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Masana'antar ƙari tana canza yadda masu bincike da masana masana'antu ke tsarawa da ƙera na'urorin sinadarai don biyan buƙatunsu na musamman. A cikin wannan aikin, mun ba da rahoton misali na farko na reactor mai kwarara wanda aka ƙirƙira ta hanyar dabarar lamination na ƙarfe mai ƙarfi na Ultrasonic Additive Manufacturing (UAM) tare da sassan catalytic da aka haɗa kai tsaye da abubuwan ji. Ba wai kawai fasahar UAM ta shawo kan yawancin ƙuntatawa da ke da alaƙa da kera ƙarin reactors na sinadarai ba, har ma tana ƙara ƙarfin irin waɗannan na'urori sosai. An haɗa jerin mahaɗan triazole masu mahimmanci na halitta guda 1,4 waɗanda aka cire daga maye gurbinsu ta hanyar amsawar cycloaddition na Huisgen 1,3-dipolar ta hanyar Cu ta amfani da saitin sunadarai na UAM. Ta hanyar amfani da kaddarorin musamman na UAM da ci gaba da sarrafa kwarara, na'urar tana iya haɓaka halayen da ke gudana yayin da kuma samar da ra'ayi na ainihin lokaci don sa ido da ingantawa.
Saboda fa'idodin da yake da su fiye da takwarorinsa na babban yawa, ilimin sunadarai na kwarara muhimmin fanni ne kuma mai girma a fannoni na ilimi da na masana'antu saboda ikonsa na ƙara zaɓi da ingancin haɗakar sinadarai. Wannan ya fara daga ƙirƙirar ƙwayoyin halitta masu sauƙi1 zuwa mahaɗan magunguna2,3 da samfuran halitta4,5,6. Fiye da kashi 50% na halayen da ake samu a masana'antar sinadarai da magunguna masu kyau za su iya amfana daga amfani da sarrafa kwarara akai-akai7.
A cikin 'yan shekarun nan, akwai karuwar yanayin ƙungiyoyi da ke neman maye gurbin kayan aikin gilashi na gargajiya ko na sinadarai masu gudana tare da "tasoshin amsawa" na sunadarai masu customizable ƙera ƙari (AM) 8. Tsarin maimaitawa, samarwa cikin sauri, da kuma damar girma 3 (3D) na waɗannan dabarun suna da amfani ga waɗanda ke son keɓance na'urorinsu zuwa takamaiman saitin martani, na'urori, ko yanayi. Zuwa yau, wannan aikin ya mayar da hankali ne kawai kan amfani da dabarun bugawa na 3D na polymer kamar stereolithography (SL)9,10,11, ƙirar deposition fused (FDM)8,12,13,14 da bugawa ta inkjet 7, 15, 16. Rashin ƙarfi da ikon irin waɗannan na'urori don yin nau'ikan halayen sinadarai/nazari iri-iri17, 18, 19, 20 babban abin da ke iyakance aiwatar da AM a wannan fanni17, 18, 19, 20.
Saboda karuwar amfani da sinadarai masu kwarara da kuma kyawawan halaye da ke da alaƙa da AM, akwai buƙatar bincika ƙarin dabarun ci gaba waɗanda ke ba masu amfani damar ƙera tasoshin amsawar kwarara tare da ingantattun ƙarfin sinadarai da na nazari. Waɗannan dabarun ya kamata su ba masu amfani damar zaɓar daga cikin nau'ikan kayan aiki masu ƙarfi ko aiki waɗanda ke iya sarrafa yanayi daban-daban na amsawa, yayin da kuma sauƙaƙe nau'ikan fitarwa na nazari daga na'urar don ba da damar sa ido da sarrafawa.
Ɗaya daga cikin hanyoyin ƙera ƙarin abubuwa da ke da yuwuwar haɓaka na'urorin sinadarai na musamman shine Manufacturing Ultrasonic Additive Manufacturing (UAM). Wannan dabarar lamination ɗin takarda mai ƙarfi tana amfani da ultrasonic oscillations zuwa ƙananan ƙarfe foils don haɗa su tare Layer by Layer tare da ƙarancin dumama mai yawa da babban matakin kwararar filastik 21, 22, 23. Ba kamar yawancin sauran fasahar AM ba, ana iya haɗa UAM kai tsaye tare da masana'antar rage abubuwa, wanda aka sani da tsarin masana'antu na haɗin gwiwa, wanda injin niƙa na'urar sarrafa lambobi ta kwamfuta (CNC) ko injin laser ke bayyana siffar layi na Layer na kayan haɗin 24, 25. Wannan yana nufin cewa mai amfani ba shi da iyaka ta matsalolin da ke tattare da cire kayan ginin da ya rage daga ƙananan tashoshi na ruwa, wanda galibi haka yake tare da tsarin foda da ruwa na AM26, 27, 28. Wannan 'yancin ƙira kuma ya haɗu da zaɓin kayan da ake da su - UAM na iya haɗa haɗin kayan da suka yi kama da na zafi da na daban a cikin mataki ɗaya na tsari. Zaɓin haɗin kayan da suka wuce tsarin narkewa yana nufin cewa ana iya biyan buƙatun injina da sinadarai na takamaiman aikace-aikace. Baya ga haɗin yanayin ƙarfi, wani abu daban An haɗu da shi yayin haɗakar ultrasonic shine yawan kwararar kayan filastik a yanayin zafi mai ƙarancin zafi29,30,31,32,33. Wannan fasalin na musamman na UAM na iya sauƙaƙe saka abubuwan injiniya/zafi tsakanin yadudduka na ƙarfe ba tare da lalacewa ba. Na'urori masu auna firikwensin da aka saka na UAM na iya sauƙaƙe isar da bayanai na ainihin lokaci daga na'urar zuwa ga mai amfani ta hanyar nazarin da aka haɗa.
Aikin marubutan da suka gabata32 ya nuna ikon tsarin UAM na ƙirƙirar tsarin microfluidic na ƙarfe na 3D tare da ƙarfin ji da aka haɗa. Wannan na'urar sa ido ce kawai. Wannan takarda ta gabatar da misali na farko na reactor na sinadarai na microfluidic da UAM ta ƙera; na'ura mai aiki wacce ba wai kawai ke sa ido ba har ma tana haifar da haɗakar sinadarai ta hanyar kayan haɓaka tsarin. Na'urar ta haɗa fa'idodi da dama da ke da alaƙa da fasahar UAM a cikin kera na'urorin sinadarai na 3D, kamar: ikon canza cikakkun zane-zane na 3D kai tsaye daga samfuran ƙira na kwamfuta (CAD) zuwa samfura; ƙera kayan aiki da yawa don haɗa babban ƙarfin zafi da kayan catalytic; da saka na'urori masu auna zafi kai tsaye tsakanin rafukan reagent don sa ido da sarrafa zafin jiki daidai. Don nuna aikin reactor, an haɗa ɗakin karatu na mahaɗan triazole masu mahimmanci 1,2,3-disposals 1,4-dispolar ta hanyar cycloaddition na Huisgen 1,3-dipolar da aka ƙera ta jan ƙarfe. Wannan aikin yana nuna yadda amfani da kimiyyar kayan aiki da ƙirar da kwamfuta ta taimaka wa kwamfuta zai iya buɗe sabbin damammaki da damar yin amfani da sinadarai ta hanyar bincike mai zurfi.
An sayi dukkan sinadaran da aka tace da kuma abubuwan da aka haɗa daga Sigma-Aldrich, Alfa Aesar, TCI ko Fischer Scientific kuma an yi amfani da su ba tare da an riga an tsarkake su ba. An samo spectra na 1H da 13C NMR da aka rubuta a 400 MHz da 100 MHz, bi da bi, ta amfani da na'urar spectrometer ta JEOL ECS-400 400 MHz ko na'urar spectrometer ta Bruker Avance II 400 MHz da kuma na'urar CDCl3 ko (CD3)2SO a matsayin abubuwan da suka rage. An yi dukkan halayen ta amfani da dandamalin sinadaran Uniqsis FlowSyn flow.
An yi amfani da UAM don ƙera dukkan na'urori a cikin wannan binciken. An ƙirƙiro fasahar a shekarar 1999, kuma ana iya yin nazarin bayanan fasaha, sigogin aiki da ci gabanta tun lokacin da aka ƙirƙira ta ta hanyar kayan da aka buga masu zuwa34,35,36,37. An aiwatar da na'urar (Hoto na 1) ta amfani da tsarin SonicLayer 4000® UAM mai ƙarfi sosai, 9kW (Fabrisonic, OH, Amurka). Kayan da aka zaɓa don ƙera na'urar kwarara sune Cu-110 da Al 6061. Cu-110 yana da babban abun ciki na jan ƙarfe (mafi ƙarancin 99.9% jan ƙarfe), wanda hakan ya sa ya zama kyakkyawan zaɓi ga halayen jan ƙarfe, don haka ana amfani da shi azaman "layi mai aiki a cikin microreactor. Ana amfani da Al 6061O azaman kayan "babban", kuma ana amfani da Layer ɗin Sakawa don bincike; Shigar da kayan haɗin ƙarfe da yanayin annealed tare da Layer Cu-110. Al 6061O abu ne da aka nuna yana dacewa sosai da UAM tsari38, 39, 40, 41 kuma an gwada shi kuma an gano cewa yana da daidaito a sinadarai tare da abubuwan da aka yi amfani da su a cikin wannan aikin. Haɗin Al 6061 O tare da Cu-110 kuma ana ɗaukarsa haɗin kayan da suka dace da UAM kuma saboda haka abu ne mai dacewa da wannan binciken. 38,42 Waɗannan na'urori an jera su a cikin Tebur 1 a ƙasa.
Matakan ƙera reactor (1) Al 6061 substrate (2) Ƙirƙirar tashar ƙasa da aka saita zuwa foil na jan ƙarfe (3) Saka thermocouples tsakanin yadudduka (4) Tashar sama (5) Shiga da fita (6) Reactor mai monolithic.
Falsafar ƙira ta hanyar ruwa ita ce amfani da hanyar da aka haɗa don ƙara nisan da ruwa ke tafiya a cikin guntu, yayin da ake kiyaye guntu a girman da za a iya sarrafawa. Wannan ƙaruwar nisa yana da kyau don ƙara lokacin hulɗar mai kara kuzari/mai amsawa da kuma samar da kyakkyawan yawan samfuri. Kwakwalwan suna amfani da lanƙwasa 90° a ƙarshen hanyar madaidaiciya don haifar da haɗuwa mai rikitarwa a cikin na'urar44 da kuma ƙara lokacin hulɗar ruwan da saman (mai kara kuzari). Don ƙara yawan haɗuwa da za a iya cimmawa, ƙirar mai kara kuzari tana da mashigar reactor guda biyu da aka haɗa a mahaɗin Y kafin shiga sashin haɗa serpentine. Mashiga ta uku, wacce ke haɗa rafin a tsakiyar wurin zama, an haɗa ta cikin ƙirar haɗakar martanin matakai da yawa na gaba.
Duk tashoshi suna da siffar murabba'i (babu kusurwoyin zane), sakamakon niƙa CNC na lokaci-lokaci da ake amfani da shi don ƙirƙirar tsarin tashar. An zaɓi girman tashar don tabbatar da fitowar girma mai girma (ga microreactor), yayin da yake ƙarami don sauƙaƙe hulɗar saman (masu haɓaka) ga yawancin ruwan da ke ciki. Girman da ya dace ya dogara ne akan ƙwarewar marubutan da suka gabata tare da na'urorin ƙarfe-ruwa don amsawar. Girman ciki na tashar ƙarshe shine 750 µm x 750 µm kuma jimlar girman reactor shine 1 ml. An haɗa mai haɗawa (1/4″—28 UNF zare) a cikin ƙirar don ba da damar sauƙaƙe hulɗar na'urar tare da kayan aikin sinadarai na kasuwanci. Girman tashar yana iyakance ta hanyar kauri na kayan foil, halayen injina, da sigogin haɗin da ake amfani da su tare da ultrasonics. A wani takamaiman faɗi na wani abu, kayan zai "ruɓe" cikin tashar da aka ƙirƙira. A halin yanzu babu takamaiman samfurin don wannan lissafi, don haka ana ƙayyade matsakaicin faɗin tashar don wani abu da ƙira da aka bayar ta hanyar gwaji; a wannan yanayin, faɗin 750 μm ba zai haifar da tsagewa ba.
Ana tantance siffar (murabba'i) ta hanyar amfani da abin yanka murabba'i. Ana iya canza siffar da girman tashoshin ta hanyar amfani da kayan aikin yankewa daban-daban don samun saurin kwarara da halaye daban-daban. Misali na ƙirƙirar tashar siffa mai lanƙwasa ta amfani da kayan aikin 125 μm za a iya samu a cikin aikin Monaghan45. Lokacin da aka ajiye layin foil a cikin salon layi, rufin kayan foil a kan tashoshin zai sami ƙarewa mai faɗi (murabba'i). A cikin wannan aikin, don kiyaye daidaiton tashar, an yi amfani da zane mai siffar murabba'i.
A lokacin da aka riga aka shirya yin ƙera, ana saka na'urorin auna zafin jiki na thermocouple (Nau'in K) kai tsaye a cikin na'urar tsakanin ƙungiyoyin tashoshi na sama da na ƙasa (Hoto na 1 - Mataki na 3). Waɗannan na'urorin auna zafin jiki na thermocouple na iya sa ido kan canje-canjen zafin jiki daga −200 zuwa 1350 °C.
Ana yin aikin adana ƙarfe ta hanyar amfani da ƙaho na UAM ta amfani da foil ɗin ƙarfe mai faɗin mm 25.4, mai kauri micron 150. Waɗannan yadudduka na foil ɗin an haɗa su cikin jerin layukan da ke maƙwabtaka don rufe dukkan yankin ginin; girman kayan da aka ajiye ya fi girma fiye da samfurin ƙarshe yayin da tsarin cirewa ke samar da siffa ta ƙarshe. Ana amfani da injin CNC don na'urar da ke cikin kayan aiki na waje da na ciki, wanda ke haifar da ƙarewar saman kayan aiki da tashoshi daidai da kayan aikin da aka zaɓa da sigogin aikin CNC (kimanin 1.6 μm Ra a cikin wannan misalin). Ana amfani da ci gaba da ci gaba da zubar da kayan ultrasonic da kera da kera a duk tsawon tsarin kera na'urar don tabbatar da daidaiton girma kuma ɓangaren da aka gama zai cika matakan daidaiton niƙa na CNC. Faɗin tashar da aka yi amfani da ita don wannan na'urar ƙarami ne don tabbatar da cewa kayan foil ɗin ba ya "rufe" cikin tashar ruwa, don haka tashar tana riƙe da sashe mai murabba'i. An ƙayyade gibin da zai yiwu a cikin kayan foil da sigogin aikin UAM ta hanyar gwaji ta hanyar abokin masana'anta (Fabrisonic LLC, Amurka).
Bincike ya nuna cewa ƙaramin yaduwar abubuwa yana faruwa a mahaɗin haɗin UAM 46, 47 ba tare da ƙarin maganin zafi ba, don haka ga na'urorin da ke cikin wannan aikin, layin Cu-110 ya bambanta da layin Al 6061 kuma yana canzawa kwatsam.
Shigar da na'urar daidaita matsin lamba ta baya mai ƙarfin 250 psi (1724 kPa) (BPR) zuwa ga mashigar reactor ɗin sannan a yi famfo da ruwa ta cikin reactor ɗin a cikin ƙimar 0.1 zuwa 1 mL min-1. An sa ido kan matsin lambar reactor ɗin ta amfani da firikwensin matsin lamba na tsarin FlowSyn da aka gina a ciki don tabbatar da cewa tsarin zai iya ci gaba da riƙe matsin lamba mai ɗorewa. An gwada yanayin zafin da zai iya faruwa a cikin reactor ɗin ta hanyar gano duk wani bambanci tsakanin thermocouples da aka saka a cikin reactor ɗin da waɗanda aka saka a cikin farantin dumama na FlowSyn. Ana samun wannan ta hanyar canza zafin zafi na farantin zafi tsakanin 100 zuwa 150 °C a cikin ƙaruwa na 25 °C da kuma lura da duk wani bambanci tsakanin yanayin zafi da aka tsara da wanda aka yi rikodin. An cimma wannan ta amfani da mai rikodin bayanai na tc-08 (PicoTech, Cambridge, UK) da software na PicoLog.
An inganta yanayin amsawar cycloaddition na phenylacetylene da iodoethane (Shiri na 1- Cycloaddition na phenylacetylene da iodoethane Tsarin 1- Cycloaddition na phenylacetylene da iodoethane). An yi wannan ingantawa ta hanyar cikakken ƙirar gwaje-gwaje (DOE), ta amfani da yanayin zafi da lokacin zama azaman sigogi masu canzawa, yayin da ake gyara rabon alkyne:azide a 1:2.
An shirya mafita daban-daban na sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), da phenylacetylene (0.125 M, DMF). An haɗa rabon 1.5 mL na kowane maganin kuma an tura shi ta cikin reactor a daidai lokacin da ake buƙata da zafin jiki. An ɗauki martanin samfurin a matsayin rabon yanki mafi girma na samfurin triazole zuwa kayan farawa na phenylacetylene kuma an ƙaddara shi ta hanyar babban aikin ruwa chromatography (HPLC). Don daidaiton bincike, an ɗauki duk halayen jim kaɗan bayan cakuda amsawar ya bar reactor. Jerin sigogi da aka zaɓa don ingantawa an nuna su a cikin Tebur 2.
An yi nazarin dukkan samfuran ta amfani da tsarin Chromaster HPLC (VWR, PA, Amurka) wanda ya ƙunshi famfo na quaternary, tanda mai shafi, na'urar gano UV mai canzawa da kuma na'urar sampler ta atomatik. Ginshiƙin ya kasance Daidaito 5 C18 (VWR, PA, Amurka), girman 4.6 × 100 mm, girman barbashi 5 µm, wanda aka kiyaye a 40 °C. Maganin narkewar ya kasance isocratic 50:50 methanol:ruwa a ƙimar kwarara na 1.5 mL.min-1. Girman allurar ya kasance 5 µL kuma tsawon na'urar ganowa shine 254 nm. An ƙididdige yankin kololuwar kashi na samfurin DOE daga yankunan kololuwar samfuran alkyne da triazole da suka rage kawai. Allurar kayan farawa tana ba da damar gano kololuwar da suka dace.
Haɗa fitowar binciken reactor zuwa software na MODDE DOE (Umetrics, Malmö, Sweden) ya ba da damar yin cikakken bincike game da yanayin sakamako da kuma tantance mafi kyawun yanayin amsawa don wannan cycloaddition. Gudanar da ingantaccen kayan aiki da zaɓar duk mahimman sharuɗɗan samfuri yana haifar da saitin yanayin amsawa wanda aka tsara don haɓaka yankin kololuwar samfuri yayin da rage yankin kololuwar kayan farawa na acetylene.
An cimma nasarar haɗakar jan ƙarfe a saman ɗakin amsawar catalytic ta amfani da maganin hydrogen peroxide (36%) da ke gudana ta cikin ɗakin amsawar (yawan kwarara = 0.4 mL min-1, lokacin zama = minti 2.5) kafin a haɗa kowane ɗakin karatu na mahaɗin triazole.
Da zarar an gano mafi kyawun yanayi, an shafa su a kan nau'ikan acetylene da haloalkane don ba da damar haɗa ƙaramin haɗin ɗakin karatu, ta haka ne aka tabbatar da ikon amfani da waɗannan yanayi ga nau'ikan reagents masu yawa (Hoto na 1).2).
Shirya mafita daban-daban na sodium azide (0.25 M, 4:1 DMF:H2O), haloalkanes (0.25 M, DMF) da alkynes (0.125 M, DMF). An haɗa rabon 3 mL na kowane maganin kuma an tura shi ta cikin reactor a 75 µL min-1 da 150 °C. An tattara jimlar adadin a cikin kwalba kuma an narkar da shi da 10 mL na ethyl acetate. An wanke samfurin maganin da 3 × 10 mL na ruwa. An haɗa yadudduka masu ruwa kuma an cire su da 10 mL na ethyl acetate; sannan aka haɗa yadudduka na halitta, aka wanke da 3 x 10 mL na brine, aka busar da su akan MgSO4 kuma aka tace, sannan aka cire sinadarin a cikin vacuo. An tsarkake samfuran ta hanyar chromatography na shafi akan silica gel ta amfani da ethyl acetate kafin a yi bincike ta hanyar haɗa HPLC, 1H NMR, 13C NMR da high resolution mass spectrometry (HR-MS).
An samo dukkan spectra ta amfani da na'urar auna ma'aunin zafi ta Thermofischer precision Orbitrap tare da ESI a matsayin tushen ionization. An shirya dukkan samfuran ta amfani da acetonitrile a matsayin mai narkewa.
An yi nazarin TLC akan faranti na silica da aka yi da aluminum. An yi amfani da hasken UV (254 nm) ko fenti da dumama vanillin wajen ganin faranti.
An yi nazarin dukkan samfuran ta amfani da tsarin VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) wanda aka sanye shi da na'urar sampler ta atomatik, famfon tanda mai kusurwa biyu da na'urar gano tsawon rai guda ɗaya. Ginshiƙin da aka yi amfani da shi shine ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
An yi allurai (5 µL) kai tsaye daga cakuda mai ɗanɗano (narkewar 1:10) kuma an yi nazari da ruwa: methanol (50:50 ko 70:30), sai dai wasu samfuran da aka yi amfani da tsarin narkewar 70:30 (wanda aka nuna a matsayin lambar tauraro) a ƙimar kwararar 1.5 mL/min. An ajiye ginshiƙin a 40 °C. Tsawon na'urar ganowa shine 254 nm.
An ƙididdige yankin % na samfurin daga yankin top na sauran alkyne, samfurin triazole kawai, kuma allurar kayan farawa ta ba da damar gano kololuwar da suka dace.
An yi nazarin dukkan samfuran ta amfani da na'urar Thermo iCAP 6000 ICP-OES. An shirya dukkan matakan daidaitawa ta amfani da maganin 1000 ppm Cu a cikin 2% nitric acid (SPEX Certi Prep). An shirya dukkan ka'idoji a cikin maganin DMF 5% da 2% HNO3, kuma an narkar da dukkan samfuran sau 20 a cikin samfurin maganin DMF-HNO3.
UAM tana amfani da walda na ƙarfe na ultrasonic a matsayin dabarar haɗa kayan ƙarfe da aka yi amfani da su don gina haɗuwa ta ƙarshe. Walda na ƙarfe na Ultrasonic yana amfani da kayan aikin ƙarfe mai girgiza (wanda ake kira ƙaho ko ƙaho na ultrasonic) don shafa matsi a kan layin foil/layin da aka haɗa a baya don a haɗa shi yayin da yake girgiza kayan. Don ci gaba da aiki, sonotrode yana da silinda kuma yana birgima a saman kayan, yana haɗa dukkan yankin. Lokacin da aka yi amfani da matsin lamba da girgiza, oxides a saman kayan na iya fashewa. Ci gaba da matsi da girgiza na iya haifar da rashin daidaituwa na kayan 36. Hulɗa ta kusa da zafi da matsin lamba da aka haifar a cikin gida sannan yana haifar da haɗin gwiwa mai ƙarfi a mahaɗin kayan; kuma yana iya taimakawa mannewa ta hanyar canje-canje a cikin kuzarin saman48. Yanayin tsarin haɗin gwiwa yana shawo kan matsalolin da yawa da ke da alaƙa da yanayin narkewa mai canzawa da tasirin zafi mai yawa da aka ambata a cikin wasu dabarun masana'antu na ƙari. Wannan yana ba da damar haɗin kai tsaye (watau, ba tare da gyaran saman ba, cikawa ko mannewa) na yadudduka da yawa na kayan daban-daban zuwa cikin tsari ɗaya mai haɗaka.
Abu na biyu mai kyau ga UAM shine babban matakin kwararar filastik da aka gani a cikin kayan ƙarfe, koda a ƙananan yanayin zafi, watau ƙasa da wurin narkewar kayan ƙarfe. Haɗin ultrasonic oscillation da matsin lamba yana haifar da babban matakan ƙaura iyaka na hatsi na gida da sake sakewa ba tare da babban ƙaruwar zafin jiki da aka saba da shi da kayan girma ba. A lokacin gina taro na ƙarshe, ana iya amfani da wannan lamari don saka abubuwan aiki da masu wucewa tsakanin yadudduka na foil na ƙarfe, layi-layi-layi. Abubuwa kamar zare na gani 49, ƙarfafawa 46, lantarki 50, da thermocouples (wannan aikin) duk an saka su cikin tsarin UAM don ƙirƙirar ƙungiyoyi masu aiki da masu wucewa.
A cikin wannan aikin, an yi amfani da hanyoyin haɗin kayan daban-daban da kuma damar haɗin UAM don ƙirƙirar babban microreactor mai sa ido kan zafin jiki mai catalytic.
Idan aka kwatanta da palladium (Pd) da sauran abubuwan kara kuzari na ƙarfe da aka saba amfani da su, Cu catalysis yana da fa'idodi da yawa: (i) A fannin tattalin arziki, Cu ba ta da tsada fiye da sauran ƙarfe da ake amfani da su a catalysis kuma saboda haka zaɓi ne mai kyau ga masana'antar sarrafa sinadarai (ii) Jerin halayen haɗin gwiwa na Cu-catalyzed yana ƙaruwa kuma yana kama da ya ɗan dace da hanyoyin da aka dogara da Pd51,52,53 (iii) Halayen Cu-catalyzed suna aiki da kyau idan babu wasu ligands, Waɗannan ligands galibi suna da sauƙi a tsarin kuma suna da araha idan ana so, yayin da waɗanda ake amfani da su a cikin sunadarai na Pd galibi suna da rikitarwa, tsada, kuma suna da sauƙin amsawa ga iska (iv) Cu, musamman sananne saboda ikonsa na ɗaure alkynes a cikin haɗakarwa, Misali, haɗin Sonogashira mai bimetallic da cycloaddition tare da azides (click chemistry) (v) Cu kuma yana iya haɓaka arylation na nucleophiles da yawa a cikin halayen Ullmann.
An nuna misalan bambance-bambancen duk waɗannan halayen kwanan nan a gaban Cu(0). Wannan ya faru ne saboda masana'antar magunguna da kuma ƙaruwar mai da hankali kan dawo da sinadarin ƙarfe da sake amfani da shi55,56.
Huisgen ne ya fara wannan aikin a shekarun 1960s57, amsawar cycloaddition mai nauyin 1,3-dipolar tsakanin acetylene da azide zuwa 1,2,3-triazole ana ɗaukarta a matsayin amsawar haɗin gwiwa. Sakamakon haka, sassan triazole 1,2,3 suna da matuƙar muhimmanci a matsayin magunguna a fannin gano magunguna saboda amfaninsu na halitta da kuma amfani da su a cikin magunguna daban-daban 58.
Wannan martanin ya sake dawowa lokacin da Sharpless da wasu suka gabatar da manufar "click chemistry"59. Kalmar "click chemistry" ana amfani da ita don bayyana wani tsari mai ƙarfi, abin dogaro da zaɓi na halayen da za a iya haɗa su cikin sauri na sabbin mahadi da ɗakunan karatu masu haɗin gwiwa ta hanyar haɗin heteroatom (CXC)60. Shahararren waɗannan halayen ya samo asali ne daga yawan amfanin da suke da shi, yanayin amsawar su mai sauƙi ne, juriyar iskar oxygen da ruwa, kuma rabuwar samfura abu ne mai sauƙi61.
Cycloaddition na gargajiya na Huisgen 1,3-dipole ba ya cikin rukunin "sinadarin dannawa". Duk da haka, Medal da Sharpless sun nuna cewa wannan taron haɗin azide-alkyne yana faruwa tsakanin 107 zuwa 108 a gaban Cu(I) idan aka kwatanta da cycloaddition mai girma 1,3-dipolar 62,63 wanda ba a catalyzed ba. Wannan ingantaccen tsarin amsawa baya buƙatar kare ƙungiyoyi ko yanayin amsawa mai tsauri kuma yana samar da kusan cikakkiyar juyawa da zaɓi zuwa 1,2,3-triazoles (anti-1,2,3-triazole) mai 1,4 a kan sikelin lokaci (Hoto na 3).
Sakamakon isometric na cycloadditions na Huisgen na gargajiya da na jan ƙarfe. cycloadditions na Huisgen da aka haɗa da Cu(I) suna samar da 1,4-triazoles kawai da aka cire, yayin da cycloadditions na Huisgen da aka haifar da zafi yawanci suna samar da cakuda stereoisomers na azoles 1,4- da 1,5-triazoles 1:1.
Yawancin ka'idoji sun haɗa da rage tushen tushen Cu(II), kamar rage nau'in CuSO4 ko Cu(II)/Cu(0) tare da haɗuwa da gishirin sodium. Idan aka kwatanta da sauran halayen da aka yi amfani da ƙarfe, amfani da Cu(I) yana da manyan fa'idodi na kasancewa mai araha kuma mai sauƙin sarrafawa.
Nazarin lakabin kinetic da isotopic na Worrell et al. 65 sun nuna cewa, a yanayin alkynes na ƙarshe, daidaikun jan ƙarfe guda biyu suna da hannu wajen kunna amsawar kowace ƙwayar halitta zuwa azide. Tsarin da aka gabatar yana gudana ta hanyar zoben ƙarfe na jan ƙarfe mai membobi shida wanda aka samar ta hanyar haɗa azide zuwa acetylide na jan ƙarfe mai haɗin σ tare da jan ƙarfe mai haɗin π azaman ligand mai ba da gudummawa mai ƙarfi. Ana samar da abubuwan da aka samo daga jan ƙarfe na Triazolyl ta hanyar raguwar zobe, sannan a biyo baya da rushewar proton don samar da samfuran triazole da rufe zagayowar catalytic.
Duk da cewa an rubuta fa'idodin na'urorin sinadarai masu kwarara, akwai sha'awar haɗa kayan aikin nazari a cikin waɗannan tsarin don sa ido kan tsari a layi, a ciki, 66,67. UAM ta tabbatar da cewa hanya ce mai dacewa don tsarawa da samar da masu samar da wutar lantarki masu ƙarfi na 3D waɗanda aka yi da kayan aiki masu aiki da zafi, masu sarrafa zafi tare da abubuwan ji da aka haɗa kai tsaye (Hoto na 4).
An ƙera na'urar samar da wutar lantarki ta aluminum-copper wadda aka ƙera ta hanyar kera ƙarin na'urori masu amfani da ultrasonic (UAM) tare da tsarin tashoshi na ciki mai rikitarwa, na'urorin thermocouples da aka haɗa da kuma ɗakin amsawar catalytic. Don ganin hanyoyin ruwa na ciki, an kuma nuna wani samfurin da aka ƙera ta amfani da stereolithography.
Domin tabbatar da cewa an ƙera na'urorin samar da wutar lantarki don halayen halitta na gaba, ana buƙatar a dumama daskararru lafiya a sama da wurin tafasa; an gwada su da matsin lamba da zafin jiki. Gwajin matsin lamba ya nuna cewa tsarin yana riƙe da matsin lamba mai ɗorewa koda tare da ƙaruwar matsin lamba na tsarin (1.7 MPa). An yi gwajin hydrostatic a zafin ɗaki ta amfani da H2O a matsayin ruwa.
Haɗa thermocouple ɗin da aka saka (Hoto na 1) da mai rikodin bayanan zafin jiki ya nuna cewa thermocouple ya fi sanyi 6 °C (± 1 °C) fiye da zafin da aka tsara akan tsarin FlowSyn. Yawanci, ƙaruwar zafin jiki na 10 °C yana haifar da ninka yawan amsawar, don haka bambancin zafin jiki na digiri kaɗan na iya canza ƙimar amsawar sosai. Wannan bambanci ya faru ne saboda asarar zafin jiki a cikin jikin reactor saboda yawan yaduwar zafi na kayan da ake amfani da su a cikin tsarin kera. Wannan jujjuyawar zafi yana da daidaito kuma saboda haka ana iya lissafa shi a cikin saitin kayan aiki don tabbatar da cewa an isa da auna daidai yanayin zafi yayin amsawar. Saboda haka, wannan kayan aikin sa ido kan layi yana sauƙaƙe sarrafa zafin amsawar sosai kuma yana sauƙaƙe inganta tsari da haɓaka yanayi mafi kyau. Hakanan ana iya amfani da waɗannan na'urori masu auna sigina don gano exotherms na amsawa da hana halayen guduwa a cikin manyan tsarin.
Reactor ɗin da aka gabatar a cikin wannan aikin shine misali na farko na amfani da fasahar UAM don ƙera reactors na sinadarai kuma yana magance wasu manyan ƙuntatawa da ke da alaƙa da buga AM/3D na waɗannan na'urori, kamar: (i) shawo kan matsalolin da aka ruwaito da suka shafi sarrafa ƙarfe ko aluminum alloy (ii) inganta ƙudurin tashar ciki idan aka kwatanta da dabarun haɗa foda (PBF) kamar narkewar laser mai zaɓi (SLM)25,69 Rashin kwararar abu da yanayin saman da ke da tsauri26 (iii) Rage zafin aiki, wanda ke sauƙaƙe haɗin kai tsaye na na'urori masu auna firikwensin, wanda ba zai yiwu ba a cikin fasahar gadon foda, (v) ya shawo kan ƙarancin halayen injiniya da kuma jin daɗin abubuwan da aka haɗa da polymer zuwa ga nau'ikan abubuwan narkewa na halitta iri-iri17,19.
An nuna aikin mai karɓar wutar lantarki ta hanyar jerin halayen cycloaddition na alkyne azide da aka kunna ta hanyar jan ƙarfe a ƙarƙashin yanayin kwarara mai ci gaba (Hoto na 2). An haɗa mai karɓar wutar lantarki da aka buga ta hanyar ultrasonic a cikin Hoto na 4 tare da tsarin kwararar kasuwanci kuma an yi amfani da shi don haɗa azides na ɗakunan karatu na nau'ikan 1,2,3-triazoles daban-daban 1,4-dissublited ta hanyar amsawar acetylene da ƙungiyoyin alkyl halides a gaban sodium chloride (Hoto na 3). Amfani da hanyar kwarara mai ci gaba yana rage damuwar aminci da ka iya tasowa a cikin tsarin tsari, saboda wannan amsawar yana samar da tsaka-tsakin azide mai amsawa da haɗari [317], [318]. Da farko, an inganta amsawar don cycloaddition na phenylacetylene da iodoethane (Shiri na 1 - Cycloaddition na phenylacetylene da iodoethane) (duba Hoto na 5).
(A sama hagu) Tsarin saitin da aka yi amfani da shi don haɗa na'urar 3DP cikin tsarin kwarara (saman dama) da aka samu a cikin tsarin da aka inganta (ƙasa) na tsarin Huisgen cycloaddition 57 tsakanin phenylacetylene da iodoethane don ingantawa da nuna ƙimar juyawar amsawar da aka inganta.
Ta hanyar sarrafa lokacin zama na reagents a cikin ɓangaren catalytic na reactor da kuma sa ido sosai kan zafin amsawar tare da binciken thermocouple kai tsaye, ana iya inganta yanayin amsawa cikin sauri da daidaito tare da ƙarancin lokaci da amfani da kayan aiki. An gano da sauri cewa an sami mafi girman juyawa lokacin da aka yi amfani da lokacin zama na mintuna 15 da zafin amsawa na 150 °C. Daga cikin tsarin coefficient na software na MODDE, ana iya ganin cewa duka lokacin zama da zafin amsawa ana ɗaukar su a matsayin mahimman sharuɗɗan samfuri. Gudanar da ingantaccen kayan aiki da aka gina ta amfani da waɗannan sharuɗɗan da aka zaɓa yana haifar da saitin yanayin amsawa wanda aka tsara don haɓaka yankunan kololuwar samfuri yayin rage yankunan kololuwar kayan farawa. Wannan haɓakawa ya haifar da juyi na 53% na samfurin triazole, wanda ya yi daidai da hasashen samfurin na 54%.
Dangane da wallafe-wallafen da suka nuna cewa jan ƙarfe (I) oxide (Cu2O) na iya aiki a matsayin nau'in catalytic mai tasiri akan saman jan ƙarfe mara sifili a cikin waɗannan halayen, an binciki ikon yin oxidizing saman reactor kafin aiwatar da amsawar a cikin kwararar ruwa70,71. Daga nan aka sake yin martanin da ke tsakanin phenylacetylene da iodoethane a ƙarƙashin yanayi mafi kyau kuma an kwatanta yawan amfanin. An lura cewa wannan shiri ya haifar da ƙaruwa mai yawa a cikin juyawar kayan farawa, wanda aka ƙididdige ya zama >99%. Duk da haka, sa ido ta HPLC ya nuna cewa wannan juyawa ya rage lokacin amsawa mai tsawo sosai har zuwa kimanin mintuna 90, inda aikin ya bayyana ya daidaita kuma ya kai ga "yanayin da ya dace". Wannan lura ya nuna cewa tushen aikin catalytic ana samunsa ne daga saman jan ƙarfe oxide maimakon sifili-valent jan ƙarfe substrate. Ana iya yin oxidize ƙarfe Cu cikin sauƙi a zafin ɗaki don samar da CuO da Cu2O waɗanda ba su da kariya ga kai. Wannan yana kawar da buƙatar ƙara tushen jan ƙarfe (II) don haɗin gwiwa71.