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Inganda zikora inyongeramusaruro zirimo guhindura uburyo abashakashatsi n'inganda bashushanya kandi bagakora ibikoresho bya chimique kugira ngo bihuze n'ibyo bakeneye byihariye. Muri aka kazi, turagaragaza urugero rwa mbere rw'icyuma gitanga amazi cyakozwe na tekiniki ya Ultrasonic Additive Manufacturing (UAM) ifite ibice bya catalytic hamwe n'ibintu byo kumva. Ikoranabuhanga rya UAM ntiritsinda gusa imbogamizi nyinshi zijyanye no gukora inyongeramusaruro z'ibikoresho bya chimique, ahubwo rinanongera cyane ubushobozi bw'ibikoresho nk'ibyo. Uruhererekane rw'ibinyabutabire 1,4-dissubstituted 1,2,3-triazole by'ingenzi mu binyabuzima byakozwe neza kandi binonosorwa na Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction hakoreshejwe uburyo bwa UAM chemistry. Binyuze mu gukoresha imiterere yihariye ya UAM no gutunganya imikorere ihoraho, igikoresho gishobora gukurura imikorere ihoraho mu gihe gitanga ibitekerezo mu buryo bufatika byo gukurikirana no kunoza imikorere y'imikorere.
Bitewe n'inyungu zayo zikomeye ugereranyije n'ibindi binini, shimi y'imiyoboro y'amazi ni ingenzi kandi ikura haba mu nzego z'ubushakashatsi no mu nganda bitewe n'ubushobozi bwayo bwo kongera uburyo bwo guhitamo no gukora neza kw'imiti. Ibi biva ku miterere yoroheje ya molecule1 kugeza ku binyabutabire by'imiti2,3 n'ibikomoka ku bimera karemano4,5,6. Ibirenga 50% by'ibisubizo mu nganda nziza z'imiti n'imiti bishobora kungukirwa no gukoresha uburyo bwo gutunganya amazi buri gihe7.
Mu myaka ya vuba aha, habayeho kwiyongera kw'amatsinda ashaka gusimbuza ibikoresho gakondo by'ibirahuri cyangwa ibikoresho bya shimi bikoreshwa mu gutunganya ibinyabutabire (AM) "ibinyabutabire by'ibinyabutabire" bya shimi bihinduka "8". Imiterere y'ubu buryo, umusaruro wihuse, n'ubushobozi bwa 3D (3D) bw'ubu buryo ni ingirakamaro ku bifuza guhindura ibikoresho byabo hakurikijwe uburyo runaka bw'ibinyabutabire, ibikoresho, cyangwa imiterere. Kugeza ubu, ubu bushakashatsi bwibanze cyane ku ikoreshwa rya tekiniki za 3D zishingiye kuri polymer nka stereolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 na inkjet printing 7, 15, 16. Kutagira imbaraga n'ubushobozi bw'ibyo bikoresho mu gukora ibikorwa byinshi bitandukanye by'ibinyabutabire17, 18, 19, 20 ni ikintu gikomeye kibangamira ishyirwa mu bikorwa ryagutse rya AM muri uru rwego17, 18, 19, 20.
Bitewe n’uko ikoreshwa ry’imiti ikoreshwa mu gukwirakwiza amazi n’imiterere myiza ijyanye na AM rikomeje kwiyongera, hakenewe gushakisha uburyo bugezweho butuma abakoresha bashobora gukora imiyoboro y’imiti ikoreshwa mu gukwirakwiza amazi hakoreshejwe ubushobozi bwo kongera ubushobozi bwa shimi n’isesengura. Ubu buryo bugomba gutuma abakoresha bahitamo ibikoresho bikomeye cyane cyangwa bikora neza bishobora guhangana n’imiterere itandukanye y’imiti, ndetse no koroshya uburyo butandukanye bwo gusesengura umusaruro uva muri icyo gikoresho kugira ngo habeho gukurikirana no kugenzura imiti.
Uburyo bumwe bwo gukora inyongeramusaruro bufite ubushobozi bwo guteza imbere reactors za chemical zihariye ni Ultrasonic Additive Manufacturing (UAM). Ubu buryo bwo gusiga irangi rya solid-state sheet lamination bukoresha ultrasonic oscillations ku byuma bito kugira ngo bihuzwe hamwe urwego ku rundi hamwe n'ubushyuhe buke n'urwego rwo hejuru rw'amazi ya pulasitiki 21, 22, 23. Bitandukanye n'izindi koranabuhanga nyinshi za AM, UAM ishobora guhuzwa mu buryo butaziguye n'inganda zigabanya ubushyuhe, zizwi nka hybrid manufacturing process, aho in-situ periodic computer numeral control (CNC) milling cyangwa laser machining bigena imiterere nyayo y'urwego rw'ibikoresho bifatanye 24, 25. Ibi bivuze ko umukoresha adakumirwa n'ibibazo bijyana no gukuraho ibikoresho by'ibanze bisigaye mu miyoboro mito y'amazi, nk'uko bikunze kubaho kuri sisitemu ya AM y'ifu n'amazi 26, 27, 28. Ubu bwigenge bwo gushushanya bunagera no ku mahitamo y'ibikoresho biboneka - UAM ishobora guhuza ibikoresho bisa n'ubushyuhe kandi bitandukanye mu ntambwe imwe y'igikorwa. Guhitamo guhuza ibikoresho birenze inzira yo gushonga bivuze ko ibisabwa na mekanike na shimi by'ikoreshwa runaka bishobora kuzuzwa neza. Uretse guhuza ibintu bikomeye, ikindi Ikintu cyagaragaye mu gihe cyo guhuza ikoranabuhanga rya ultrasound ni urujya n'uruza rwinshi rw'ibikoresho bya pulasitiki ku bushyuhe buri hasi 29, 30, 31, 32, 33. Iki kintu cyihariye cya UAM gishobora koroshya gushyiramo ibintu bya mekanike/ubushyuhe hagati y'ibyuma bitangiritse. Ibikoresho bya UAM bifasha mu gutanga amakuru mu buryo bwihuse uhereye ku gikoresho ukagera ku mukoresha binyuze mu isesengura ryakozwe.
Imirimo y’abanditsi yashize32 yagaragaje ubushobozi bwa gahunda ya UAM bwo gukora imiterere y’icyuma ya 3D microfluidic ifite ubushobozi bwo kumva. Iki ni igikoresho cyo kugenzura gusa. Iyi nyandiko igaragaza urugero rwa mbere rw’icyuma cya microfluidic chemical reactor cyakozwe na UAM; igikoresho gikora kitagenzura gusa ahubwo kinatera imikorere ya chemical binyuze mu bikoresho bya catalyst bihujwe n’imiterere. Iki gikoresho gihuza ibyiza byinshi bifitanye isano n’ikoranabuhanga rya UAM mu gukora ibikoresho bya 3D chemical, nko: ubushobozi bwo guhindura imiterere yuzuye ya 3D mu buryo butaziguye uhereye kuri moderi za mudasobwa (CAD) mo ibicuruzwa; gukora ibikoresho byinshi kugira ngo bihuze ubwiyongere bw’ubushyuhe n’ibikoresho bya catalytic; no gushyiramo ibikoresho by’ubushyuhe hagati y’imigezi ya reagent kugira ngo hagenzurwe neza ubushyuhe bw’impinduka. Kugira ngo hagaragazwe imikorere ya reactor, hakozwe isomero ry’ibintu by’ingenzi bya 1,4-dismissated 1,2,3-triazole byakozwe mu rwego rw’imiti hakoreshejwe Huisgen 1,3-dipolar cycloaddition yakozwe na umuringa. Uyu murimo ugaragaza uburyo ikoreshwa ry’ubumenyi bw’ibikoresho n’igishushanyo mbonera gifashijwe na mudasobwa bishobora gutanga amahirwe mashya n’amahirwe yo gukora chimie binyuze mu bushakashatsi butandukanye.
Ibinyabutabire n'ibinyabutabire byose byaguzwe muri Sigma-Aldrich, Alfa Aesar, TCI cyangwa Fischer Scientific kandi byakoreshejwe bitabanje gusukurwa. 1H na 13C NMR spectra byafashwe kuri 400 MHz na 100 MHz, uko bikurikirana, byabonetse hakoreshejwe spectrometer ya JEOL ECS-400 400 MHz cyangwa spectrometer ya Bruker Avance II 400 MHz na CDCl3 cyangwa (CD3) 2SO nk'ibinyabutabire. Ibinyabutabire byose byakozwe hakoreshejwe urubuga rwa Uniqsis FlowSyn flow chemistry.
UAM yakoreshejwe mu gukora ibikoresho byose muri ubu bushakashatsi. Ikoranabuhanga ryavumbuwe mu 1999, kandi ibisobanuro byaryo bya tekiniki, ibipimo by'imikorere n'iterambere kuva ryavumburwa bishobora kwigwa binyuze mu bikoresho bikurikira byasohotse34,35,36,37. Iki gikoresho (Ishusho ya 1) cyashyizwe mu bikorwa hakoreshejwe sisitemu ya 9kW SonicLayer 4000® UAM (Fabrisonic, OH, USA). Ibikoresho byatoranijwe mu gukora igikoresho cy'amazi ni Cu-110 na Al 6061. Cu-110 ifite umuringa mwinshi (nibura 99.9% by'umuringa), bigatuma iba nziza mu gukora umuringa ukoresha ibyuma, bityo ikaba ikoreshwa nk'"urwego rukora muri microreactor. Al 6061 O ikoreshwa nk'ibikoresho "byinshi", ndetse n'urwego rwo gushoramo ibikoresho rukoreshwa mu gusesengura; Gushyiramo ibice by'inyongera bya Alloy n'imiterere yo gufunga hamwe n'urwego rwa Cu-110. Al 6061 O ni ibikoresho byagaragaye ko bihuye cyane na gahunda za UAM38, 39, 40, 41 kandi byageragejwe kandi byagaragaye ko bitangiza imiti hamwe n’ibisubizo byakoreshejwe muri uyu murimo. Guhuza Al 6061 O na Cu-110 nabyo bifatwa nk’uruvange rw’ibikoresho bihuye na UAM bityo bikaba ari ibikoresho bikwiye muri ubu bushakashatsi. 38,42 Ibi bikoresho bikubiye mu mbonerahamwe ya 1 hepfo.
Ibyiciro byo gukora Reactor (1) Al 6061 substrate (2) Gukora umuyoboro wo hasi ushyizwe kuri foil y'umuringa (3) Gushyiramo thermocouples hagati y'ibice (4) Umuyoboro wo hejuru (5) Injira n'aho isohoka (6) Reactor ya Monolithic.
Filozofiya y’igishushanyo mbonera cy’inzira y’amazi ni ugukoresha inzira ivanze kugira ngo wongere intera amazi agenda muri chip, ariko ugakomeza chip ku bunini bushoboka. Uku kwiyongera kw’intera ni byiza kugira ngo wongere igihe cyo gukorana na catalyst/reagent kandi utange umusaruro mwiza w’ibicuruzwa. Utu duce dukoresha 90° ku mpera z’inzira igororotse kugira ngo dutere kuvanga mu buryo butunguranye mu gikoresho44 kandi twongere igihe amazi ahurira n’ubuso (catalyst). Kugira ngo wongere kuvanga bishobora kugerwaho, igishushanyo mbonera cya reactor gifite inlets ebyiri za reagent zihujwe ku murongo wa Y mbere yo kwinjira mu gice cyo kuvanga cy’imisemburo. Inlets ya gatatu, ihurira n’umugezi hagati mu gice cyayo, iri mu gishushanyo cy’intambwe nyinshi z’imikorere.
Imiyoboro yose ifite ishusho kare (nta nguni z’inguni zikoreshwa), umusaruro w’imashini isya ya CNC ikoreshwa mu gukora imiterere y’umuyoboro. Ingano z’umuyoboro zitoranywa kugira ngo haboneke ingano nini (kuri microreactor), mu gihe ari nto bihagije kugira ngo yorohereze imikoranire y’ubuso (catalysts) ku mazi menshi arimo. Ingano ikwiye ishingiye ku bunararibonye bw’abanditsi ba kera ku bikoresho by’icyuma n’amazi byo gukora reaction. Ingano z’imbere z’umuyoboro wa nyuma zari 750 µm x 750 µm kandi ingano yose ya reactor yari 1 ml. Umuyoboro uhujwe (1/4″—28 UNF thread) urimo mu gishushanyo kugira ngo wemererwe guhuza igikoresho n’ibikoresho bya shimi byo mu bucuruzi. Ingano y’umuyoboro igengwa n’ubunini bw’ibikoresho bya foil, imiterere yabyo ya mekanike, n’ibipimo byo guhuza bikoreshwa na ultrasonic. Ku bugari bwihariye bw’ibikoresho runaka, ibikoresho "bizagwa" mu muyoboro wakozwe. Ubu nta gishushanyo cyihariye gihari cy’iki gikorwa cyo kubara, bityo ubugari ntarengwa bw’umuyoboro ku bikoresho runaka n’igishushanyo mbonera bigenwa mu buryo bw’igerageza; muri iki gihe, ubugari bwa 750 μm ntabwo buzatuma habaho kugwa.
Imiterere (kare) y'umuyoboro igenwa hakoreshejwe icyuma gikata kare. Imiterere n'ingano by'imiyoboro bishobora guhindurwa n'imashini za CNC zikoresha ibikoresho bitandukanye byo gukata kugira ngo haboneke uburyo butandukanye bwo gutembera n'imiterere. Urugero rwo gukora umuyoboro w'imiterere ugonze ukoresheje igikoresho cya 125 μm ruboneka mu gikorwa cya Monaghan45. Iyo urwego rwa foil rushyizwe mu buryo bugaragara, hejuru y'ibikoresho bya foil hejuru y'imiyoboro hazaba hari iherezo rirambuye (kare). Muri uyu murimo, kugira ngo umuyoboro ukomeze kungana, hakoreshejwe imiterere ya kare.
Mu gihe cyo guhagarika gukora, ibikoresho by'ubushyuhe bya thermocouple (Ubwoko bwa K) bishyirwa mu gikoresho hagati y'amatsinda y'imiyoboro yo hejuru n'iyo hasi (Ishusho ya 1 - Icyiciro cya 3). Izi thermocouple zishobora gukurikirana imihindagurikire y'ubushyuhe kuva kuri -200 kugeza kuri 1350 °C.
Uburyo bwo gushyira icyuma mu cyuma bukorwa n'ihembe rya UAM hakoreshejwe urupapuro rw'icyuma rufite ubugari bwa mm 25.4 n'ubugari bwa mikoroni 150. Utu duce tw'urupapuro dufatanye mu ruhererekane rw'uduce twegeranye kugira ngo dutwikire ahantu hose hubatswe; ingano y'ibikoresho byashyizwemo ni nini kuruta umusaruro wa nyuma kuko inzira yo gukuramo ikora imiterere ya nyuma. Uburyo bwo gutunganya CNC bukoreshwa mu gutunganya imiterere y'inyuma n'iy'imbere y'ibikoresho, bigatuma ibikoresho n'imiyoboro birangirana n'ibipimo byatoranijwe by'igikoresho na CNC (hafi 1.6 μm Ra muri uru rugero). Uburyo bwo gushyira ibikoresho bya ultrasonic buri gihe no gutunganya ibyuma bikoreshwa mu gihe cyose cyo gukora ibikoresho kugira ngo hamenyekane ko imiterere y'ibipimo ikomeza kandi igice cyarangiye kizahura n'urwego rwo gutunganya neza rwa CNC. Ubugari bw'umuyoboro ukoreshwa kuri iki gikoresho ni buto bihagije kugira ngo ibikoresho bya aluminiyumu bitagwa mu muyoboro w'amazi, bityo umuyoboro ugakomeza kugira igice cya kare. Icyuho gishoboka mu bikoresho bya aluminiyumu n'ibipimo bya UAM byagenwe mu buryo bw'igerageza n'umufatanyabikorwa mu gukora (Fabrisonic LLC, USA).
Ubushakashatsi bwagaragaje ko hari ahantu hato ho gukwirakwiza ibintu ku buryo bwa UAM bonding interface 46, 47 hatabayeho ubundi buryo bwo kuvura ubushyuhe, bityo ku bikoresho biri muri iki gikorwa, urwego rwa Cu-110 ruguma ruto n'urwego rwa Al 6061 kandi rugahinduka mu buryo butunguranye.
Shyiramo icyuma gipima umuvuduko w’inyuma cya psi 250 (1724 kPa) cyagenwe mbere (BPR) mu nzira yo gusohokeramo icyuma hanyuma uvome amazi muri icyuma gipima umuvuduko ku kigero cya 0.1 kugeza kuri 1 mL min-1. Umuvuduko w’icyuma gipima umuvuduko wa icyuma cyagenzuwe hakoreshejwe uburyo bwa FlowSyn bwo kugenzura umuvuduko kugira ngo harebwe ko igikoresho gishobora kugumana umuvuduko uhoraho. Ingano y’ubushyuhe ishobora kugaragara muri icyuma gipima umuvuduko yageragejwe hagaragazwa itandukaniro riri hagati ya thermocouples ziri muri icyuma gipima umuvuduko n’iziri muri plate ya FlowSyn ishyushya. Ibi bigerwaho hakoreshejwe guhindura ubushyuhe bwa plate ishyushya umuvuduko hagati ya 100 na 150 °C mu nyongera za 25 °C no kureba itandukaniro riri hagati y’ubushyuhe bwateguwe n’ubwanditswe. Ibi byagezweho hakoreshejwe uburyo bwa tc-08 bwo kwandika amakuru (PicoTech, Cambridge, UK) hamwe na porogaramu ya PicoLog ijyana nabwo.
Imiterere y’imikorere ya cycloaddition ya phenylacetylene na iodoethane yanogejwe (Igipimo cya 1- Cycloaddition ya phenylacetylene na iodoethane Gahunda ya 1- Cycloaddition ya phenylacetylene na iodoethane). Uku kunoza kwakozwe hakoreshejwe uburyo bwose bwo gushushanya ibizamini (DOE), hakoreshejwe ubushyuhe n'igihe cyo gutura nk'ibipimo bihinduka, mu gihe hashyirwaho igipimo cya alkyne:azide kuri 1:2.
Hateguwe ibisubizo bitandukanye bya sodium azide (0.25 M, 4:1 DMF: H2O), iodoethane (0.25 M, DMF), na fenilacetylene (0.125 M, DMF). Hakozwe 1.5 mL ya buri gisubizo ivanze kandi inyuzwa muri reactor ku muvuduko n'ubushyuhe byifuzwaga. Igisubizo cya moderi cyafashwe nk'ikigereranyo cy'ubuso bw'umusaruro wa triazole ugera ku bikoresho byo gutangira bya phenylacetylene kandi bigenwa na chromatography y'amazi ifite imikorere myiza (HPLC). Kugira ngo habeho uburyo buhamye bwo gusesengura, ibisubizo byose byapimwe nyuma gato y'uko uruvange rw'ibisubizo ruvuye muri reactor. Urutonde rw'ibipimo byatoranijwe kugira ngo binoze rugaragara mu mbonerahamwe ya 2.
Ingero zose zasesenguwe hakoreshejwe sisitemu ya Chromaster HPLC (VWR, PA, USA) igizwe na pompe ya quaternary, ifuru y'inkingi, detector ya UV ihinduka na autosampler. Inkingi yari Equivalence 5 C18 (VWR, PA, USA), ingano ya mm 4.6 × 100, ingano y'uduce twa µm 5, iguma kuri 40 °C. Umushongi wari isocratic 50:50 methanol: amazi ku gipimo cy'amazi cya 1.5 mL. min-1. Ingano y'inshinge yari 5 µL naho uburebure bw'inshinge bwari 254 nm. % by'ubuso bw'icyitegererezo cya DOE cyabazwe uhereye ku duce tw'ubuso bw'ibikomoka kuri alkyne na triazole gusa. Gutera ibikoresho byo gutangira bituma hamenyekana imisozi ijyanye n'ibyo.
Guhuza umusaruro w’isesengura rya reactor na porogaramu ya MODDE DOE (Umetrics, Malmö, Suwede) byatumye habaho isesengura ryimbitse ry’imigendekere y’ibyavuye mu bushakashatsi no kumenya imiterere myiza y’isesengura kuri iyi cycloaddition. Gukoresha optimizer yubatswemo no guhitamo amagambo yose y’ingenzi y’icyitegererezo bitanga urutonde rw’imiterere y’isesengura igenewe kongera ubuso bw’umusaruro mu gihe bigabanya ubuso bw’umusaruro ku bikoresho bitangiriraho acetylene.
Gushyira ogisijeni ku buso bw'umuringa mu cyumba cy'ingufu za kataletiki byagezweho hakoreshejwe umuti wa peroxide ya hydrogen (36%) unyura mu cyumba cy'ingufu (umuvuduko w'amazi = 0.4 mL min-1, igihe cyo gutura = iminota 2.5) mbere yo gukora buri bubiko bw'ibitabo bya triazole.
Iyo habonetse ubwoko bwiza bw'ibintu, byashyizwe ku bwoko butandukanye bwa acetylene na haloalkane kugira ngo byemererwe gukusanya ingano nto y'ibintu biri mu bubiko, bityo bigashyiraho ubushobozi bwo gukoresha ibi bintu ku bwoko bwinshi bw'ibintu bishobora kuba bihari (Ishusho ya 1).2).
Tegura ibisubizo bitandukanye bya sodium azide (0.25 M, 4:1 DMF: H2O), haloalkanes (0.25 M, DMF) na alkynes (0.125 M, DMF). 3 mL aliquots za buri gisubizo zavanzwe hanyuma zinyuzwa muri reactor kuri 75 µL. min-1 na 150 °C. Ingano yose yakusanyijwe mu kabari hanyuma ivangwa na 10 mL ya ethyl acetate. Icyitegererezo cy'igisubizo cyogejwe na 3 × 10 mL z'amazi. Uduce tw'amazi twahujwe hanyuma dukurwamo 10 mL ya ethyl acetate; utwo duce tw'umwimerere twahujwe, twogezwa na 3 x 10 mL ya brine, twumishwa kuri MgSO4 hanyuma tuyungururwa, hanyuma umuti uvanwa mu cyuma gisukuye. Ingero zasukuwe hakoreshejwe column chromatography kuri silica gel hakoreshejwe ethyl acetate mbere yo gusesengura hakoreshejwe HPLC, 1H NMR, 13C NMR na high resolution mass spectrometry (HR-MS).
Spektara zose zabonetse hakoreshejwe spectrometero ya Thermofischer precision Orbitrap resolution mass spectrometero ifite ESI nk'isoko ya ionization. Ingero zose zateguwe hakoreshejwe acetonitrile nk'umusemburo.
Isesengura rya TLC ryakozwe ku masahani ya silica akozwe kuri aluminiyumu. Amasahani yagaragajwe n'urumuri rwa UV (254 nm) cyangwa irangi rya vanillin n'ubushyuhe.
Ingero zose zasesenguwe hakoreshejwe sisitemu ya VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) ifite icyuma gipima autosampler, pompe y'ifuru y'inkingi na detector y'uburebure bumwe. Inkingi yakoreshejwe yari ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
Inshinge (5 µL) zakozwe mu buryo butaziguye mu mvange y’ibinyabutabire bivanze (1:10 dilution) kandi zigasesengurwa hakoreshejwe amazi: methanol (50:50 cyangwa 70:30), uretse ingero zimwe na zimwe zakoreshejwe sisitemu ya solvent ya 70:30 (yerekanwe nk'umubare w'inyenyeri) ku gipimo cya 1.5 mL/umunota. Inkingi yagumye kuri 40 °C. Uburebure bw'umuvuduko w'amazi ni 254 nm.
Ubuso bw'impeshyi y'icyitegererezo bwabazwe uhereye ku gasongero k'agace k'inyongera ka alkyne gasigaye, hagafatwa gusa umusaruro wa triazole, kandi gutera ibikoresho byo gutangira byatumye hamenyekana impeshyi zikenewe.
Ingero zose zasesenguwe hakoreshejwe Thermo iCAP 6000 ICP-OES. Ibipimo byose byo gupima byateguwe hakoreshejwe igisubizo gisanzwe cya 1000 ppm Cu muri aside nitrike ya 2% (SPEX Certi Prep). Ibipimo byose byateguwe muri 5% DMF na 2% HNO3, kandi ingero zose zavanzwe inshuro 20 muri sampuli ya DMF-HNO3.
UAM ikoresha ubushuhe bw'icyuma bukoresheje ikoranabuhanga rya ultrasonic nk'uburyo bwo guhuza ibikoresho bya foil by'icyuma bikoreshwa mu kubaka ihuriro rya nyuma. Ubushuhe bw'icyuma bukoresheje igikoresho cy'icyuma gihindagurika (cyitwa horn cyangwa ultrasound horn) kugira ngo gishyire igitutu ku gice cya foil/urwego rwari rwahujwe mbere kugira ngo rufatanye mu gihe ruzunguza ibikoresho. Kugira ngo bikomeze gukora, sonotrode iba uruziga kandi izunguruka hejuru y'ikintu, igahuza igice cyose. Iyo igitutu n'ihindagurika bishyizweho, oxyde ziri ku buso bw'ikintu zishobora kwangirika. Igitutu gikomeje n'ihindagurika bishobora gutuma ibintu bigwa nabi 36. Guhura cyane n'ubushyuhe n'igitutu bikomoka aho hantu bituma habaho guhuza ibintu mu buryo buhamye; bishobora kandi gufasha gufatana binyuze mu mpinduka mu ngufu z'ubuso48. Imiterere y'uburyo bwo guhuza itsinda ibibazo byinshi bifitanye isano n'ubushyuhe buhindagurika n'ingaruka z'ubushyuhe bwinshi bivugwa mu bundi buryo bwo gukora inyongera. Ibi bituma habaho guhuza mu buryo butaziguye (ni ukuvuga, hatabayeho guhindura ubuso, kuzuza cyangwa kole) by'ibice byinshi by'ibikoresho bitandukanye mu buryo bumwe buhuriweho.
Ikindi kintu cyiza kuri UAM ni urwego rwo hejuru rw'amazi ya pulasitiki agaragara mu bikoresho by'icyuma, ndetse no mu bushyuhe buke, ni ukuvuga munsi cyane y'aho ibintu by'icyuma bishongesherezwa. Guhuza imikorere ya ultrasonic oscillation n'umuvuduko bitera urwego rwo hejuru rw'imipaka y'ingano yo mu gace no kongera guhindurwa nta kwiyongera gukomeye k'ubushyuhe busanzwe bufitanye isano n'ibikoresho byinshi. Mu gihe cyo kubaka ihuriro rya nyuma, iki kintu gishobora gukoreshwa mu gushyira ibice bikora n'ibidakora hagati y'ibice by'icyuma, urwego ku rundi. Ibintu nka fibre optique 49, reinforcements 46, electronics 50, na thermocouples (iki gikorwa) byose byashyizwe mu miterere ya UAM kugira ngo bikore ihuriro rikora kandi ridakora.
Muri iki gikorwa, uburyo butandukanye bwo guhuza ibikoresho n'uburyo bwo guhuza UAM byakoreshejwe mu gukora microreactor ikurikirana ubushyuhe bwa catalytic.
Ugereranyije na palladium (Pd) n'izindi catalysts zikoreshwa cyane mu byuma, Cu catalysis ifite ibyiza byinshi: (i) Mu bukungu, Cu irahendutse ugereranyije n'ibindi byuma byinshi bikoreshwa mu gukata, bityo ikaba ari amahitamo meza ku nganda zitunganya imiti (ii) Uruhererekane rw'ibikorwa byo guhuza Cu-catalyzed cross-coupling ruriyongera kandi rusa nkaho rwuzuzanya n'uburyo bushingiye kuri Pd51,52,53 (iii) Ibikorwa bya Cu-catalyzed bikora neza mu gihe nta zindi ligands zihari. Izi ligands akenshi ziba zoroshye mu miterere kandi zihendutse iyo zifujwe, mu gihe izikoreshwa muri chimie ya Pd akenshi ziba zigoye, zihenze, kandi zifata umwuka (iv) Cu, izwi cyane cyane ku bushobozi bwayo bwo guhuza alkynes mu guhuza, Urugero, Sonogashira coupling ya bimetallic-catalyzed na cycloaddition hamwe na azides (click chemistry) (v) Cu ishobora kandi guteza imbere arylation ya nucleophiles nyinshi mu bikorwa bya Ullmann.
Ingero z'uburyo ibi byose bihinduka mu buryo butandukanye zagaragaye vuba aha iyo hari Cu (0). Ibi ahanini biterwa n'inganda zikora imiti ndetse n'uburyo hibandwa cyane ku kugarura no kongera gukoresha ibyuma bya catalyst55,56.
Yatangijwe na Huisgen mu myaka ya 196057, igisubizo cya 1,3-dipolar cycloaddition hagati ya acetylene na azide kuri 1,2,3-triazole gifatwa nk'igikorwa cyo kwerekana ko kirimo gukorana. Ibice 1,2,3 bya triazole bikomokaho ni ingenzi cyane nk'imiti ikoreshwa mu kuvumbura imiti bitewe n'uburyo ikoreshwa mu buryo bw'ibinyabuzima n'uburyo ikoreshwa mu miti itandukanye ivura 58.
Iyi reaction yongeye kwibandwaho ubwo Sharpless n'abandi bashyiragaho igitekerezo cya "click chemistry"59. Ijambo "click chemistry" rikoreshwa mu gusobanura urutonde rukomeye, rwizewe kandi rutoranyije rw'ibyiciro byo guhuza vuba ibintu bishya n'amasomero ahuza ibintu binyuze mu guhuza heteroatom (CXC)60. Kurushaho gukurura ibi bipimo bikomoka ku musaruro mwinshi bifitanye isano nabyo, imiterere y'ibyiciro ni yoroshye, ubushobozi bwo kwirinda ogisijeni n'amazi, kandi gutandukanya ibicuruzwa biroroshye61.
Uburyo bwa Huisgen 1,3-dipole cycloaddition ntabwo buri mu cyiciro cya "click chemistry". Ariko, Medal na Sharpless bagaragaje ko iki gikorwa cyo guhuza azide-alkyne kiba hagati ya 107 na 108 imbere ya Cu (I) ugereranije no kwihuta kwa cycloaddition 62,63 ku kigero cy'ingenzi. Ubu buryo bwo kunoza uburyo bwo gusubiza ntibusaba kurinda amatsinda cyangwa imimerere mibi yo gusubiza kandi butanga impinduka hafi ya zose no guhitamo 1,4-dissubstituted 1,2,3-triazole (anti-1,2,3-triazole) ku gipimo cy'igihe (Ishusho ya 3).
Ibisubizo bya isometric bya Huisgen cycloadditions isanzwe n'ifite umuringa. Huisgen cycloadditions ya Cu(I) itanga gusa triazoles 1,4-dissubstituted 1,2,3-triazoles, mu gihe Huisgen cycloadditions iterwa n'ubushyuhe ikunze gutanga uruvange rwa 1,4 na 1,5-triazoles 1:1 rwa stereoisomers za azoles.
Inyinshi muri gahunda zirimo kugabanya amasoko ya Cu (II) ahamye, nko kugabanya ubwoko bwa CuSO4 cyangwa Cu (II) / Cu (0) hamwe n'umunyu wa sodium. Ugereranyije n'izindi reactions ziterwa n'icyuma, gukoresha Cu (I) bifite inyungu zikomeye zo kuba bihendutse kandi byoroshye gukoresha.
Ubushakashatsi bwa Worrell et al. 65 ku bijyanye no gushyira ibimenyetso mu buryo bwa Kinetic na isotopic bwagaragaje ko, ku birebana na alkynes za nyuma, ibintu bibiri bingana na umuringa bigira uruhare mu gutuma buri molekyuli ikora neza kuri azide. Uburyo bwatanzwe bunyura mu mpeta y'umuringa ifite ibice bitandatu ikorwa n'imikoranire ya azide na acetylene y'umuringa ifite σ hamwe n'umuringa ufite π nk'umuteranyi w'umusanzu uhamye. Ibikomoka ku muringa wa Triazolyl bikorwa no kugabanuka kw'impeta, hagakurikiraho kuvunika kwa proton kugira ngo hatange ibicuruzwa bya triazole kandi bifunge uruziga rw'ingufu.
Nubwo ibyiza by'ibikoresho bya shimi bikoreshwa mu gukwirakwiza amazi byagaragajwe neza, habayeho icyifuzo cyo guhuza ibikoresho by'isesengura muri izi sisitemu kugira ngo harebwe uburyo bwo gukurikirana ibikorwa biri mu murongo, aho biri,67. UAM yagaragaye ko ari uburyo bwiza bwo gushushanya no gukora reactors zikomeye cyane za 3D zikozwe mu bikoresho bikora cyane, biyobora ubushyuhe hamwe n'ibintu byo kumva byinjijwemo (Ishusho ya 4).
Imashini ikora amashanyarazi ya aluminiyumu n'umuringa yakozwe n'inyongeramusaruro za ultrasonic (UAM) ifite imiterere y'imiyoboro y'imbere ikomeye, thermocouples zishyizwemo hamwe n'icyumba cy'imyitozo ngororamubiri. Kugira ngo harebwe inzira z'amazi imbere, hagaragazwa kandi icyitegererezo cy'ishusho cyakozwe hakoreshejwe stereolithography.
Kugira ngo hamenyekane ko imashini zikora ibikoresho bya 'reactor' zizakoreshwa mu gihe kizaza, imashini zikenera gushyushya neza hejuru y'ubushyuhe bukabije; zipimwa umuvuduko n'ubushyuhe. Ikizamini cy'umuvuduko cyagaragaje ko sisitemu igumana umuvuduko uhamye kandi uhoraho nubwo umuvuduko w'isi wiyongera (1.7 MPa). Ikizamini cya hydrostatic cyakozwe ku bushyuhe bw'icyumba hakoreshejwe H2O nk'amazi.
Guhuza thermocouple iri mu ifoto (Ishusho ya 1) n'ikimenyetso cy'ubushyuhe byagaragaje ko thermocouple yari ikonje kuri dogere selisiyusi 6 (± 1 °C) kurusha ubushyuhe bwateguwe kuri sisitemu ya FlowSyn. Ubusanzwe, kwiyongera kwa dogere selisiyusi 10 bituma igipimo cy'ubushyuhe cyikuba kabiri, bityo itandukaniro ry'ubushyuhe bwa dogere nke gusa rishobora guhindura cyane igipimo cy'ubushyuhe. Iri tandukaniro riterwa n'igihombo cy'ubushyuhe mu mubiri wose wa reactor bitewe n'ubushyuhe bwinshi bw'ibikoresho bikoreshwa mu gukora. Uku kunyurana kw'ubushyuhe kurahoraho bityo rero gushobora kubarwa mu miterere y'ibikoresho kugira ngo hamenyekane ubushyuhe nyabwo bugerwaho kandi bupimwe mu gihe cy'ubushyuhe. Kubwibyo, iki gikoresho cyo kugenzura kuri interineti cyorohereza kugenzura ubushyuhe bw'ubushyuhe kandi cyorohereza kunoza imikorere no guteza imbere imiterere myiza. Izi sensor zishobora kandi gukoreshwa mu kumenya exotherms z'ubushyuhe no gukumira ingaruka zigenda mu buryo bunini.
Reactor igaragazwa muri iki gikorwa ni urugero rwa mbere rw'ikoreshwa ry'ikoranabuhanga rya UAM mu gukora reactor za chemical kandi ikemura imbogamizi nyinshi zikomeye zijyanye no gucapa AM/3D kuri ibi bikoresho, nka: (i) gukemura ibibazo byavuzwe bijyanye no gutunganya umuringa cyangwa aluminiyumu (ii) kunoza ubushobozi bwo guhuza imiyoboro y'imbere ugereranije n'uburyo bwo guhuza ifu (PBF) nko gushonga kwa laser (SLM)25,69 Uburyo ibintu bigenda nabi n'imiterere y'ubuso buke26 (iii) Ubushyuhe bugabanuka, butuma sensor zifatana neza, ibyo bikaba bidashoboka mu ikoranabuhanga rya poda, (v) bitsinda imiterere mibi ya mekanike n'uburyo ibice bishingiye kuri polymer bikorana n'ibintu bitandukanye bisanzwe bisukura organic17,19.
Imikorere y'iyi reactor yagaragajwe n'urukurikirane rw'ibikorwa bya alkyne azide cycloaddition byakozwe n'umuringa mu gihe cy'imivuduko ihoraho (Ishusho ya 2). Iyi reactor y'umuringa yacapwe na ultrasonic ivugwa ku Ishusho ya 4 yahujwe n'uburyo bwo gutembera mu bucuruzi kandi yakoreshejwe mu gukora azide zo muri library za 1,4-dissubstituted 1,2,3-triazoles binyuze mu buryo bugenzurwa n'ubushyuhe bwa acetylene na halide zo mu matsinda ya alkyl imbere ya sodium chloride (Ishusho ya 3). Gukoresha uburyo bwo gutembera buhoraho bigabanya impungenge z'umutekano zishobora kuvuka mu mikorere y'itsinda, kuko iyi reaction itanga aside intermediates zikora cyane kandi ziteje akaga [317], [318]. Mbere na mbere, reaction yakozwe neza kugira ngo ikoreshwe muri cycloaddition ya phenylecetylene na iodoethane (Igishushanyo cya 1 - Cycloaddition ya phenylecetylene na iodoethane) (reba Ishusho ya 5).
(Hejuru ibumoso) Igishushanyo mbonera cy'uburyo bwakoreshejwe mu gushyira reactor ya 3DP muri sisitemu y'amazi (hejuru iburyo) cyabonetse muri gahunda yakozwe neza (hejuru) ya gahunda ya Huisgen cycloaddition 57 hagati ya phenylacetylene na iodoethane kugira ngo irusheho kunozwa kandi yerekane igipimo cyo guhindura reaction yakozwe neza.
Mu kugenzura igihe cy’aho ibintu bibera mu gice cy’ingufu cya reactor biherereye no gukurikirana neza ubushyuhe bw’aho ibintu bibera hakoreshejwe probe ya thermocouple, imiterere y’aho ibintu bibera ishobora kunozwa vuba kandi neza hamwe n’igihe gito n’ibikoresho bikoreshwa. Byahise byemezwa ko impinduka nini zabonetse iyo igihe cyo gutura cyari iminota 15 n’ubushyuhe bwa reaction bwa 150 °C byakoreshejwe. Ukurikije imiterere ya porogaramu ya MODDE, bigaragara ko igihe cyo gutura n’ubushyuhe bw’aho ibintu bibera ari amagambo y’ingenzi. Gukoresha optimizer yubatswemo hakoreshejwe aya magambo yatoranijwe bitanga urutonde rw’imiterere y’aho ibintu bibera hagamijwe kongera ubuso bw’ibicuruzwa mu gihe bigabanya ubuso bw’ibicuruzwa bitangira. Uku kunoza kwatanze 53% by’ihinduka ry’ibicuruzwa bya triazole, byahuye neza n’icyitegererezo cya 54%.
Hashingiwe ku nyandiko zerekana ko oxide y'umuringa (I) (Cu2O) ishobora gukora nk'ubwoko bw'ibintu bihindura imiterere y'umuringa ku buso bwa zero-valent muri ubwo buryo, hasuzumwe ubushobozi bwo gushyira oxide ku buso bwa reactor mbere yo gukora reaction mu mazi70,71. Nyuma yaho, reaction hagati ya phenylacetylene na iodoethane yongeye gukorwa mu bihe byiza kandi umusaruro uragereranywa. Byagaragaye ko iyi gahunda yatumye habaho kwiyongera gukomeye mu guhindura ibikoresho byo gutangira, byagereranyijwe ko ari >99%. Ariko, igenzura rya HPLC ryagaragaje ko iri hinduka ryagabanyije cyane igihe kinini cyo gukora reaction kugeza ku minota 90, aho igikorwa cyasaga n'aho kiringaniye kandi kigera ku "buzima buhamye". Iyi nyigo igaragaza ko isoko y'ibikorwa bihindura imiterere y'umubiri ituruka kuri oxide y'umuringa ku buso aho kuba kuri zero-valent umuringa. Cu metal ishyirwa mu bushyuhe bw'icyumba byoroshye kugira ngo ikore CuO na Cu2O bitari urwego rwo kwirinda. Ibi bikuraho ko hakenewe kongeramo isoko y'umuringa (II) y'inyongera kugira ngo habeho imiterere y'umubiri71.