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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 iyi nyandiko, turagaragaza urugero rwa mbere rw'icyuma gitanga amazi cyakozwe na ultrason additive manufacturing (UAM) cyakozwe n'icyuma gikomeye gifite ibice bya catalytic hamwe n'ibintu byo kumva. Ikoranabuhanga rya UAM ntiritsinda gusa imbogamizi nyinshi zijyanye no gukora inyongeramusaruro z'ibikoresho bya chimique, ahubwo rinagura cyane ubushobozi bw'ibikoresho nk'ibyo. Ibigize byinshi by'ingenzi bya 1,4-dissubstituted 1,2,3-triazole byakozwe neza kandi binonosorwa neza na Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction hakoreshejwe ikoranabuhanga rya chimie rya UAM. Dukoresheje imiterere yihariye ya UAM no gutunganya inyongeramusaruro mu buryo buhoraho, igikoresho gishobora gukurura inyongeramusaruro zihoraho ndetse no gutanga ibitekerezo mu gihe nyacyo kugira ngo gikurikirane kandi gikore neza inyongeramusaruro.
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 ikorwa rya molekile zoroshye za organic1 kugeza ku binyabutabire bya farumasi2,3 n'ibikomoka ku bimera karemano4,5,6. Hejuru ya 50% by'ibitera imbaraga mu nganda nziza za farumasi n'iza farumasi bishobora kungukirwa n'imiyoboro ihoraho7.
Mu myaka ya vuba aha, habayeho kwiyongera kw'amatsinda ashakisha gusimbuza ibikoresho gakondo by'ibirahuri cyangwa ibikoresho bya chimie bikoreshwa mu gukwirakwiza amashanyarazi n'ibikoresho bya "reactors" bya chimique bishobora guhinduka8. Imiterere isubiramo, gukora vuba, n'ubushobozi bwa 3D (3D) bw'ubu buryo ni ingirakamaro ku bashaka guhindura ibikoresho byabo hakurikijwe ubwoko runaka bw'ibikorwa, ibikoresho, cyangwa imiterere. Kugeza ubu, uyu murimo wibanze 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 printing7,15. , 16. Kutagira icyizere n'ubushobozi bw'ibyo bikoresho mu gukora ibikorwa byinshi by'ibinyabutabire/isesengura17, 18, 19, 20 ni ikintu gikomeye kibangamira ikoreshwa 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 uburyo bwiza bwo gushakisha buzafasha abakoresha gukora imiyoboro y’imyakura ifite ubushobozi bwo kunoza imikorere ya shimi n’isesengura. Ubu buryo bugomba gutuma abakoresha bahitamo ibikoresho bikomeye cyangwa imikorere ishobora gukora mu bihe bitandukanye byo gukwirakwiza amazi, ndetse no koroshya uburyo butandukanye bwo gusesengura igikoresho kugira ngo kibashe gukurikirana no kugenzura uburyo kikoreshwa.
Uburyo bumwe bwo gukora inyongeramusaruro bushobora gukoreshwa mu guteza imbere reactors za chemical zihariye ni Ultrasonic Additive Manufacturing (UAM). Ubu buryo bwo gusimbuza impapuro zikomeye bukoresha vibration za ultrasonic ku byuma bito kugira ngo bifatanye 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'umusaruro ugabanya ibintu, uzwi nka hybrid manufacturing process, aho gusya no gutunganya laser bigena imiterere y'urwego rw'ibikoresho bifatanye 24, 25. Ibi bivuze ko umukoresha adahagarikwa n'ibibazo bifitanye isano no gukuraho ibikoresho by'ibanze bisigaye mu miyoboro mito y'amazi, nk'uko bikunze kugaragara muri sisitemu y'ifu n'amazi AM26, 27, 28. Ubu bwigenge bwo gushushanya bunagera no ku guhitamo ibikoresho biboneka - UAM ishobora guhuza ibikoresho bisa n'ubushyuhe n'ibindi bitandukanye mu ntambwe imwe. Guhitamo guhuza ibikoresho birenze inzira yo gushonga bivuze ko ibisabwa na mekanike na shimi mu bikorwa byihariye bishobora kuzuzwa neza. Uretse guhuza bikomeye, ikindi kintu kibaho iyo ibikoresho bya pulasitiki bifatanye ni ukugenda cyane kw'ibikoresho bya pulasitiki ku bushyuhe buri hasi 29, 30, 31, 32, 33. Iki kintu cyihariye cya UAM cyemerera ibintu bya mekanike/ubushyuhe gushyirwa hagati y'ibyuma bitangiritse. Ibikoresho bya UAM bishyirwamo bishobora koroshya gutanga amakuru mu buryo nyabwo kuva kuri igikoresho kugeza ku mukoresha binyuze mu isesengura ryakozwe.
Imirimo yakozwe n'abanditsi32 yagaragaje ubushobozi bwa gahunda ya UAM bwo gukora imiterere y'icyuma ya 3D microfluidic ifite ubushobozi bwo kumenya ibintu. Iki gikoresho ni icyo kugenzura gusa. Iyi ngingo igaragaza urugero rwa mbere rw'icyuma cya microfluidic chemical reactor cyakozwe na UAM, igikoresho gikora kitagenzura gusa ahubwo kinatera imikorere ya chemical hamwe n'ibikoresho bya catalytic bihujwe n'imiterere. Iki gikoresho gihuza ibyiza byinshi bifitanye isano n'ikoranabuhanga rya UAM mu gukora ibikoresho bya 3D chemical, nko: ubushobozi bwo guhindura igishushanyo cyuzuye cya 3D uhereye ku gishushanyo cya mudasobwa (CAD) kikajyamo ikintu; gukora ibikoresho byinshi kugira ngo habeho uburyo bwinshi bwo gutwara ubushyuhe n'ibikoresho bya catalytic, ndetse n'ibikoresho by'ubushyuhe bishyirwa hagati y'imigezi ya reactant kugira ngo hagenzurwe neza kandi hacungwe ubushyuhe bw'ikirahure. Kugira ngo herekanwe imikorere ya reactor, hakozwe isomero ry'ibintu by'ingenzi bya 1,4-dissubstituted 1,2,3-triazole byakozwe n'umuringa-catalyzed 1,3-dipolar Huisgen cycloaddition. Iki gikorwa kigaragaza uburyo ikoreshwa ry’ubumenyi bw’ibikoresho n’igishushanyo mbonera gifashijwe na mudasobwa bishobora gutanga amahirwe mashya n’amahirwe ku bijyanye na chimie binyuze mu bushakashatsi buhuriweho n’inzego zitandukanye.
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 na 100 MHz, uko bikurikirana, byabonetse kuri spectrometer ya JEOL ECS-400 400 MHz cyangwa spectrometer ya Bruker Avance II 400 MHz ifite 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 ryavumbuwe bishobora kwigwa hakoreshejwe ibikoresho bikurikira byasohotse34,35,36,37. Igikoresho (Ishusho ya 1) cyakoreshejwe hakoreshejwe sisitemu ikomeye ya 9 kW SonicLayer 4000® UAM (Fabrisonic, Ohio, USA). Ibikoresho byatoranijwe mu gikoresho cyo gutemba ni Cu-110 na Al 6061. Cu-110 ifite umuringa mwinshi (nibura 99.9% by'umuringa), bigatuma iba nziza mu gukora ibikorwa bya catalyzed by'umuringa bityo ikaba ikoreshwa nk'"urwego rukora imbere muri microreactor. Al 6061 O ikoreshwa nk'ibikoresho "byinshi". , kimwe n'urwego rw'intercalation rukoreshwa mu gusesengura; intercalation y'ibice by'inyongera bya alloy hamwe na annealed state hamwe na Cu-110 layer. byagaragaye ko bidahinduka mu buryo bwa shimi hamwe na reagents zakoreshejwe muri iki gikorwa. Al 6061 O hamwe na Cu-110 nabyo bifatwa nk'uruvange rw'ibikoresho bihuye na UAM bityo bikaba ari ibikoresho bikwiye muri ubu bushakashatsi38,42. Ibi bikoresho bikubiye mu mbonerahamwe ya 1 hepfo.
Intambwe zo gukora Reactor (1) 6061 substrate ya aluminiyumu (2) Gukora umuyoboro wo hasi uvuye kuri foil y'umuringa (3) Gushyiramo thermocouples hagati y'ibice (4) Umuyoboro wo hejuru (5) Injira n'aho isohoka (6) Reactor ya monolithic.
Filozofiya yo gushushanya umuyoboro w'amazi ni ugukoresha inzira igoramye kugira ngo wongere intera igenda n'amazi ari mu gice cy'urukuta mu gihe ukomeza kuba mwiza. Uku kwiyongera kw'intera ni byiza kugira ngo wongere igihe cyo gukorana na catalyst-reactant no gutanga umusaruro mwiza w'ibicuruzwa. Utwo duce dukoresha 90° ku mpera z'inzira igororotse kugira ngo dutere kuvanga mu buryo butunguranye mu gikoresho44 kandi twongere igihe cyo gukorana n'amazi n'ubuso (catalyst). Kugira ngo twongere imbaraga zo kuvanga zishobora kugerwaho, igishushanyo cya reactor kirimo inlets ebyiri za reactant zihujwe mu gice cya Y mbere yo kwinjira mu gice cy'urukuta rwo kuvanga. Irembo rya gatatu, rinyura hagati mu nzira hagati mu gice cyaryo, riri muri gahunda y'ibikorwa byinshi byo gukorana mu byiciro byinshi bizaza.
Imiyoboro yose ifite ishusho kare (nta nguni zitagira inguni zigoye), ibi bikaba ari umusaruro w’imashini isya ya CNC ikoreshwa mu gukora imiterere y’imiyoboro. Ingano z’imiyoboro zitoranywa kugira ngo zitange umusaruro mwinshi (kuri microreactor), ariko nto bihagije kugira ngo yorohereze imikoranire n’ubuso (catalysts) ku bintu byinshi birimo. Ingano ikwiye ishingiye ku bunararibonye bw’abanditsi ba kera ku bikoresho by’imikorere y’icyuma n’amazi. Ingano z’imbere z’umuyoboro wa nyuma zari 750 µm x 750 µm kandi ingano yose ya reactor yari 1 ml. Igishushanyo cyubatswemo (1/4″-28 UNF thread) kirimo mu gishushanyo kugira ngo byoroshye guhuza igikoresho n’ibikoresho bya shimi bikoreshwa mu bucuruzi. Ingano y’umuyoboro igengwa n’ubunini bw’ibikoresho bya foil, imiterere yabyo, n’ibipimo byo guhuza bikoreshwa na ultrasonic. Ku bugari runaka bw’ibikoresho runaka, ibikoresho "bizagwa" mu muyoboro wakozwe. Ubu nta cyitegererezo cyihariye cy'iki gikorwa cyo kubara gihari, bityo ubugari ntarengwa bw'umuyoboro ku bikoresho n'igishushanyo runaka bugenwa mu buryo bw'igerageza, muri icyo gihe ubugari bwa µm 750 ntibuzatuma habaho kugwa.
Imiterere (kare) y'umuyoboro igenwa hakoreshejwe icyuma gikata kare. Imiterere n'ingano by'imiyoboro bishobora guhindurwa ku mashini za CNC hakoreshejwe ibikoresho bitandukanye byo gukata kugira ngo haboneke uburyo butandukanye bwo gutembera n'imiterere. Urugero rwo gukora umuyoboro ugonze ufite igikoresho cya µm 125 ruboneka muri Monaghan45. Iyo urwego rwa foil rushyizwe mu buryo burambuye, ikoreshwa ry'ibikoresho bya foil ku miyoboro rizagira ubuso burambuye (kare). Muri uyu murimo, hakoreshejwe igishushanyo mbonera cya kare kugira ngo habungabungwe uburinganire bw'umuyoboro.
Mu gihe cyo guhagarika gukora, ibikoresho by'ubushyuhe bya thermocouple (ubwoko bwa K) byubatswe mu buryo butaziguye mu gikoresho hagati y'amatsinda y'imiyoboro yo hejuru n'iyo hasi (Ishusho ya 1 - icyiciro cya 3). Ibi bikoresho by'ubushyuhe bishobora kugenzura impinduka z'ubushyuhe kuva kuri -200 kugeza kuri 1350 °C.
Uburyo bwo gushyira icyuma mu ihembe rya UAM bukoreshwa n'icyuma gifata impapuro gifite ubugari bwa mm 25.4 n'ubugari bwa mikoroni 150. Izi ngingo za kopi zihujwe mu ruhererekane rw'imirongo yegeranye kugira ngo zitwikire ahantu hose hubatswe; ingano y'ibikoresho byashyizwemo ni nini kuruta umusaruro wa nyuma kuko uburyo bwo gukuramo butanga imiterere ya nyuma isukuye. Uburyo bwo gutunganya CNC bukoreshwa mu gutunganya impande zo hanze n'iz'imbere z'ibikoresho, bigatuma ibikoresho n'imiyoboro bihura n'ibipimo byatoranyijwe by'igikoresho na CNC (muri uru rugero, hafi 1.6 µm Ra). Uburyo bwo gutera no gutunganya ibikoresho bya ultrasonic buri gihe bukoreshwa mu gihe cyose cyo gukora ibikoresho kugira ngo habeho ubuziranenge bw'ibipimo kandi igice cyarangiye kijyanye n'urwego rwo gusya neza rwa CNC. Ubugari bw'umuyoboro ukoreshwa kuri iki gikoresho ni buto bihagije kugira ngo hamenyekane ko ibikoresho bya kopi "bitagwa" mu muyoboro w'amazi, bityo umuyoboro ufite igice cya kare. Icyuho gishoboka mu bikoresho bya kopi n'ibipimo bya gahunda ya UAM byagenzuwe mu buryo bw'igerageza n'umufatanyabikorwa mu gukora (Fabrisonic LLC, USA).
Ubushakashatsi bwagaragaje ko ku gice cya 46, 47 cy’urusobe rwa UAM nta gukwirakwira guke kw’ibintu bidafite ubundi buryo bwo kuvura ubushyuhe, bityo ku bikoresho biri muri iki gikorwa, urwego rwa Cu-110 ruguma rutandukanye n’urwego rwa Al 6061 kandi rurahinduka cyane.
Shyiramo icyuma gipima umuvuduko w’inyuma (BPR) kiri kuri 250 psi (1724 kPa) munsi y’icyuma gipima umuvuduko w’inyuma hanyuma uvome amazi muri icyuma gipima umuvuduko w’ingufu ku kigero cya 0.1 kugeza kuri 1 ml min-1. Umuvuduko w’icyuma gipima umuvuduko w’ingufu wagenzuwe hakoreshejwe icyuma gipima umuvuduko wa FlowSyn cyubatswe muri sisitemu kugira ngo harebwe ko sisitemu ishobora kugumana umuvuduko uhoraho. Ingano y’ubushyuhe ishobora kubaho muri icyuma gipima umuvuduko w’ingufu zagenzuwe hashakishwa itandukaniro riri hagati ya thermocouples zubatswe muri icyuma gipima umuvuduko n’utwo dushyushya twa thermocouples twubatswe mu gipimo cy’ubushyuhe cya firigo ya FlowSyn. Ibi bigerwaho hahinduwe ubushyuhe bwa firigo iri hagati ya 100 na 150 °C mu nyongera ya 25 °C no gukurikirana itandukaniro riri hagati y’ubushyuhe bwateguwe n’ubwanditswe. Ibi byagezweho hakoreshejwe tc-08 data logger (PicoTech, Cambridge, UK) na porogaramu ya PicoLog ijyana nayo.
Imiterere y’uburyo phenylacetylene na iodoethane zikora neza (Scheme 1-Cycloaddition of phenylacetylene na iodoethane, Scheme 1-Cycloaddition of phenylacetylene na iodoethane). Uku kunoza kwakozwe hakoreshejwe uburyo bwose bwa factorial design of experiments (DOE), hakoreshejwe ubushyuhe n'igihe cyo gutura nk'ibintu bihinduka mu gihe hakosorwa alkyne:azide ratio kuri 1:2.
Hateguwe ibisubizo bitandukanye bya sodium azide (0.25 M, 4:1 DMF: H2O), iodoethane (0.25 M, DMF), na phenylacetylene (0.125 M, DMF). Hakozwe aliquot ya 1.5 ml ya buri gisubizo maze inyuzwa muri reactor ku muvuduko n'ubushyuhe byifuzwaga. Igisubizo cy'icyitegererezo cyafashwe nk'igipimo cy'agace k'umusozo w'umusaruro wa triazole n'ibikoresho bya phenylacetylene kandi byagenwe hakoreshejwe chromatography y'amazi ifite imikorere myiza (HPLC). Kugira ngo hakorwe isesengura, ibisubizo byose byafashwe ako kanya nyuma y'uko uruvange rw'ibisubizo ruvuye muri reactor. Urutonde rw'ibipimo byatoranijwe kugira ngo bikosorwe 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), 4.6 x 100 mm, 5 µm ingano y'uduce, iguma kuri 40°C. Umushongi wari isocratic methanol: amazi 50:50 ku gipimo cy'amazi cya 1.5 ml·min-1. Ingano y'umushongi yari 5 μl naho uburebure bw'umushongi bwari 254 nm. % by'ubuso bw'ingero ya DOE byabazwe uhereye ku duce tw'ubuso bw'ibikomoka kuri alkyne na triazole gusa. Kwinjizwa kw'ibikoresho byo gutangira bituma bishoboka kumenya imisozi ijyanye nayo.
Guhuza ibyavuye mu isesengura rya reactor na porogaramu ya MODDE DOE (Umetrics, Malmö, Suwede) byatumye habaho isesengura ryimbitse ry’ibyavuye mu isuzuma no kumenya imiterere myiza y’isuzuma kuri iyi cycloaddition. Gukoresha optimizer yubatswemo no guhitamo amagambo yose y’ingenzi y’icyitegererezo birema urutonde rw’imiterere y’isuzuma ryagenewe kongera ubuso bw’umusaruro mu gihe bigabanya ubuso bw’umusaruro ku gicuruzwa.
Gushyira ogisijeni ku buso bw'umuringa mu cyumba cy'ingufu za kataletiki byagezweho hakoreshejwe umuti wa hydrogen peroxide (36%) unyura mu cyumba cy'ingufu (umuvuduko w'amazi = 0.4 ml min-1, igihe cyo gutura = iminota 2.5) mbere yo gukora buri ruganda rwa triazole.
Iyo imiterere myiza imaze kumenyekana, yashyizwe ku bwoko bwa acetylene na haloalkane derivatives kugira ngo habeho icyegeranyo cy’isomero rito rya synthesis, bityo bigashyirwaho uburyo bwo gukoresha ibi bintu ku bwoko bwa reagents bushoboka (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). Ibipimo bya mililitiro 3 bya buri gisubizo byavanzwe binyuzwa muri reactor ku gipimo cya 75 µl/min n'ubushyuhe bwa 150°C. Ingano yose yakusanyijwe mu kabari hanyuma ivangwa na mililitiro 10 za ethyl acetate. Icyitegererezo cy'igisubizo cyogejwe na mililitiro 3 x 10 z'amazi. Uduce tw'amazi twahujwe hanyuma dukurwamo mililitiro 10 za ethyl acetate, hanyuma utwo duce tw'umwimerere duhuzwa, twogezwa na mililitiro 3 × 10 z'amazi y'umunyu, twumishwa kuri MgSO 4 hanyuma tuyungururwa, hanyuma umuti uvanwa mu cyuma gisukuye. Ingero zasukuwe hakoreshejwe chromatography ya silica gel column 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 mass hamwe na ESI nk'isoko ya ionization. Ingero zose zateguwe hakoreshejwe acetonitrile nk'umusemburo.
Isesengura rya TLC ryakozwe ku masahani ya silica afite substrate ya aluminiyumu. Amasahani yashushanyijwe hakoreshejwe 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 autosampler, pompe ya binary ifite ifuru y'inkingi n'icyuma gipima ubunini bw'uburebure. Hakoreshejwe inkingi ya ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
Inshinge (5 µl) zakozwe mu buryo butaziguye mu mvange y’ibinyabutabire byavanzwe (1:10 dilution) kandi zigasesengurwa hakoreshejwe amazi:methanol (50:50 cyangwa 70:30), uretse ingero zimwe na zimwe zakoreshejwe sisitemu ya 70:30 solvent (yerekanwe nk'umubare w'inyenyeri ) ku gipimo cya 1.5 ml/min. Inkingi yagumye kuri 40°C. Uburebure bw'umuvuduko w'icyuma gipima ni 254 nm.
Ubuso bw'impeshyi y'icyitegererezo bwabazwe uhereye ku gasongero k'agace k'inyongera ka alkyne gasigaye, umusaruro wa triazole gusa, kandi gushyiramo ibikoresho byo gutangira byatumye bishoboka kumenya impeshyi zijyanye nabyo.
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 mu gisubizo cya 5% DMF na 2% HNO3, kandi ingero zose zavanzwe inshuro 20 hakoreshejwe igisubizo cy'icyitegererezo cya DMF-HNO3.
UAM ikoresha ubushuhe bw'icyuma bukoresheje ikoranabuhanga nk'uburyo bwo guhuza icyuma gikoreshwa mu gukora ihuriro rya nyuma. Ubushuhe bw'icyuma bukoresheje icyuma gikoresha ikoranabuhanga rihindagurika (ryitwa ihembe cyangwa ihembe rya ultrasonic) kugira ngo ishyire igitutu kuri icyuma/urwego rwahoze ruhujwe kugira ngo gifatanye/cyahoze gihujwe binyuze mu gutigisa ibikoresho. Kugira ngo ikore neza, sonotrode ifite imiterere isa n'uruziga kandi izunguruka hejuru y'ibikoresho, igafata kole ahantu hose. Iyo igitutu n'ihindagurika bikoreshejwe, okiside ziri ku buso bw'ibikoresho zishobora kwangirika. Igitutu n'ihindagurika rihoraho bishobora gutuma ibikoresho byangirika 36. Guhura cyane n'ubushyuhe n'ihungabana byaho bitera guhuza kw'ibyiciro bikomeye ku miyoboro y'ibikoresho; bishobora kandi guteza imbere guhuza binyuze mu guhindura ingufu z'ubuso48. Imiterere y'uburyo bwo guhuza itsinda ibibazo byinshi bifitanye isano n'ubushyuhe buhindagurika n'ingaruka z'ubushyuhe bwinshi bivugwa mu zindi koranabuhanga zo gukora inyongera. Ibi byemerera guhuza mu buryo butaziguye (ni ukuvuga hatabayeho guhindura ubuso, kuzuza cyangwa kole) by'imiterere myinshi y'ibikoresho bitandukanye mu buryo bumwe buhuriweho.
Ikintu cya kabiri cyiza kuri CAM ni urugero rwinshi 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 imitingito ya ultrasonic 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 gukora 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, reinforcement 46, electronics 50 na thermocouples (iki gikorwa) byashyizwe mu buryo bwiza mu miterere ya UAM kugira ngo habeho ihuriro rikora n'iridakora.
Muri uyu murimo, ubushobozi butandukanye bwo gufatanya ibikoresho n'ubushobozi bwo guhuza UAM byakoreshejwe kugira ngo hakorwe microreactor nziza yo kugenzura ubushyuhe bwa catalytic.
Ugereranije na palladium (Pd) n'izindi catalysts zikoreshwa cyane mu byuma, Cu catalysis ifite ibyiza byinshi: (i) Mu bukungu, Cu irahendutse kurusha izindi metals nyinshi zikoreshwa muri catalysis bityo ikaba ari amahitamo meza ku nganda zikora imiti (ii) urwego rw'ibikorwa bya Cu-catalyzed cross-coupling reactions rurimo kwaguka kandi rusa nkaho rwuzuzanya na Pd51, 52, 53-based methodologies (iii) Ibikorwa bya Cu-catalyzed reactions bikora neza mu gihe nta zindi ligands zihari. Izi ligands akenshi ziba zoroshye mu miterere kandi zidahenze. Iyo ubyifuje, mu gihe izikoreshwa muri shimi ya Pd akenshi ziba zigoye, zihenze, kandi zifata umwuka (iv) Cu, izwi cyane cyane ku bushobozi bwayo bwo guhuza alkynes mu guhuza, nka Sonogashira's bimetallic catalyzed coupling na cycloaddition na azides (click chemistry) (v) Cu ishobora kandi guteza imbere arylation ya nucleophiles zimwe na zimwe mu bikorwa bya Ullmann.
Vuba aha, ingero z'uburyo ibi byose bihinduka mu buryo butandukanye mu gihe hari Cu (0) zagaragaye. Ibi ahanini biterwa n'inganda zikora imiti n'uburyo zibanda ku kugarura no kongera gukoresha catalysts z'ibyuma55,56.
Uburyo bwa 1,3-dipolar cycloaddition reaction hagati ya acetylene na azide kuri 1,2,3-triazole, bwatanzwe bwa mbere na Huisgen mu myaka ya 196057, bufatwa nk'uburyo bwo kwerekana ko ibintu bifitanye isano. Uduce twa triazole 1,2,3 twavuyemo ni ingenzi cyane nk'uburyo bwo kuvumbura imiti bitewe n'uburyo ikoreshwa mu buryo bw'ibinyabuzima n'uburyo ikoreshwa mu buryo butandukanye bwo kuvura 58.
Iyi reaction yongeye kwitabwaho ubwo Sharpless n'abandi bashyiragaho igitekerezo cya "click chemistry"59. Ijambo "click chemistry" rikoreshwa mu gusobanura uburyo bukomeye kandi butoranyije bwo guhuza vuba ibintu bishya n'amasomero ahuza hakoreshejwe uburyo bwa heteroatomic bonding (CXC)60. Ubuhanga bw'iyi reactions buterwa n'umusaruro mwinshi ujyanye na byo. imiterere ni yoroshye, kurwanya ogisijeni n'amazi, kandi gutandukanya ibicuruzwa biroroshye61.
Uburyo bwa kera bwo guhuza 1,3-dipole Huisgen cycloaddition ntabwo buri mu cyiciro cya "click chemistry". Ariko, Medal na Sharpless bagaragaje ko iki gikorwa cyo guhuza azide-alkyne kiba hagati ya 107-108 imbere ya Cu (I) ugereranije no kwihuta gukomeye mu gipimo cya 1,3-dipolar cycloaddition 62,63 idakoresha catalytic. Ubu buryo bwo gukora reaction buteye imbere ntibusaba kurinda amatsinda cyangwa imimerere mibi yo gukora reaction kandi butanga ihinduka ryuzuye n'uburyo bwo guhitamo 1,4-dissubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) uko igihe kigenda gihita (Ishusho ya 3).
Ibisubizo bya isometric bya Huisgen cycloadditions isanzwe n'ifite umuringa. Huisgen cycloadditions ya Cu(I) itanga gusa 1,4-dissubstituted 1,2,3-triazoles, mu gihe Huisgen cycloadditions iterwa n'ubushyuhe ikunze gutanga 1,4- na 1,5-triazoles uruvange rwa stereoisomers ya azole ya 1:1.
Inyinshi muri gahunda zigamije kugabanya amasoko ahamye ya Cu (II), nko kugabanya CuSO4 cyangwa Cu (II) / Cu (0) hamwe n'umunyu wa sodium. Ugereranyije n'izindi reactions za catalyzed metal, gukoresha Cu (I) bifite inyungu nyamukuru zo kuba bihendutse kandi byoroshye gukoresha.
Ubushakashatsi bwa Kinetic na isotopic bwakozwe na Worrell et al. 65 bwagaragaje ko ku bijyanye na alkynes za nyuma, ibintu bibiri bingana na umuringa bigira uruhare mu gutuma buri molekyuli ikora neza ku bijyanye na azide. Uburyo bwatanzwe bunyura mu mpeta y'umuringa ifite ibice bitandatu ikorwa n'imikoranire ya azide na acetylede y'umuringa ifite σ hamwe n'umuringa ufite π nk'umuteranyi w'umusanzu uhamye. Ibikomoka kuri triazolyl by'umuringa bikorwa bitewe no gucika kw'impeta hagakurikiraho gusenyuka kwa proton kugira ngo hakorwe ibicuruzwa bya triazole kandi bifunge uruziga rwa catalytic.
Nubwo ibyiza by'ibikoresho bya shimi bikoreshwa mu gukwirakwiza amazi byagaragajwe neza, habayeho icyifuzo cyo kwinjiza ibikoresho by'isesengura muri izi sisitemu kugira ngo hagenzurwe ibikorwa mu buryo bwihuse muri situ66,67. UAM yagaragaje ko ari uburyo bwiza bwo gushushanya no gukora reactors zikomeye cyane za 3D ziturutse ku bikoresho bikora cyane, bitwara ubushyuhe hamwe n'ibintu byo kumva byinjijwemo (Ishusho ya 4).
Imashini ikora amashanyarazi ya aluminiyumu n'umuringa ikorwa n'inganda zikora ibikoresho bya ultrasonic additives (UAM) ifite imiterere y'imbere y'umuyoboro igoye, thermocouples zubatswemo n'icyumba cy'ingufu zikora amashanyarazi. Kugira ngo harebwe inzira z'amazi y'imbere, hagaragajwe kandi icyitegererezo kigaragara cyakozwe hakoreshejwe stereolithography.
Kugira ngo harebwe ko reactors zikorwa kugira ngo zikoreshwe mu gihe kizaza, solvents zigomba gushyushya neza hejuru y’aho zibira; zirapimwa umuvuduko n’ubushyuhe. Isuzuma ry’umuvuduko ryagaragaje ko sisitemu igumana umuvuduko uhamye kandi uhoraho nubwo haba hari umuvuduko mwinshi muri sisitemu (1.7 MPa). Ibizamini bya hydrostatic byakozwe ku bushyuhe bw’icyumba hakoreshejwe H2O nk’amazi.
Guhuza thermocouple yubatswemo (Ishusho ya 1) n'ikimenyetso cyerekana ubushyuhe byagaragaje ko ubushyuhe bwa thermocouple bwari 6 °C (± 1 °C) munsi y'ubushyuhe bwateguwe muri sisitemu ya FlowSyn. Ubusanzwe, kwiyongera kwa 10 °C mu bushyuhe byikubye kabiri igipimo cy'ubushyuhe, bityo itandukaniro ry'ubushyuhe rya dogere nke gusa rishobora guhindura igipimo cy'ubushyuhe cyane. Iri tandukaniro riterwa n'igihombo cy'ubushyuhe muri RPV yose bitewe n'ubushyuhe bwinshi bw'ibikoresho bikoreshwa mu gukora. Uku guhindagurika k'ubushyuhe ni ukw'igihe kirekire bityo bishobora kwitabwaho mu gushyiraho ibikoresho kugira ngo ubushyuhe nyabwo bugerweho kandi bupimwe mu gihe cy'ubushyuhe. Bityo, iki gikoresho cyo kugenzura kuri interineti cyorohereza kugenzura ubushyuhe bw'ubushyuhe kandi bigafasha mu kunoza neza inzira no guteza imbere imiterere myiza. Izi sensor zishobora kandi gukoreshwa mu kumenya ingaruka za exothermic no gukumira ingaruka za hato na hato muri sisitemu nini.
Reactor igaragazwa muri iyi nyandiko 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 byagaragaye bijyanye no gutunganya umuringa cyangwa aluminiyumu (ii) kunoza uburyo bwo gushonga imbere mu miyoboro ugereranije n'uburyo bwo gushonga ifu (PBF) nko gushonga ifu (SLM)25,69 Uburyo bubi bwo gutembera n'imiterere y'ubuso bugoye26 (iii) ubushyuhe buke bwo gutunganya, byoroshya uburyo bwo guhuza ibintu mu buryo butaziguye, ibyo bidashoboka mu ikoranabuhanga rya puderi, (v) gutsinda 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 alkinazide cycloaddition byakozwe n'umuringa mu gihe cy'imivuduko ihoraho (Ishusho ya 2). Imashini ya ultrasonic francérateur y'umuringa yacapwe igaragara ku ishusho ya 4 yahujwe n'uburyo bwo gutembera mu bucuruzi kandi yakoreshejwe mu gukora isomero rya azide ry'ubwoko butandukanye bwa 1,4-dissubstituted 1,2,3-triazoles hakoreshejwe uburyo bwo kugenzura ubushyuhe bwa acetylene na alkyl group halides mu gihe hari sodium chloride (Ishusho ya 3). Gukoresha uburyo bwo gutembera buhoraho bigabanya ibibazo by'umutekano bishobora 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 cycloaddition ya phenylacetylene na iodoethane (Ishusho ya 1 - Cycloaddition ya phenylacetylene na iodoethane) (reba Ishusho ya 5).
(Hejuru ibumoso) Igishushanyo mbonera cy'uburyo bwakoreshejwe mu gushyira reactor ya 3DP muri sisitemu y'amazi (hejuru iburyo) yakuwe muri gahunda yakozwe neza (yo hepfo) ya gahunda ya Huisgen 57 cycloaddition hagati ya phenylacetylene na iodoethane kugira ngo irusheho kunozwa no kwerekana ibipimo by'igipimo cyo guhindura ibintu mu buryo bwiza.
Mu kugenzura igihe cy’aho ibintu bihurira mu gice cy’ingufu cya reactor biherereye no gukurikirana neza ubushyuhe bw’aho ibintu bihurira hakoreshejwe sensor ya thermocouple, imiterere y’ibikorwa ishobora kunozwa vuba kandi neza hakoreshejwe igihe gito n’ibikoresho. Byagaragaye vuba ko impinduka nini yagezweho hakoreshejwe igihe cy’aho ibintu bihurira iminota 15 n’ubushyuhe bw’aho ibintu bihurira bwa 150°C. Bigaragara ku gishushanyo mbonera cya porogaramu ya MODDE ko igihe cyo gutura n’ubushyuhe bw’aho ibintu bihurira ari ibintu by’ingenzi by’icyitegererezo. Gukoresha optimizer yubatswemo hakoreshejwe izi mimerere yatoranijwe birema urutonde rw’imiterere y’ibikorwa byagenewe kongera ubuso bw’ibicuruzwa mu gihe bigabanya ubuso bw’ibicuruzwa bitangira. Uku kunoza kwatanze impinduka ya 53% by’ibicuruzwa bya triazole, bihuye neza n’ibyari byarahanuwe na moderi ya 54%.