no yog qhov tseem ceeb hauv kev xaiv txoj kev no. Cov txheej txheem tso dej txias yog ua tiav los ntawm kev siv cov khoom me me uas hloov lub zog kinetic ntawm cov khoom me me mus rau hauv cov yas deformation, deformation thiab cua sov thaum cuam tshuam nrog lub substrate lossis cov khoom me me uas tau tso ua ntej.
Cov duab thaij teb qhia txog cov txheej txheem txau txias siv rau tsib qhov kev npaj sib law liag ntawm MG/SUS 304 ntawm 550°C.
Lub zog kinetic ntawm cov khoom me me, nrog rau lub zog ntawm txhua lub khoom me me thaum lub sijhawm tsim cov txheej txheem, yuav tsum tau hloov mus rau lwm hom zog los ntawm cov txheej txheem xws li kev hloov pauv yas (cov khoom me me thiab kev sib cuam tshuam ntawm cov khoom me me hauv lub matrix thiab kev sib cuam tshuam ntawm cov khoom me me), cov pob caus interstitial ntawm cov khoom khov, kev sib hloov ntawm cov khoom me me, kev hloov pauv thiab kev txwv cua sov 39. Tsis tas li ntawd, yog tias tsis yog tag nrho cov zog kinetic nkag mus rau hauv lub zog thermal thiab lub zog deformation, qhov tshwm sim yuav yog kev sib tsoo elastic, uas txhais tau tias cov khoom me me tsuas yog dhia tawm tom qab kev cuam tshuam. Nws tau sau tseg tias 90% ntawm lub zog cuam tshuam siv rau cov khoom me me / substrate yog hloov mus rau hauv cua sov hauv zos 40. Tsis tas li ntawd, thaum muaj kev ntxhov siab cuam tshuam, cov nqi yas siab tau ua tiav hauv thaj chaw sib cuag ntawm cov khoom me me / substrate hauv lub sijhawm luv luv heev 41,42.
Feem ntau, kev hloov pauv yas yog suav hais tias yog ib qho txheej txheem ntawm kev tshem tawm lub zog, lossis qhov tseeb, ua qhov chaw cua sov hauv thaj chaw sib tshuam. Txawm li cas los xij, qhov nce ntawm qhov kub hauv thaj chaw sib tshuam feem ntau tsis txaus rau qhov tshwm sim ntawm kev yaj ntawm kev sib tshuam lossis kev txhawb nqa tseem ceeb ntawm kev sib kis ntawm cov atoms. Tsis muaj ntawv tshaj tawm uas cov kws sau ntawv paub tau tshawb nrhiav qhov cuam tshuam ntawm cov khoom ntawm cov hmoov hlau vitreous no ntawm kev nplaum hmoov thiab kev sib sau ua ke thaum siv cov txheej txheem txau txias.
Tus BFI ntawm MG Cu50Zr20Ni30 alloy hmoov tuaj yeem pom hauv daim duab 12a, uas tau tso rau ntawm SUS 304 substrate (Daim duab 11, 12b). Raws li tuaj yeem pom los ntawm daim duab, cov hmoov coated khaws lawv cov qauv amorphous qub vim lawv muaj cov qauv labyrinth mos mos tsis muaj cov yam ntxwv crystalline lossis lattice defects. Ntawm qhov tod tes, daim duab qhia txog qhov muaj nyob ntawm theem txawv teb chaws, raws li pov thawj los ntawm cov nanoparticles suav nrog hauv MG-coated hmoov matrix (Daim duab 12a). Daim duab 12c qhia txog cov qauv indexed nanobeam diffraction (NBDP) cuam tshuam nrog thaj tsam I (Daim duab 12a). Raws li pom hauv daim duab 12c, NBDP qhia txog cov qauv halo-diffusion tsis muaj zog ntawm cov qauv amorphous thiab coexists nrog cov chaw ntse sib raug rau crystalline loj cubic metastable Zr2Ni theem ntxiv rau tetragonal CuO theem. Qhov kev tsim ntawm CuO tuaj yeem piav qhia los ntawm kev oxidation ntawm cov hmoov thaum txav mus los ntawm lub nozzle ntawm rab phom tsuag mus rau SUS 304 hauv qhov chaw qhib hauv qhov ntws supersonic. Ntawm qhov tod tes, devitrification ntawm cov hmoov hlau iav ua rau muaj cov theem loj cubic tom qab kev kho mob txias ntawm 550 ° C rau 30 feeb.
(a) Duab FE-HRTEM ntawm MG hmoov tso rau ntawm (b) SUS 304 substrate (Duab inset). Tus lej NBDP ntawm lub cim puag ncig uas pom hauv (a) yog pom hauv (c).
Txhawm rau sim qhov mechanism no rau kev tsim cov loj cubic Zr2Ni nanoparticles, ib qho kev sim ywj pheej tau ua tiav. Hauv qhov kev sim no, cov hmoov tau txau los ntawm lub atomizer ntawm 550 ° C mus rau hauv qhov kev taw qhia ntawm SUS 304 substrate; txawm li cas los xij, txhawm rau txiav txim siab qhov cuam tshuam annealing, cov hmoov tau raug tshem tawm ntawm SUS304 strip sai li sai tau (kwv yees li 60 s). ). Lwm cov kev sim tau ua tiav uas cov hmoov tau raug tshem tawm ntawm lub substrate kwv yees li 180 vib nas this tom qab thov.
Cov Duab 13a, b qhia txog Scanning Transmission Electron Microscopy (STEM) cov duab tsaus ntuj (DFI) ntawm ob yam khoom siv sputtered uas tau muab tso rau ntawm SUS 304 substrates rau 60 vib nas this thiab 180 vib nas this, raws li. Cov duab hmoov uas tau muab tso rau 60 vib nas this tsis muaj cov ntsiab lus morphological, qhia txog qhov tsis muaj featurelessness (Daim Duab 13a). Qhov no kuj tau lees paub los ntawm XRD, uas qhia tau tias cov qauv tag nrho ntawm cov hmoov no yog amorphous, raws li qhia los ntawm cov dav dav thawj zaug thiab theem nrab diffraction peaks qhia hauv Daim Duab 14a. Qhov no qhia txog qhov tsis muaj metastable/mesophase precipitates, uas cov hmoov khaws nws cov qauv amorphous qub. Hauv kev sib piv, cov hmoov uas tau muab tso rau ntawm tib qhov kub (550 ° C) tab sis tso rau ntawm substrate rau 180 vib nas this qhia txog kev tso cov noob nanosized, raws li qhia los ntawm cov xub hauv Daim Duab 13b.