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I-Cellulose nanofibers (CNF) ingatholakala emithonjeni yemvelo efana nezitshalo nezihlahla zokhuni.Izinhlanganisela ze-CNF-reinforced thermoplastic resin zinenani lezinto, okuhlanganisa amandla angcono kakhulu emishini.Njengoba izakhiwo zemishini ye-CNF-reinforced composite zithintwa inani le-fiber eyengeziwe, kubalulekile ukunquma ukugxila kwe-CNF filler ku-matrix ngemva kokubunjwa komjovo noma ukubunjwa kwe-extrusion.Siqinisekise ubudlelwano obuhle bomugqa phakathi kokugxilisa ingqondo kwe-CNF nokumuncwa kwe-terahertz.Singakwazi ukubona umehluko ekugxilweni kwe-CNF kumaphoyinti angu-1% sisebenzisa isizinda sesizinda sesikhathi se-terahertz.Ngaphezu kwalokho, sihlole izakhiwo zemishini ze-CNF nanocomposites sisebenzisa ulwazi lwe-terahertz.
Ama-Cellulose nanofibers (CNFs) ngokuvamile angaphansi kuka-100 nm ububanzi futhi atholakala emithonjeni yemvelo efana nezitshalo nezihlahla zokhuni1,2.Ama-CNF anamandla amakhulu emishini3, ukukhanya okuphezulu kwe-optical4,5,6, indawo enkulu, kanye ne-coefficient ephansi yokwandisa okushisayo7,8.Ngakho-ke, kulindeleke ukuthi zisetshenziswe njengezinto ezisimeme nezisezingeni eliphezulu ekusebenzeni okuhlukahlukene, okuhlanganisa izinto zikagesi9, izinto zokwelapha10 kanye nezinto zokwakha11.Izinhlanganisela eziqiniswe nge-UNV zilula futhi ziqinile.Ngakho-ke, izinhlanganisela eziqiniswe yi-CNF zingasiza ukuthuthukisa ukusebenza kahle kukaphethiloli wezimoto ngenxa yesisindo sazo esilula.
Ukuze kuzuzwe ukusebenza okuphezulu, ukusatshalaliswa okufanayo kwama-CNF kumatrices e-hydrophobic polymer njenge-polypropylene (PP) kubalulekile.Ngakho-ke, kunesidingo sokuhlolwa okungabhubhisi kwezinhlanganisela eziqiniswe nge-CNF.Ukuhlolwa okungabhubhisi kwezinhlanganisela ze-polymer kubikwe12,13,14,15,16.Ukwengeza, ukuhlolwa okungabhubhisi kwe-CNF-reinforced composite ngokusekelwe ku-X-ray computed tomography (CT) kuye kwabikwa i-17.Nokho, kunzima ukuhlukanisa ama-CNF kumatrices ngenxa yokuhluka kwesithombe esiphansi.Ukuhlaziywa kwamalebula e-fluorescent18 kanye nokuhlaziywa kwe-infrared19 kunikeza ukubonwa okucacile kwama-CNF nezifanekiso.Nokho, singathola ulwazi olukha phezulu kuphela.Ngakho-ke, lezi zindlela zidinga ukusika (ukuhlola okulimazayo) ukuze uthole ulwazi lwangaphakathi.Ngakho-ke, sinikeza ukuhlolwa okungabhubhisi okusekelwe kubuchwepheshe be-terahertz (THz).Amagagasi eTerahertz amagagasi kagesi anamaza asukela ku-0.1 kuya ku-10 terahertz.Amagagasi eTerahertz asobala ezintweni ezisetshenziswayo.Ikakhulukazi, i-polymer nezinto zokhuni zisobala kumagagasi e-terahertz.Ukuhlolwa kokuma kwe-liquid crystal polymers21 kanye nesilinganiso sokuguqulwa kwama-elastomers22,23 kusetshenziswa indlela ye-terahertz kuye kwabikwa.Ngaphezu kwalokho, ukutholwa kwe-terahertz kokulimala kwezinkuni okubangelwa izinambuzane kanye nezifo zesikhunta okhunini kuye kwaboniswa24,25.
Siphakamisa ukusebenzisa indlela yokuhlola engacekeli phansi ukuze sithole izakhiwo zemishini yezinhlanganisela eziqiniswe yi-CNF kusetshenziswa ubuchwepheshe be-terahertz.Kulolu cwaningo, siphenya i-terahertz ye-CNF-reinforced composite (CNF/PP) futhi sibonisa ukusetshenziswa kolwazi lwe-terahertz ukuze silinganisele ukuhlangana kwe-CNF.
Njengoba amasampuli alungiswa ngokubumba umjovo, angase athintwe ukuhlukaniswa kwe-polarization.Emkhiwaneni.1 ibonisa ubudlelwano phakathi kwe-polarization yegagasi le-terahertz kanye nokuma kwesampula.Ukuqinisekisa ukuncika kwe-polarization kwama-CNF, izakhiwo zabo ze-optical zikalwa kuye ngokuthi mpo (Fig. 1a) kanye ne-polarization enezingqimba (Fig. 1b).Ngokuvamile, izinto ezihambisanayo zisetshenziselwa ukusabalalisa ama-CNF ngokufanayo ku-matrix.Kodwa-ke, umphumela wabahambisanayo ezilinganisweni ze-THz awukafundwa.Izilinganiso zokuthutha zinzima uma ukumuncwa kwe-terahertz kwe-compatibilizer kuphezulu.Ukwengeza, izakhiwo ze-THz optical (inkomba ye-refractive kanye ne-coefficient yokumunca) zingathinteka ngokugxila kwe-compatibilizer.Ngaphezu kwalokho, kukhona i-polypropylene e-homopolymerized kanye ne-block polypropylene matrices yezinhlanganisela ze-CNF.I-Homo-PP imane iyi-homopolymer ye-polypropylene enokuqina okuhle kakhulu nokumelana nokushisa.I-block polypropylene, eyaziwa nangokuthi i- impact copolymer, inokumelana nomthelela ongcono kune-homopolymer polypropylene.Ngaphezu kwe-PP ye-homopolymerized, i-block PP iqukethe izingxenye ze-ethylene-propylene copolymer, futhi isigaba se-amorphous esitholakala ku-copolymer sidlala indima efanayo nerabha ekumunceni ukushaqeka.I-spectra ye-terahertz ayizange iqhathaniswe.Ngakho-ke, siqale salinganisela i-spectrum ye-THz ye-OP, okuhlanganisa ne-compatibilizer.Ngaphezu kwalokho, siqhathanise i-spectra ye-terahertz ye-homopolypropylene kanye ne-block polypropylene.
Umdwebo wohlelo lokulinganisa kokudlulisela kwezinhlanganisela eziqiniswe yi-CNF.(a) i-polarization eqondile, (b) i-polarization evundlile.
Amasampula e-block PP alungiswa kusetshenziswa i-maleic anhydride polypropylene (MAPP) njenge-compatibilizer (Umex, Sanyo Chemical Industries, Ltd.).Emkhiwaneni.2a,b ikhombisa inkomba ye-THz etholwe ukuhlukanisa okuqondile nokuvundlile, ngokulandelanayo.Emkhiwaneni.I-2c,d ibonisa ama-coefficients wokumunca we-THz atholakalele ukuhlukaniswa okuqondile nokuvundlile, ngokulandelanayo.Njengoba kuboniswe emkhiwaneni.I-2a-2d, awukho umehluko obalulekile owabonwa phakathi kwezakhiwo ze-terahertz optical (inkomba ye-refractive kanye ne-coefficient yokumunca) ye-polarizations eqondile nevundlile.Ngaphezu kwalokho, ama-compatibilizer anomphumela omncane emiphumeleni yokumuncwa kwe-THz.
Izici zokubonwayo zama-PP amaningana anokugxilisa okuhlukene okuhambisanayo: (a) inkomba ye-refractive etholwe endaweni eqondile, (b) inkomba ye-refractive etholwe endaweni evundlile, (c) i-coefficient yokumuncwa etholwe ohlangothini oluqondile, kanye (d) ne-coefficient yokumunca etholiwe. ohlangothini oluvundlile.
Sabe sesilinganisa i-block-PP emsulwa kanye ne-homo-PP emsulwa.Emkhiwaneni.Amanani 3a kanye no-3b abonisa izinkomba ze-THz eziphindaphindayo ze-PP yenqwaba kanye ne-PP ehlanzekile e-homogeneous, etholwe ukuhlukaniswa okuqondile nokuvundlile, ngokulandelanayo.Inkomba ye-refractive ye-block PP ne-homo PP ihluke kancane.Emkhiwaneni.Izibalo 3c kanye ne-3d zibonisa ama-coefficients wokumunca we-THz we-block PP emsulwa kanye ne-homo-PP emsulwa etholwe ukuhlukaniswa okuqondile nokuvundlile, ngokulandelana.Akukho mehluko obonwe phakathi kwama-coefficients wokumunca we-block PP ne-homo-PP.
(a) vimba i-PP refractive index, (b) i-homo PP refractive index, (c) vimba i-PP coefficient, (d) i-homo PP coefficient yokumuncwa.
Ngaphezu kwalokho, sihlole izinhlanganisela eziqiniswe nge-CNF.Ezilinganisweni ze-THz zezinhlanganisela eziqiniswe yi-CNF, kuyadingeka ukuqinisekisa ukuhlakazeka kwe-CNF kuzinhlanganisela.Ngakho-ke, siqale sahlola ukuhlakazeka kwe-CNF kuzinhlanganisela sisebenzisa i-imaging ye-infrared ngaphambi kokulinganisa izakhiwo zokubona zomshini kanye ne-terahertz.Lungiselela izingxenye eziphambene zamasampuli usebenzisa i-microtome.Izithombe ze-infrared zitholwe kusetshenziswa isistimu ye-imaging ye-Attenuated Total Reflection (ATR) (Frontier-Spotlight400, ukulungiswa okungu-8 cm-1, usayizi wephikseli 1.56 µm, ukunqwabelana izikhathi ezingu-2/pixel, indawo yokulinganisa 200 × 200 µm, PerkinElmer).Ngokusekelwe endleleni ehlongozwe u-Wang et al.17,26, i-pixel ngayinye ibonisa inani elitholwe ngokuhlukanisa indawo yokuphakama kwe-1050 cm-1 ukusuka ku-cellulose ngendawo yokuphakama kwe-1380 cm-1 kusuka ku-polypropylene.Umfanekiso wesi-4 ubonisa izithombe zokubuka ngeso lengqondo ukusatshalaliswa kwe-CNF ku-PP ebalwa kusukela ku-coefficient yokumunca ehlanganisiwe ye-CNF ne-PP.Siqaphele ukuthi kunezindawo ezimbalwa lapho ama-CNF ayehlanganiswe khona kakhulu.Ngaphezu kwalokho, i-coefficient of variation (CV) ibalwe ngokusebenzisa izihlungi ezimaphakathi ezinosayizi abahlukene bewindi.Emkhiwaneni.6 ibonisa ubudlelwano phakathi kosayizi wewindi lokuhlunga ne-CV.
Ukusatshalaliswa kwezinhlangothi ezimbili kwe-CNF ku-PP, kubalwe kusetshenziswa i-coefficient yokumunca ebalulekile ye-CNF kuya ku-PP: (a) Block-PP/1 wt.% CNF, (b) vimba-PP/5 wt.% CNF, (c) vimba -PP/10 wt% CNF, (d) vimba-PP/20 wt% CNF, (e) i-homo-PP/1 wt% CNF, (f) i-homo-PP/5 wt% CNF, (g) i-homo -PP /10 wt.%% CNF, (h) HomoPP/20 wt% CNF (bona Ulwazi Olwengeziwe).
Nakuba ukuqhathanisa phakathi kokugxila okuhlukile kungalungile, njengoba kuboniswe ku-Fig. 5, sibonile ukuthi ama-CNF ku-block PP kanye ne-homo-PP abonise ukuhlakazeka okuseduze.Kukho konke ukugxilisa ingqondo, ngaphandle kwe-1 wt% CNF, amanani e-CV abengaphansi kuka-1.0 ngomthambeka othambile we-gradient.Ngakho-ke, zibhekwa njengezihlakazekile kakhulu.Ngokuvamile, amanani e-CV avame ukuba phezulu kumasayizi amawindi amancane ezindaweni eziphansi.
Ubudlelwano phakathi kosayizi wewindi lesihlungi esimaphakathi kanye ne-coefficient yokusabalalisa ye-coefficient yokumunca ebalulekile: (a) Block-PP/CNF, (b) Homo-PP/CNF.
Izinto ezibonakalayo ze-terahertz zezinhlanganisela eziqiniswe ngama-CNF zitholiwe.Emkhiwaneni.I-6 ibonisa izici zokubona zezinhlanganisela ezimbalwa ze-PP/CNF ezinokugxilisa okuhlukahlukene kwe-CNF.Njengoba kuboniswe emkhiwaneni.I-6a ne-6b, ngokuvamile, inkomba ye-terahertz ye-refractive ye-block PP kanye ne-homo-PP iyanda ngokukhula kwe-CNF.Nokho, bekunzima ukuhlukanisa phakathi kwamasampula ano-0 kanye no-1 wt.% ngenxa yokugqagqana.Ngokungeziwe kunkomba ye-refractive, siphinde saqinisekisa ukuthi i-terahertz yokumuncwa kwe-terahertz yenqwaba ye-PP kanye ne-homo-PP iyanda ngokugxila kwe-CNF okwandayo.Ngaphezu kwalokho, singakwazi ukuhlukanisa phakathi kwamasampuli ngo-0 no-1 wt.% emiphumeleni ye-coefficient yokumuncwa, kungakhathaliseki ukuthi ikuphi ukuqondiswa kwe-polarization.
Izici zokubonwa kwezinhlanganisela ze-PP/CNF eziningana ezinokugxilisa okuhlukile kwe-CNF: (a) inkomba ye-refractive ye-block-PP/CNF, (b) inkomba ye-refractive ye-homo-PP/CNF, (c) i-coefficient yokumuncwa ye-block-PP/CNF, ( d) i-coefficient yokumuncwa i-homo-PP/UNV.
Siqinisekise ubudlelwano bomugqa phakathi kokumuncwa kwe-THz nokugxila kwe-CNF.Ubudlelwano phakathi kokugxilisa ingqondo ye-CNF kanye ne-THz yokumunca coefficient kuboniswa ku-Fig.7.Imiphumela ye-block-PP ne-homo-PP ibonise ubudlelwano obuhle bomugqa phakathi kokumuncwa kwe-THz nokugxila kwe-CNF.Isizathu salokhu kulandelana okuhle singachazwa kanje.Ububanzi befayibha ye-UNV mncane kakhulu kunobubanzi be-wavelength ye-terahertz.Ngakho-ke, akukho cishe ukusakazeka kwamagagasi e-terahertz kusampula.Kumasampuli angahlakazi, ukumuncwa kanye nokugxilisa ingqondo kunobudlelwano obulandelayo (umthetho we-Beer-Lambert)27.
lapho u-A, ε, l, kanye no-c kungukumunca, ukumuncwa kwe-molar, ubude bendlela esebenzayo yokukhanya ngesampula ye-matrix, nokugxila, ngokulandelana.Uma u-ε kanye no-l engashintshi, ukumuncwa kuhambisana nokugxilisa ingqondo.
Ubudlelwano phakathi kokumunca ekugxiliseni kwe-THz ne-CNF nokulingana komugqa okutholwe ngendlela yezikwele ezincane kakhulu: (a) I-Block-PP (1 THz), (b) I-Block-PP (2 THz), (c) i-Homo-PP (1 THz) , (d) I-Homo-PP (2 THz).Umugqa oqinile: umugqa omncane ulingana izikwele.
Izakhiwo zemishini zezinhlanganisela ze-PP/CNF zatholwa ekugxiliseni okuhlukahlukene kwe-CNF.Ukuze uthole amandla aqinile, amandla okugoba, ne-modulus egobayo, inani lamasampuli lalingu-5 (N = 5).Ngamandla omthelela we-Charpy, usayizi wesampula ngu-10 (N = 10).Lawa manani ahambisana namazinga okuhlola alimazayo (i-JIS: Amazinga Emboni YaseJapane) okulinganisa amandla omshini.Emkhiwaneni.Umfanekiso we-8 ubonisa ubudlelwane phakathi kwezakhiwo zemishini kanye nokugxila kwe-CNF, okuhlanganisa amanani alinganiselwe, lapho iziqephu zithathwe ku-curve yokulinganisa ye-1 THz eboniswe ku-Figure 8. 7a, p.Amajika ahlelwe ngokusekelwe ebudlelwaneni obuphakathi kokugxila (0% wt., 1% wt., 5% wt., 10% wt. kanye no-20% wt.) kanye nezakhiwo zemishini.Amaphuzu okuhlakazeka ahlelwe kugrafu yokugxila okubaliwe ngokumelene nezakhiwo zemishini ku-0% wt., 1% wt., 5% wt., 10% wt.kanye no-20% wt.
Izakhiwo zemishini ye-block-PP (umugqa oqinile) kanye ne-homo-PP (umugqa odayishiwe) njengomsebenzi wokugxila kwe-CNF, ukuhlushwa kwe-CNF ku-block-PP kulinganiselwa ku-THz ukumuncwa kwe-coefficient etholwe ku-polarization eqondile (onxantathu), ukugxila kwe-CNF ku-block- I-PP PP Ukugxiliswa kwe-CNF kulinganiselwa ku-THz yokumuncwa kwe-coefficient etholwe ku-polarization evundlile (imibuthano), ukugxiliswa kwe-CNF ku-PP ehlobene kulinganiselwa ku-THz coefficient yokumuncwa etholwe ku-polarization eqondile (amadayimane), ukugxila kwe-CNF kokuhlobene I-PP ilinganiselwa ku-THz etholwe ku-polarization evundlile Ilinganisa i-coefficient yokumunca (izikwele): (a) amandla aqinile, (b) amandla okuguquguquka, (c) i-flexural modulus, (d) Amandla womthelela we-Charpy.
Ngokuvamile, njengoba kuboniswe ku-Fig. 8, izakhiwo zemishini ye-block polypropylene composites zingcono kunezinhlanganisela ze-homopolymer polypropylene.Amandla omthelela webhulokhi ye-PP ngokusho kuka-Charpy ehla ngokunyuka kokugxila kwe-CNF.Endabeni ye-block PP, lapho i-PP kanye ne-CNF-containing masterbatch (MB) ixubene ukuze yakhe inhlanganisela, i-CNF yakha ama-entanglements namaketanga e-PP, noma kunjalo, amanye amaketanga e-PP ahlanganiswe ne-copolymer.Ngaphezu kwalokho, ukuhlakazeka kuyacindezelwa.Njengomphumela, i-copolymer emunca umthelela ivinjwa ama-CNF ahlakazeke ngokunganele, okuholela ekwehliseni ukumelana komthelela.Endabeni ye-homopolymer PP, i-CNF ne-PP zihlakazeke kahle futhi isakhiwo senethiwekhi ye-CNF kucatshangwa ukuthi sinesibopho sokumisa.
Ngaphezu kwalokho, amanani okugxila e-CNF abaliwe ahlelwa kumajika abonisa ubudlelwano phakathi kwezakhiwo zemishini nokugxilisa ingqondo kwe-CNF kwangempela.Le miphumela itholwe izimele ku-terahertz polarization.Ngakho-ke, singakwazi ukuphenya ngokungekonakali izakhiwo zemishini ye-CNF-reinforced composite, kungakhathaliseki ukuthi i-terahertz polarization, sisebenzisa izilinganiso ze-terahertz.
Izinhlanganisela ze-CNF-reinforced thermoplastic resin zinenani lezinto, okuhlanganisa amandla angcono kakhulu emishini.Izakhiwo zemishini ye-CNF-reinforced composite zithinteka inani le-fiber eyengeziwe.Siphakamisa ukusebenzisa indlela yokuhlola okungabhubhisi kusetshenziswa ulwazi lwe-terahertz ukuze sithole izakhiwo zemishini zezinhlanganisela eziqiniswe nge-CNF.Siqaphele ukuthi izihlanganisi ezivame ukungezwa kuzinhlanganisela ze-CNF azithinti izilinganiso ze-THz.Singasebenzisa i-coefficient yokumunca ebangeni le-terahertz ukuze sihlole izinto ezingomshini zezinhlanganisela eziqiniswe yi-CNF, kungakhathaliseki ukuthi i-polarization ebangeni le-terahertz.Ngaphezu kwalokho, le ndlela iyasebenza ku-UNV block-PP (UNV/block-PP) kanye ne-UNV homo-PP (UNV/homo-PP) izinhlanganisela.Kulolu cwaningo, amasampula e-CNF ayinhlanganisela anohlakazeka okuhle alungiswa.Kodwa-ke, kuye ngezimo zokukhiqiza, ama-CNF angahlakazeka kancane ezinhlanganisela.Ngenxa yalokhu, izakhiwo zemishini zezinhlanganisela ze-CNF zonakala ngenxa yokuhlakazeka okubi.I-Terahertz imaging28 ingasetshenziselwa ukuthola ngokungonakalisi ukusatshalaliswa kwe-CNF.Kodwa-ke, ulwazi ekuqondeni kokujula luyafingqwa futhi lulinganiselwe.I-THz tomography24 yokwakhiwa kabusha kwe-3D kwezakhiwo zangaphakathi ingaqinisekisa ukusatshalaliswa okujulile.Ngakho, imaging ye-terahertz kanye ne-terahertz tomography inikeza ulwazi oluningiliziwe esingaphenya ngalo ukucekelwa phansi kwezakhiwo zemishini okubangelwa ukungafani kwe-CNF.Ngokuzayo, sihlela ukusebenzisa imaging ye-terahertz kanye ne-terahertz tomography yezinhlanganisela eziqiniswe yi-CNF.
Isistimu yokulinganisa ye-THz-TDS isekelwe kulaser ye-femtosecond (izinga lokushisa legumbi 25 °C, umswakama 20%).I-femtosecond laser beam ihlukaniswa ibe yiphampu yesigxobo kanye ne-probe beam kusetshenziswa i-beam splitter (BR) ukuze kukhiqizwe futhi kutholwe amaza e-terahertz, ngokulandelanayo.I-pump beam igxile ku-emitter (i-antenna ye-photoresistive).Ibeam ekhiqiziwe ye-terahertz igxile kusayithi lesampula.Ukhalo lwe-terahertz egxilile lucishe lube ngu-1.5 mm (FWHM).Usebe lwe-terahertz lube seludlula kusampula bese luhlanganiswa.I-collimated beam ifinyelela kumamukeli (i-photoconductive antenna).Endleleni yokuhlaziywa kokulinganisa kwe-THz-TDS, inkambu kagesi ye-terahertz etholiwe yesiginali yereferensi kanye nesampula yesiginali esizindeni sesikhathi iguqulwa ibe inkambu kagesi yesizinda samafrikhwensi esiyinkimbinkimbi (ngokulandelana i-Eref(ω) ne-Esam(ω)), ngokusebenzisa i-Fourier transform esheshayo (FFT).Umsebenzi wokudlulisa okuyinkimbinkimbi T(ω) ungavezwa kusetshenziswa isibalo esilandelayo 29
lapho u-A eyisilinganiso sama-amplitudes wereferensi namasignali ereferensi, futhi φ umehluko wesigaba phakathi kwereferensi namasignali ereferensi.Khona-ke inkomba ye-refractive n(ω) kanye ne-coefficient yokumuncwa α(ω) ingabalwa kusetshenziswa izibalo ezilandelayo:
Amasethi edatha akhiqizwe kanye/noma ahlaziywa ngesikhathi socwaningo lwamanje ayatholakala kubabhali abafanele uma kunesicelo esifanele.
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