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Cellulose nanofibers (CNF) inogona kuwanikwa kubva kune zvakasikwa zvakadai semiti uye huni fibers.CNF-reinforced thermoplastic resin composites ine zvivakwa zvakati wandei, zvinosanganisira kusimba kwemagetsi.Sezvo ma mechanical properties eCNF-reinforced composites inobatwa nehuwandu hwefiber yakawedzerwa, zvakakosha kuti uone kusangana kweCNF filler mumatrix mushure mekugadzira jekiseni kana extrusion molding.Isu takasimbisa hukama hwakanaka hwemutsara pakati peCNF yekumisikidza uye kutora terahertz.Isu taigona kuona mutsauko muCNF kutariswa pa1% mapoinzi tichishandisa terahertz time domain spectroscopy.Pamusoro pezvo, takaongorora michina yeCNF nanocomposites tichishandisa ruzivo rweterahertz.
Cellulose nanofibers (CNFs) inowanzoita isingasviki 100 nm muhupamhi uye inotorwa kubva kune zvakasikwa zvakadai semiti uye huni fibers1,2.CNFs dzine high mechanical simba3, high optical transparency4,5,6, nzvimbo yakakura yepamusoro, uye yakaderera kupisa kwekuwedzera kwekoefficient7,8.Naizvozvo, ivo vanotarisirwa kushandiswa seyakagadzikana uye yakakwirira kuita zvinhu mumhando dzakasiyana dzekushandisa, zvinosanganisira zvemagetsi zvinhu9, zvekurapa10 uye zvekuvaka11.Macomposites akasimbiswa neUNV akareruka uye akasimba.Naizvozvo, CNF-yakasimbiswa composites inogona kubatsira kuvandudza kunaka kwemafuta emotokari nekuda kwehuremu hwadzo.
Kuti uwane kushanda kwepamusoro, kugovera yunifomu yeCNFs mu hydrophobic polymer matrices akadai se polypropylene (PP) inokosha.Nokudaro, pane kudiwa kwekuongororwa kusingaparadzi kwemakombuta akasimbiswa neCNF.Kusina-kuparadza kuyedzwa kwepolymer kompositi kwanzi12,13,14,15,16.Mukuwedzera, kuongororwa kusingaparadzi kweCNF-yakasimbiswa composites inobva pa X-ray computed tomography (CT) yakashumwa 17.Zvisinei, zvakaoma kusiyanisa maCNF kubva kumatrices nekuda kwekusiyana kwemufananidzo wakaderera.Fluorescent labeling analysis18 uye infrared analysis19 inopa maonero akajeka eCNFs uye matemplate.Nekudaro, isu tinogona chete kuwana ruzivo rwepamusoro.Naizvozvo, nzira idzi dzinoda kucheka (kukuvadza kuyedzwa) kuwana ruzivo rwemukati.Naizvozvo, isu tinopa kusiri-kuparadza kuyedzwa kwakavakirwa pane terahertz (THz) tekinoroji.Mafungu eTerahertz mafungu emagetsi emagetsi ane frequencies kubva pa0.1 kusvika ku10 terahertz.Mafungu eTerahertz ari pachena kune zvinhu.Kunyanya, polymer uye matanda zvinhu zviri pachena kune terahertz mafungu.Ongororo yekutarisa kweiyo liquid crystal polymers21 uye kuyerwa kwe deformation ye elastomers22,23 uchishandisa nzira ye terahertz yakataurwa.Pamusoro pezvo, kuona terahertz kwekukuvadzwa kwehuni kunokonzerwa nezvipembenene uye fungal utachiona muhuni kwakaratidzwa24,25.
Isu tinopa zano rekushandisa iyo isingaparadze nzira yekuyedza kuwana iyo mechaniki zvivakwa zveCNF-yakasimbiswa macomposites uchishandisa terahertz tekinoroji.Muchidzidzo ichi, tinoongorora terahertz spectra yeCNF-reinforced composites (CNF/PP) uye tinoratidza kushandiswa kwemashoko eterahertz kufungidzira kuwanda kweCNF.
Sezvo sampuli dzakagadzirwa nekuumbwa kwejekiseni, dzinogona kukanganiswa nepolarization.Pamusoro pemuonde.1 inoratidza hukama pakati pepolarization ye terahertz wave uye kutaridzika kwemuenzaniso.Kuti asimbise kutsamira kwepolarization kweCNFs, maitiro avo optical akayerwa zvichienderana nekumira (Fig. 1a) uye horizontal polarization (Fig. 1b).Kazhinji, macompatibilizer anoshandiswa kuparadzira zvakafanana CNFs mumatrix.Nekudaro, mhedzisiro yeanopindirana paTHz zviyero haina kudzidzwa.Zviyero zvekufambisa zvakaoma kana kutorwa kwe terahertz yecompatibilizer kwakakwira.Mukuwedzera, iyo THz optical properties (refractive index uye absorption coefficient) inogona kukanganiswa nekugadzirisa kwekugadzirisa.Mukuwedzera, kune homopolymerized polypropylene uye block polypropylene matrices eCNF composites.Homo-PP ingori polypropylene homopolymer ine kuomarara kwakanyanya uye kudzivirira kupisa.Block polypropylene, inozivikanwawo se impact copolymer, ine zvirinani kupikisa pane homopolymer polypropylene.Pamusoro pehomopolymerized PP, block PP inewo zvikamu zveethylene-propylene copolymer, uye chikamu cheamorphous chinowanikwa kubva kucopolymer chinoita basa rakafanana nerabha mukuvhunduka.Iyo terahertz spectra haina kuenzaniswa.Naizvozvo, isu takatanga kufungidzira iyo THz spectrum yeOP, kusanganisira iyo inopindirana.Mukuwedzera, isu takafananidza terahertz spectra yehomopolypropylene uye block polypropylene.
Schematic dhayagiramu yekutapurirana kuyerwa kweCNF-yakasimbiswa macomposites.(a) vertical polarization, (b) horizontal polarization.
Samples ye block PP yakagadziridzwa uchishandisa maleic anhydride polypropylene (MAPP) seanopindirana (Umex, Sanyo Chemical Industries, Ltd.).Pamusoro pemuonde.2a,b inoratidza iyo THz refractive index yakawanikwa kune yakatwasuka uye yakachinjika polarizations, zvichiteerana.Pamusoro pemuonde.2c, d inoratidza THz absorption coefficients yakawanikwa kune yakatwasuka uye yakachinjika polarizations, zvichiteerana.Sezvinoratidzwa mufig.2a-2d, hapana mutsauko wakakosha wakaonekwa pakati peiyo terahertz optical properties (refractive index uye absorption coefficient) kune vertical uye horizontal polarizations.Uye zvakare, anopindirana ane mhedzisiro shoma pane zvabuda zvekutorwa kweTHz.
Optical zvimiro zvemaPP akati wandei ane akasiyana compatibilizer concentrations: (a) refractive index inowanikwa munzira yakatwasuka, (b) refractive index inowanikwa munzira yakachinjika, (c) absorption coefficient inowanikwa munzira yakatwasuka, uye (d) absorption coefficient yakawanikwa. munzira yakachinjika.
Isu takazoyera yakachena block-PP uye yakachena homo-PP.Pamusoro pemuonde.Mifananidzo 3a uye 3b inoratidza iyo THz refractive indices yeyakachena bulk PP uye yakachena homogeneous PP, inowanikwa kune yakatwasuka uye yakachinjika polarizations, zvichiteerana.Iyo refractive index ye block PP uye homo PP yakasiyana zvishoma.Pamusoro pemuonde.Mifananidzo 3c uye 3d inoratidza iyo THz yekunyudza coefficients yeyakachena block PP uye yakachena homo-PP inowanikwa kune yakatwasuka uye yakatwasuka polarizations, zvichiteerana.Hapana mutsauko wakaonekwa pakati peabsorption coefficients ye block PP uye homo-PP.
(a) block PP refractive index, (b) homo PP refractive index, (c) block PP absorption coefficient, (d) homo PP absorption coefficient.
Pamusoro pezvo, takaongorora macomposites akasimbiswa neCNF.Muchiyero cheTHz cheCNF-yakasimbiswa composites, zvinodikanwa kusimbisa kupararira kweCNF mumakombisi.Naizvozvo, takatanga taongorora kupararira kweCNF mumakombisi tichishandisa infrared imaging tisati tayera mechanical uye terahertz optical properties.Gadzirira zvikamu zvemuchinjikwa zvemasampuli uchishandisa microtome.Mifananidzo yeInfrared yakawanikwa uchishandisa Attenuated Total Reflection (ATR) imaging system (Frontier-Spotlight400, resolution 8 cm-1, pixel size 1.56 µm, kuunganidza 2 nguva / pixel, nzvimbo yekuyera 200 × 200 µm, PerkinElmer).Zvichienderana nenzira yakatsanangurwa naWang et al.17,26, pixel yega yega inoratidza kukosha kunowanikwa nekupatsanura nzvimbo ye1050 cm-1 peak kubva ku cellulose nenzvimbo ye1380 cm-1 peak kubva papolypropylene.Mufananidzo 4 unoratidza mifananidzo yekuona kugoverwa kweCNF muPP yakaverengerwa kubva pamubatanidzwa wekunyudza coefficient yeCNF nePP.Takaona kuti kwaive nenzvimbo dzinoverengeka uko maCNF aive akaunganidzwa zvakanyanya.Pamusoro pezvo, iyo coefficient of variation (CV) yakaverengerwa nekushandisa avhareji mafirita ane masaizi akasiyana ehwindo.Pamusoro pemuonde.6 inoratidza hukama pakati peavhareji sefa hwindo saizi neCV.
Maviri-dimensional kugoverwa kweCNF muPP, yakaverengerwa pachishandiswa iyo integral absorption coefficient yeCNF kuenda kuPP: (a) Block-PP/1 wt.% CNF, (b) block-PP/5 wt.% CNF, (c) block -PP/10 wt% CNF, (d) vhara-PP/20 wt% CNF, (e) homo-PP/1 wt% CNF, (f) homo-PP/5 wt% CNF, (g) homo -PP /10 wt.%% CNF, (h) HomoPP/20 wt% CNF (ona Supplementary Information).
Kunyange zvazvo kuenzanisa pakati pezvikamu zvakasiyana-siyana zvisina kukodzera, sezvakaratidzwa mumufananidzo 5, takaona kuti CNFs mu block PP uye homo-PP yakaratidza kupararira kwepedyo.Kune ese mafungidziro, kunze kwe1 wt% CNF, CV tsika dzaive pasi pe1.0 ine zvinyoro nyoro mutserendende.Nokudaro, vanoonekwa sevakapararira zvakanyanya.Kazhinji, CV tsika dzinoita kunge dzakakwira kune madiki mahwindo saizi pane yakaderera concentration.
Ukama huri pakati peavhareji sefafitera saizi yefafitera uye kupatsanurwa kweiyo integral absorption coefficient: (a) Block-PP/CNF, (b) Homo-PP/CNF.
Iyo terahertz optical properties yecomposites yakasimbiswa neCNFs yakawanikwa.Pamusoro pemuonde.6 inoratidza maoptical properties yeanoverengeka PP/CNF macomposites ane akasiyana CNF concentrations.Sezvinoratidzwa mufig.6a uye 6b, kazhinji, terahertz refractive index ye block PP uye homo-PP inowedzera nekuwedzera CNF concentration.Zvakadaro, zvaive zvakaoma kusiyanisa pakati pemasampuli ane 0 ne1 wt.% nekuda kwekupindirana.Pamusoro peiyo refractive index, isu takasimbisawo kuti terahertz absorption coefficient yeyakawanda PP uye homo-PP inowedzera nekuwedzera CNF concentration.Mukuwedzera, tinogona kusiyanisa pakati pemasampuli ne 0 uye 1 wt.% pamigumisiro yeabsorption coefficient, pasinei nekutungamirirwa kwepolarization.
Optical properties yezvikamu zvakawanda zvePP/CNF zvinosanganiswa zvakasiyana-siyana zveCNF: (a) refractive index ye block-PP/CNF, (b) refractive index ye homo-PP/CNF, (c) absorption coefficient of block-PP/CNF, ( d) kunyura coefficient homo-PP/UNV.
Isu takasimbisa hukama hwemutsara pakati peTHz kunyura uye CNF concentration.Ukama huri pakati peCNF concentration uye THz absorption coefficient inoratidzwa muFig.7.Iyo block-PP uye homo-PP mhedzisiro yakaratidza hukama hwakanaka hwemutsara pakati peTHz kutora uye CNF concentration.Chikonzero cheiyi mutsara wakanaka unogona kutsanangurwa sezvinotevera.Iyo dhayamita yeUNV fiber idiki zvakanyanya pane iyo yeterahertz wavelength renji.Naizvozvo, hapana kana kupararira kwemafungu eterahertz mumuenzaniso.Kune masampuli asingaparadzire, kutora uye kuisa pfungwa kune hukama hunotevera (mutemo weBeer-Lambert)27.
uko A, ε, l, uye c zvinotora, molar absorptivity, inobudirira nzira kureba kwechiedza kuburikidza nemuenzaniso matrix, uye kuisa pfungwa, zvichiteerana.Kana ε uye l zvisingaperi, kunyura kunoenderana nekufungisisa.
Hukama pakati pekunyura muTHz neCNF yekumisikidza uye mutsara wakakodzera unowanikwa neashoma masikweya nzira: (a) Block-PP (1 THz), (b) Block-PP (2 THz), (c) Homo-PP (1 THz) , (d) Homo-PP (2 THz).Mutsara wakaoma: mutsara masikweya mashoma anokodzera.
Iyo mechanical properties yePP/CNF composite yakawanikwa pane zvakasiyana-siyana zveCNF.Kune simba rekusimba, simba rekukotama, uye kupeta modulus, nhamba yemasampuli yaive 5 (N = 5).Kune Charpy simba rekuita, saizi yemuenzaniso ndeye gumi (N = 10).Aya makoshero anoenderana neanoparadza bvunzo zviyero (JIS: Japanese Industrial Standards) yekuyera simba remuchina.Pamusoro pemuonde.Mufananidzo 8 unoratidza hukama huri pakati pema mechanical properties uye CNF concentration, kusanganisira maitiro anofungidzirwa, apo zvirongwa zvakatorwa kubva ku1 THz calibration curve inoratidzwa mumufananidzo 8. 7a, p.Macurves akarongwa zvichienderana nehukama huri pakati pehuwandu (0% wt., 1% wt., 5% wt., 10% wt. uye 20% wt.) uye mechanical properties.Mapoinzi ekuparadzira akarongedzerwa pagirafu yeakaverengerwa kutariswa maringe ne mechanical properties pa 0% wt., 1% wt., 5% wt., 10% wt.uye 20% wt.
Mechanical properties ye block-PP (yakasimba mutsara) uye homo-PP (dashed line) sekushanda kweCNF concentration, CNF concentration mu block-PP inofungidzirwa kubva kuTHz absorption coefficient inowanikwa kubva vertical polarization (triangles), CNF concentration mu block- PP PP CNF concentration inofungidzirwa kubva kuTHz absorption coefficient yakawanikwa kubva kune horizontal polarization (madenderedzwa), iyo CNF concentration muPP yakabatana inofungidzirwa kubva kune THz absorption coefficient yakawanikwa kubva ku vertical polarization (madhaimondi), iyo CNF concentration mune yakabatana. PP inofungidzirwa kubva kuTHz yakawanikwa kubva kune yakachinjika polarization Inofungidzira absorption coefficient (square): (a) kusimba kwesimba, (b) flexural simba, (c) flexural modulus, (d) Charpy kukanganisa simba.
Kazhinji, sezvinoratidzwa mumufananidzo 8, maitiro emagetsi e block polypropylene composites ari nani kupfuura homopolymer polypropylene composites.Kusimba kwesimba rePP block zvinoenderana naCharpy inodzikira nekuwedzera kweiyo CNF.Panyaya ye block PP, apo PP neCNF-containing masterbatch (MB) yakasanganiswa kuti iite mubatanidzwa, CNF yakagadzira kusungirirwa nemaketani ePP, zvisinei, mamwe maketani ePP akabatanidzwa necopolymer.Mukuwedzera, kupararira kunodzvinyirirwa.Nekuda kweizvozvo, iyo inobata-inobata copolymer inodzivirirwa nekusakwana kupararira CNFs, zvichikonzera kudzikiswa kwekusagadzikana.Panyaya yehomopolymer PP, CNF nePP zvakapararira zvakanaka uye network yeCNF inofungidzirwa kuti ndiyo inokonzera kusungirirwa.
Uye zvakare, yakaverengerwa CNF yekumisikidza kukosha yakarongerwa pamacurves anoratidza hukama pakati pemakanika zvivakwa uye chaiyo CNF kusungwa.Izvi zvakawanikwa zvakazvimiririra kubva kune terahertz polarization.Nokudaro, isu tinogona kusaita-kuparadza kuongorora maitiro emagetsi eCNF-reinforced composite, pasinei ne terahertz polarization, tichishandisa terahertz zviyero.
CNF-reinforced thermoplastic resin composites ine zvivakwa zvakati wandei, zvinosanganisira kusimba kwemagetsi.Iyo mechanical properties yeCNF-reinforced composite inobatwa nehuwandu hwefiber yakawedzerwa.Isu tinopa zano rekushandisa nzira yekusaparadza kuyedza tichishandisa terahertz ruzivo kuti tiwane ma mechanic zvimiro zvemakompositi akasimbiswa neCNF.Isu takaona kuti macompatibilizer anowanzo wedzerwa kuCNF macomposites haakonzerese kuyerwa kweTHz.Tinogona kushandisa iyo absorption coefficient mu terahertz renji yekusakanganisa kuongororwa kweiyo mechanical properties yeCNF-reinforced composite, zvisinei nepolarization mumutsara weterahertz.Mukuwedzera, iyi nzira inoshandiswa kune UNV block-PP (UNV/block-PP) uye UNV homo-PP (UNV/homo-PP) maumbirwo.Muchidzidzo ichi, composite CNF samples nekupararira kwakanaka kwakagadzirwa.Nekudaro, zvichienderana nemamiriro ekugadzira, CNFs inogona kushoma yakapararira mucomposites.Nekuda kweizvozvo, ma mechanical eCNF macomposites akadzikira nekuda kwekusapararira zvakanaka.Terahertz imaging28 inogona kushandiswa kusaparadza kuwana kugovera kweCNF.Nekudaro, ruzivo rwuri mugwara rakadzama rwunopfupikiswa uye kuverengerwa.THz tomography24 ye 3D kuvakwazve kwemukati maumbirwo anogona kusimbisa kudzika kwekugovera.Nokudaro, imaging ye terahertz uye terahertz tomography inopa ruzivo rwakadzama rwatinogona kuongorora narwo kusvibiswa kwemagetsi emagetsi anokonzerwa neCNF inhomogeneity.Mune ramangwana, tinoronga kushandisa terahertz imaging uye terahertz tomography yeCNF-yakasimbiswa composites.
Iyo THz-TDS yekuyera sisitimu yakavakirwa pane femtosecond laser (tembiricha yekamuri 25 °C, humidity 20%).Iyo femtosecond laser beam inopatsanurwa kuita pombi danda uye probe danda uchishandisa danda kupatsanura (BR) kugadzira uye kuona mafungu eterahertz, zvichiteerana.Iyo pombi danda inotariswa pane emitter (photoresistive antenna).Iyo yakagadzirwa terahertz beam inotariswa pane saiti yemuenzaniso.Chiuno chetarehertz danda rakatariswa rinenge 1.5 mm (FWHM).Iyo terahertz danda rinobva rapfuura nemumuenzaniso uye rinobatanidzwa.Iyo collimated danda inosvika kune inogamuchira (photoconductive antenna).Muiyo THz-TDS yekuyera nzira yekuongorora, iyo yakagashirwa terahertz yemagetsi ndima yechiratidzo chechiratidzo uye chiratidzo chechiratidzo mudura renguva inoshandurwa kuita magetsi emagetsi eiyo yakaoma frequency domain (zvichienderana Eref (ω) uye Esam (ω)), kuburikidza. a fast Fourier transform (FFT).Complex transfer function T(ω) inogona kuratidzwa uchishandisa inotevera equation 29
apo A ndiyo reshiyo yeamplitudes yereferenzi uye masaini masaini, uye φ ndiyo mutsauko wechikamu pakati pereferenzi uye masaini masaini.Ipapo iyo refractive index n(ω) uye iyo absorption coefficient α(ω) inogona kuverengerwa uchishandisa anotevera equations:
Datasets akagadzirwa uye / kana kuongororwa panguva yechidzidzo chazvino anowanikwa kubva kune vakasiyana vanyori pakukumbira zvine musoro.
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