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Ka puta he raruraru nui i te whānui o te kirikiri i roto i ngā puna wai kirikiri, ka hua ake te kore pumau o te poka wai. Mō ngā take taiao, ko te whakamahinga o te wai keri wai me ngā aukati kirikiri tāpiri he pai ake i te wai keri hinu. Kua aro nuitia ngā wai katote (IL) hei aukati kirikiri nā ō rātou āhuatanga ka taea te whakarerekē me ngā āhuatanga hiko kaha. Heoi, kua kitea he paitini, he kore pirau, he utu nui hoki ngā wai katote (IL) e hangai ana ki te imidazolyl, e whakamahia whānuitia ana i roto i ngā wai keri. E kiia ana ko ngā whakarewa hohonu eutectic (DES) he mea utu nui ake, he iti ake te paitini hei whakakapi i ngā wai katote, engari kāore tonu i te tutuki i te pumau taiao e hiahiatia ana. Nā ngā whanaketanga hou o tēnei mara kua puta ai te whakaurunga o ngā whakarewa hohonu eutectic taiao (NADES), e mōhiotia ana mō tō rātou tino hoa taiao. I rangahauhia e tēnei rangahau ngā NADES, kei roto ko te waikawa citric (hei kaiwhiwhi here hauwai) me te glycerol (hei kaituku here hauwai) hei tāpiri wai keri. I whakawhanakehia ngā wai keri e hangai ana ki te NADES i runga anō i te API 13B-1, ā, i whakaritea tō rātou mahi ki ngā wai keri e hangai ana ki te pāhare pākawa waro, ngā wai ionic e hangai ana ki te imidazolium, me ngā wai keri e hangai ana ki te choline chloride:urea-DES. Kua whakaahuahia ngā āhuatanga ā-tinana me te matū o ngā NADES motuhake. I aromatawaihia ngā āhuatanga rheological, te ngaronga wai, me ngā āhuatanga aukati shale o te wai keri i te wā o te rangahau, ā, i whakaaturia i te kukū o te 3% NADES, i piki ake te ōwehenga ahotea hua/mātotoru kirihou (YP/PV), i heke te matotoru o te keke paru mā te 26%, ā, i heke te rōrahi tātari mā te 30.1%. He mea nui, i eke a NADES ki te tere aukati whānui whakamiharo o te 49.14% me te whakanui ake i te hanga shale mā te 86.36%. Ko ēnei hua e pā ana ki te kaha o NADES ki te whakarerekē i te ngohe mata, te pūmanawa zeta, me te tawhiti i waenga i ngā paparanga o ngā uku, e kōrerohia ana i roto i tēnei pepa hei mārama ki ngā tikanga matua. E matapaetia ana ka hurihia e tēnei wai keri tauwhiro te umanga keri mā te whakarato i tētahi huarahi kē atu kāore he paitini, he iti te utu, he tino whai hua hoki hei whakakapi i ngā aukati waikura tuku iho, ā, ka whakatakoto i te ara mō ngā mahi keri e pai ana ki te taiao.
He toka maha ngā mahi a te kirikiri, he pūtake, he putunga hoki mō ngā warowaihā, ā, nā tōna hanganga pūwero1 ka taea te whakaputa me te penapena i ēnei rauemi utu nui. Heoi, he nui ngā kohuke uku o te kirikiri pērā i te montmorillonite, te smectite, te kaolinite me te illite, ka ngawari ai te pupuhi ina pāngia e te wai, ka kore e pumau te poka i te wā e keri ana2,3. Ka taea e ēnei take te arahi ki te wā kore hua (NPT) me te maha o ngā raruraru whakahaere tae atu ki ngā paipa kua piri, te ngaronga o te tohanga paru, te hinga o te poka me te poke o ngā moka, ka piki ake te wā whakaora me te utu. I ngā wā o mua, ko ngā wai keri hinu (OBDF) te mea pai mō ngā hanganga kirikiri nā te mea ka taea e rātou te ātete i te whānui o te kirikiri4. Heoi, ko te whakamahinga o ngā wai keri hinu he nui ake ngā utu me ngā mōrearea taiao. Kua whakaarohia ngā wai keri hangai (SBDF) hei huarahi kē atu, engari kāore i te pai te pai ki ngā pāmahana teitei. He otinga ātaahua ngā wai keri wai (WBDF) nā te mea he haumaru ake, he pai ake te taiao, ā, he iti ake te utu i te OBDF5. Kua whakamahia ngā momo aukati kirikiri hei whakarei ake i te kaha aukati kirikiri o te WBDF, tae atu ki ngā aukati tuku iho pēnei i te pāhare pākawa waro, te raima, te silicate, me te polymer. Heoi, he iti noa iho ngā herenga o ēnei aukati mō te whai huatanga me te pānga ki te taiao, inā koa nā te nui o te K+ i roto i ngā aukati pāhare pākawa waro me te aro o ngā silicate ki te pH.6 Kua tūhuratia e ngā kairangahau te āheinga ki te whakamahi i ngā wai ionic hei tāpiri wai keri hei whakapai ake i te rheology wai keri me te aukati i te pupuhi kirikiri me te hanganga hydrate. Heoi, ko ēnei wai ionic, inā koa ko ērā kei roto ngā cations imidazolyl, he paitini te nuinga, he utu nui, kāore e pirau, ā, me whai tukanga whakarite uaua. Hei whakaoti i ēnei raruraru, ka tīmata te tangata ki te rapu i tētahi atu huarahi whai hua ake, ā, he pai ake hoki ki te taiao, ā, i puta ai ngā whakarewa hohonu eutectic (DES). Ko te DES he ranunga eutectic i hangaia e te kaituku here hauwai (HBD) me te kaiwhiwhi here hauwai (HBA) i tētahi ōwehenga molar me te pāmahana motuhake. He iti ake ngā ira rewa o ēnei ranunga eutectic i ō rātou wāhanga takitahi, ko te nuinga nā te tango utu i puta mai i ngā here hauwai. He maha ngā āhuatanga, tae atu ki te pūngao whatunga, te huringa entropy, me ngā taunekeneke i waenga i ngā anion me te HBD, e whai wāhi nui ana ki te whakaheke i te ira rewa o DES.
I roto i ngā rangahau o mua, i tāpirihia ngā momo tāpiri ki te wai keri wai hei whakaoti i te raruraru whakawhanui o te kirikiri. Hei tauira, i tāpirihia e Ofei me ētahi atu te 1-butyl-3-methylimidazolium chloride (BMIM-Cl), i tino whakaitihia ai te matotoru o te keke paru (tae atu ki te 50%) me te whakaiti i te uara YP/PV mā te 11 i ngā pāmahana rerekē. I whakamahia e Huang me ētahi atu ngā wai ionic (ina koa, te 1-hexyl-3-methylimidazolium bromide me te 1,2-bis(3-hexylimidazol-1-yl)ethane bromide) me ngā matūriki Na-Bt, ā, i tino whakaitihia ai te pupuhi kirikiri mā te 86.43% me te 94.17%, ia12. Hei tāpiri, i whakamahia e Yang me ētahi atu te 1-vinyl-3-dodecylimidazolium bromide me te 1-vinyl-3-tetradecylimidazolium bromide hei whakaiti i te pupuhi kirikiri mā te 16.91% me te 5.81%. 13 I whakamahia anō hoki e Yang me ētahi atu te 1-vinyl-3-ethylimidazolium bromide, ā, i whakaitihia te whānui o te kirikiri mā te 31.62%, me te pupuri tonu i te whakaoranga kirikiri ki te 40.60%. 14 I tua atu, i whakamahia e Luo me ētahi atu te 1-octyl-3-methylimidazolium tetrafluoroborate hei whakaiti i te pupuhi kirikiri mā te 80%. 15, 16 I whakamahia e Dai me ētahi atu ngā copolymers wai ionic hei aukati i te kirikiri, ā, i tutuki i a rātou te pikinga 18% o te whakaoranga raina ki te whakataurite ki ngā aukati amine. 17
He ngoikoretanga anō hoki ō ngā wai ionic, ā, nā ēnei i akiaki ngā kaipūtaiao ki te rapu huarahi pai ake mō te taiao hei whakakapi i ngā wai ionic, ā, nō reira i whānau mai ai a DES. Ko Hanjia te tuatahi ki te whakamahi i ngā whakarewa eutectic hohonu (DES) kei roto ko te waikawa propionic vinyl chloride (1:1), te waikawa 3-phenylpropionic vinyl chloride (1:2), me te waikawa 3-mercaptopropionic + waikawa itaconic + vinyl chloride (1:1:2), i aukati i te pupuhi o te bentonite mā te 68%, 58%, me te 58%, ia18. I roto i tētahi whakamātautau kore utu, i whakamahia e MH Rasul he ōwehenga 2:1 o te glycerol me te potassium carbonate (DES) ā, i tino whakaiti i te pupuhi o ngā tauira shale mā te 87%.19,20. I whakamahia e Ma te urea:vinyl chloride hei whakaiti i te whānui o te shale mā te 67%.21 I whakamahia e Rasul et al. Ko te huinga o te DES me te polymer hei aukati shale mahi-rua, i tutuki ai te pānga aukati shale tino pai22.
Ahakoa e kiia ana ko ngā whakarewa hohonu eutectic (DES) he huarahi kē atu i ngā wai ionic, kei roto hoki i a rātou ngā wāhanga paitini pea pērā i ngā tote ammonium, e whakapaetia ai tō rātou pai ki te taiao. Nā tēnei raruraru i arahi ki te whanaketanga o ngā whakarewa hohonu eutectic tūturu (NADES). Kei te whakarōpūtia tonutia rātou hei DES, engari he mea tito mai i ngā matū me ngā tote tūturu, tae atu ki te pāhare pākawa waro (KCl), te konupūmā waro (CaCl2), ngā tote Epsom (MgSO4.7H2O), me ētahi atu. Ko ngā huinga maha pea o DES me NADES e whakatuwhera ana i te whānuitanga mō te rangahau i tēnei wāhanga, ā, e tika ana kia kitea ngā tono i roto i ngā momo mara. He maha ngā kairangahau kua angitu ki te whakawhanake i ngā huinga DES hou kua whakamātauhia he whai hua i roto i ngā momo tono. Hei tauira, i hangaia e Naser et al. 2013 he DES e ahu mai ana i te pāhare pākawa waro, ā, i ako i ōna āhuatanga wera-tinana, ā, i muri mai ka kitea ngā tono i roto i ngā wāhanga o te aukati hydrate, ngā tāpiringa wai keri, te tango i te wera, me te nanofibrillation. 23 I whakawhanakehia e Jordy Kim me ōna hoa mahi he NADES e ahu mai ana i te waikawa ascorbic, ā, i arotakehia ōna āhuatanga antioxidant i roto i ngā momo tono. 24 I whakawhanakehia e Christer me ētahi atu te NADES e ahu mai ana i te waikawa citric, ā, i tautuhia tōna pūmanawa hei tāpiri mō ngā hua collagen. 25 I whakarāpopototia e Liu Yi me ōna hoa mahi ngā whakamahinga o NADES hei rauemi tango me te chromatography i roto i tētahi arotake whānui, i te wā i kōrerohia ai e Misan me ētahi atu ngā whakamahinga angitu o NADES i roto i te rāngai ahuwhenua-kai. He mea nui kia tīmata ngā kairangahau wai keri ki te aro ki te whai huatanga o NADES i roto i ā rātou whakamahinga. tata nei. I te tau 2023, i whakamahia e Rasul me ētahi atu ngā huinga rerekē o ngā whakarewa eutectic hohonu taiao e ahu mai ana i te waikawa ascorbic26, te konupūmā chloride27, te pāhare pākawa waro28 me te tote Epsom29, ā, i tutuki i a rātou te aukati shale me te whakaora shale whakamiharo. Ko tēnei rangahau tētahi o ngā rangahau tuatahi ki te whakauru i te NADES (ina koa ko te waikawa citric me te hanganga e ahu mai ana i te glycerol) hei aukati shale e pai ana ki te taiao me te whai hua i roto i ngā wai keri e ahu mai ana i te wai, e whakaatu ana i te pumau taiao pai rawa atu, te kaha aukati shale kua pai ake, me te mahi wai kua pai ake ki te whakataurite ki ngā aukati tuku iho pēnei i te KCl, ngā wai ionic e ahu mai ana i te imidazolyl me te DES tuku iho.
Ka uru atu ki te rangahau te whakarite ā-roto o te NADES e ahu mai ana i te waikawa citric (CA) ā, ka whai muri ko te whakaahuatanga taipitopito o te āhua ā-tinana me te whakamahinga hei tāpiri wai keri hei aromatawai i ngā āhuatanga o te wai keri me tōna kaha ki te aukati i te pupuhi. I roto i tēnei rangahau, ka mahi te CA hei kaiwhiwhi here hauwai, ko te glycerol (Gly) ka mahi hei kaituku here hauwai i tīpakohia i runga i ngā paearu tirotiro MH mō te hanganga/kōwhiringa NADES i roto i ngā rangahau aukati shale30. Mā te inenga Fourier transform infrared spectroscopy (FTIR), te X-ray diffraction (XRD) me te zeta potential (ZP) ka whakamārama i ngā taunekeneke NADES-clay me te tikanga kei raro i te aukati pupuhi uku. Hei tāpiri, ka whakatauritea e tēnei rangahau te wai keri e ahu mai ana i te CA NADES ki te DES32 e ahu mai ana i te 1-ethyl-3-methylimidazolium chloride [EMIM]Cl7,12,14,17,31, KCl me te choline chloride:urea (1:2) hei tirotiro i tō rātou whai huatanga ki te aukati shale me te whakapai ake i te mahi wai keri.
I hokona mai te waikawa citric (monohydrate), te glycerol (99 USP), me te urea mai i EvaChem, Kuala Lumpur, Malaysia. I hokona mai te choline chloride (>98%), te [EMIM]Cl 98%, me te potassium chloride mai i Sigma Aldrich, Malaysia. Kei te Pikitia 1 ngā hanganga matū o ngā matū katoa. E whakataurite ana te tūtohi matomato i ngā matū matua i whakamahia i roto i tēnei rangahau: te wai imidazolyl ionic, te choline chloride (DES), te waikawa citric, te glycerol, te potassium chloride, me te NADES (te waikawa citric me te glycerol). Kei te Ripanga 1 te ripanga hoahoa taiao o ngā matū i whakamahia i roto i tēnei rangahau. I roto i te ripanga, ka whakatauria ia matū i runga i te paitini, te pirau koiora, te utu, me te pumau o te taiao.
Ngā hanganga matū o ngā rauemi i whakamahia i tēnei rangahau: (a) waikawa citric, (b) [EMIM]Cl, (c) choline chloride, me (d) glycerol.
I whiriwhiria marietia ngā kaitono kaituku here hauwai (HBD) me te kaiwhiwhi here hauwai (HBA) mō te whakawhanaketanga o ngā NADES e ahu mai ana i te CA (te whakarewa hohonu taiao eutectic) i runga i ngā paearu kōwhiringa MH 30, e hāngai ana ki te whakawhanaketanga o ngā NADES hei aukati shale whai hua. E ai ki tēnei paearu, ko ngā wāhanga he nui ngā kaituku me ngā kaiwhiwhi here hauwai me ngā rōpū mahi porowhita e kiia ana he pai mō te whakawhanaketanga o ngā NADES.
Hei tāpiritanga, i tīpakohia te wai ionic [EMIM]Cl me te whakarewa choline chloride:urea deep eutectic (DES) hei whakataurite i roto i tēnei rangahau nā te mea he whānuitia te whakamahinga hei tāpiri wai keri33,34,35,36. Hei tāpiritanga, i whakaritea te pāhare pākawa waro (KCl) nā te mea he aukati noa.
I konatunatua te waikawa citric me te glycerol ki ngā ōwehenga molar rerekē hei whiwhi i ngā ranunga eutectic. I whakaatuhia e te tirohanga he wai ōrite, mārama te ranunga eutectic, kāore he pōuri, e tohu ana i te angitu o te konatunatua o te kaituku here hauwai (HBD) me te kaiwhiwhi here hauwai (HBA) ki tēnei hanganga eutectic. I whakahaerehia ngā whakamātautau tuatahi hei tirotiro i te whanonga e pā ana ki te pāmahana o te tukanga whakaranu o HBD me HBA. E ai ki ngā tuhinga e wātea ana, i aromatawaihia te ōwehenga o ngā ranunga eutectic i ngā pāmahana motuhake e toru i runga ake i te 50 °C, 70 °C me te 100 °C, e tohu ana ko te pāmahana eutectic kei roto i te awhe o te 50–80 °C. I whakamahia he pauna matihiko Mettler hei pauna tika i ngā wāhanga HBD me HBA, ā, i whakamahia he pereti wera Thermo Fisher hei whakamahana me te whakaoho i te HBD me te HBA i te 100 rpm i raro i ngā āhuatanga whakahaere.
I ine tikahia ngā āhuatanga wera-tinana o tā mātou whakarewa hohonu eutectic (DES) i hangaia, tae atu ki te mātotoru, te kukū mata, te taupū whakaata, me te matotoru, i runga i te awhe pāmahana mai i te 289.15 ki te 333.15 K. Me mārama ko te take i whiriwhiria ai tēnei awhe pāmahana nā ngā herenga o ngā taputapu o nāianei. I roto i te tātari whānui he rangahau hōhonu mō ngā āhuatanga wera-tinana o tēnei hanganga NADES, e whakaatu ana i ō rātou whanonga i runga i te awhe pāmahana. Mā te arotahi ki tēnei awhe pāmahana motuhake ka kitea ngā āhuatanga o NADES he mea nui mō te maha o ngā tono.
I inehia te kukū mata o ngā NADES i whakaritea i waenga i te 289.15 ki te 333.15 K mā te whakamahi i tētahi mita kukū ā-mata (IFT700). Ka hangaia ngā pata NADES i roto i tētahi rūma kua whakakiia ki te nui o te wai mā te whakamahi i tētahi ngira capillary i raro i ngā āhuatanga pāmahana me te pēhanga motuhake. Ka whakauruhia e ngā pūnaha whakaahua hou ngā tawhā āhuahanga e tika ana hei tatau i te kukū ā-mata mā te whakamahi i te whārite Laplace.
I whakamahia he ine whakamātao ATAGO hei whakatau i te taupū whakaata o ngā NADES hou i whakaritea i waenga i te 289.15 ki te 333.15 K. Ka whakamahia e te taputapu he kōwae wera hei whakahaere i te pāmahana hei whakatau tata i te nui o te whakaata o te mārama, ā, kāore e hiahiatia he kaukau wai pāmahana pumau. Me horoi te mata porowhita o te ine whakamātao, ā, me tohatoha ōrite te otinga tauira ki runga. Whakamātauria ki tētahi otinga paerewa e mōhiotia ana, kātahi ka pānuihia te taupū whakaata mai i te mata.
I inehia te matotoru o ngā NADES kua whakaritea i roto i te awhe pāmahana mai i te 289.15 ki te 333.15 K mā te whakamahi i te mita hurihuri Brookfield (momo cryogenic) i te tere kutikuti o te 30 rpm me te rahi o te porowhita o te 6. Ka ine te mita matotoru mā te whakatau i te taipana e hiahiatia ana hei huri i te porowhita i te tere pumau i roto i te tauira wai. I muri i te whakatakotoranga o te tauira ki runga i te mata i raro i te porowhita me te whakakī, ka whakaatuhia e te mita matotoru te matotoru i roto i te centipoise (cP), e whakarato ana i ngā mōhiohio whai hua mō ngā āhuatanga rheological o te wai.
I whakamahia he mita mātotoru kawe DMA 35 Basic hei whakatau i te mātotoru o te whakarewa hohonu eutectic taiao hou (NDEES) i roto i te awhe pāmahana 289.15–333.15 K. Nā te mea kāore he whakamahana kua whakauruhia ki roto i te taputapu, me whakamahana anō ki te pāmahana kua tohua (± 2 °C) i mua i te whakamahinga o te mita mātotoru NADES. Tōia kia 2 ml te iti rawa o te tauira mā roto i te ngongo, ā, ka whakaaturia tonutia te mātotoru ki te mata. He mea tika kia mōhiotia, nā te korenga o te whakamahana kua whakauruhia, he hapa ngā hua ine o te ± 2 °C.
Hei aromatawai i te pH o ngā NADES hou i takaia i te awhe pāmahana o te 289.15–333.15 K, i whakamahia e mātou he mita pH papa Kenis. Nā te mea kāore he taputapu whakamahana i roto, i whakamahana tuatahitia a NADES ki te pāmahana e hiahiatia ana (±2 °C) mā te whakamahi i tētahi pereti wera, kātahi ka ine tika ki te mita pH. Rukuhia katoatia te mata o te mita pH ki roto i te NADES, ā, tuhia te uara whakamutunga i muri i te pumau o te pānui.
I whakamahia te tātaritanga wera-rahi (TGA) hei aromatawai i te pumau wera o ngā whakarewa eutectic hohonu taiao (NADES). I tātarihia ngā tauira i te wā whakamahana. Mā te whakamahi i te taurite tino tika me te aroturuki i te tukanga whakamahana, i hangaia he kauwhata o te ngaronga papatipu ki te pāmahana. I whakamahanahia te NADES mai i te 0 ki te 500 °C i te tere o te 1 °C ia meneti.
Hei tīmatanga i te tukanga, me whakaranu pai te tauira NADES, me whakaranu kia ōrite, ā, me tango te makuku o te mata. Kātahi ka whakanohoia te tauira kua whakaritea ki roto i te cuvette TGA, he mea hanga i te nuinga o te wā mai i tētahi rauemi kore mahi pērā i te konumohe. Hei whakarite i ngā hua tika, ka whakatauritea ngā taputapu TGA mā te whakamahi i ngā rauemi tohutoro, arā, ko ngā paerewa taumaha. Kia whakatauritea, ka tīmata te whakamātautau TGA, ā, ka whakamahanahia te tauira i roto i te tikanga whakahaere, i te nuinga o te wā i te tere pumau. Ko te aroturuki tonu i te whanaungatanga i waenga i te taumaha tauira me te pāmahana he wāhanga nui o te whakamātautau. Ka kohia e ngā taputapu TGA ngā raraunga mō te pāmahana, te taumaha, me ētahi atu tawhā pērā i te rere o te hau, te pāmahana tauira rānei. Kia oti te whakamātautau TGA, ka tātarihia ngā raraunga kua kohia hei whakatau i te huringa o te taumaha tauira hei pānga o te pāmahana. He mea nui ēnei mōhiohio ki te whakatau i ngā awhe pāmahana e pā ana ki ngā huringa ā-tinana me te matū i roto i te tauira, tae atu ki ngā tukanga pērā i te rewa, te mimiti, te waikura, te pirau rānei.
I āta hangaia te wai keri wai-wai kia rite ki te paerewa API 13B-1, ā, kei te Ripanga 2 tōna hanganga motuhake hei tohutoro. I hokona te waikawa citric me te glycerol (99 USP) mai i Sigma Aldrich, Malaysia hei whakarite i te whakarewa eutectic hohonu taiao (NADES). Hei tāpiri, i hokona hoki te aukati shale tikanga potassium chloride (KCl) mai i Sigma Aldrich, Malaysia. I tīpakohia te 1-ethyl, 3-methylimidazolium chloride ([EMIM]Cl) me te parakore neke atu i te 98% nā tōna pānga nui ki te whakapai ake i te rheology o te wai keri me te aukati shale, i whakaūtia i roto i ngā rangahau o mua. Ka whakamahia a KCl me te ([EMIM]Cl) i roto i te tātari whakatairite hei aromatawai i te mahi aukati shale o NADES.
He maha ngā kairangahau e pai ake ana ki te whakamahi i ngā kirikiri bentonite hei ako i te pupuhi o te kirikiri nā te mea kei roto i te bentonite te rōpū "montmorillonite" kotahi e puta ai te pupuhi o te kirikiri. He uaua te tiki i ngā tauira matua kirikiri tūturu nā te mea ka whakararuraru te tukanga keri i te kirikiri, ka hua ake he tauira ehara i te kirikiri katoa engari he ranunga o ngā paparanga onepū me te kōhatu. Hei tāpiri, ko ngā tauira kirikiri kāore i te nuinga o te wā he rōpū montmorillonite e puta ai te pupuhi o te kirikiri, nō reira kāore i te pai mō ngā whakamātautau aukati pupuhi.
I roto i tēnei rangahau, i whakamahia e mātou he matūriki bentonite kua hangaia anō, he whānui tata ki te 2.54 cm. I hangaia ngā kirikiri mā te pēhi i te 11.5 karamu o te paura bentonite konutai i roto i te mīhini pēhi waipēhi i te 1600 psi. I ine tikahia te matotoru o ngā kirikiri i mua i te whakanoho ki roto i te mīhini whakawhāiti raina (LD). Kātahi ka rumakina ngā matūriki ki roto i ngā tauira wai keri, tae atu ki ngā tauira turanga me ngā tauira i werohia ki ngā aukati hei ārai i te pupuhi o te kirikiri. Kātahi ka aro turukihia te huringa o te matotoru o te kirikiri mā te whakamahi i te LD, me te tuhi i ngā inenga i ia wā 60-hekona mō ngā haora 24.
I whakaatuhia e te hihi-X te hanganga o te bentonite, inā koa ko tōna wāhanga montmorillonite 47%, he mea nui ki te mārama ki ōna āhuatanga whenua. I roto i ngā wāhanga montmorillonite o te bentonite, ko te montmorillonite te wāhanga matua, e 88.6% o ngā wāhanga katoa. I taua wā, ko te quartz e 29%, ko te illite e 7%, me te carbonate e 9%. He wāhanga iti (tata ki te 3.2%) he ranunga o te illite me te montmorillonite. Hei tāpiri, kei roto ko ngā huānga iti pēnei i te Fe2O3 (4.7%), te aluminosilicate hiriwa (1.2%), te muscovite (4%), me te phosphate (2.3%). Hei tāpiri, he iti noa te Na2O (1.83%) me te silicate rino (2.17%) kei reira, e taea ai te tino mārama ki ngā huānga o te bentonite me ō rātou ōwehenga.
Kei roto i tēnei wāhanga rangahau whānui ngā āhuatanga tātari me te rheological o ngā tauira wai keri i whakaritea mā te whakamahi i te whakarewa hohonu eutectic taiao (NADES) ā, i whakamahia hei tāpiri wai keri i ngā kukū rerekē (1%, 3% me te 5%). Kātahi ka whakatauritea, ka tātarihia hoki ngā tauira paru i ahu mai i te NADES me ngā tauira paru kei roto ko te pāhare pākawa waro (KCl), CC:urea DES (choline chloride deep eutectic solvent:urea) me ngā wai ionic. He maha ngā tawhā matua i hipokina i roto i tēnei rangahau tae atu ki ngā pānui matotoru i whiwhi mā te whakamahi i te ine matotoru FANN i mua atu me muri i te whakamātautanga ki ngā āhuatanga tawhito i te 100°C me te 150°C. I tangohia ngā inenga i ngā tere hurihuri rerekē (3 rpm, 6 rpm, 300 rpm me te 600 rpm) e āhei ai te tātari whānui i te whanonga wai keri. Kātahi ka taea te whakamahi i ngā raraunga i whiwhi hei whakatau i ngā āhuatanga matua pēnei i te pūwāhi hua (YP) me te matotoru kirihou (PV), e whakarato ana i te māramatanga ki te mahi wai i raro i ngā āhuatanga rerekē. Mā ngā whakamātautau tātari pāmahana teitei pēhanga teitei (HPHT) i te 400 psi me te 150°C (ngā pāmahana noa i roto i ngā puna pāmahana teitei) ka whakatau i te mahi tātari (te matotoru o te keke me te rōrahi tātari).
Ka whakamahia e tēnei wāhanga ngā taputapu hou, te Grace HPHT Linear Dilatometer (M4600), hei aromatawai i ngā āhuatanga aukati pupuhi kirikiri o ā mātou wai keri wai. He mīhini hou te LSM, e rua ngā wāhanga: he pereti whakakī me te pereti whakakī raina (tauira: M4600). I whakaritea ngā pereti bentonite mō te tātari mā te whakamahi i te Grace Core/Plate Compacter. Kātahi ka whakaratohia e te LSM ngā raraunga pupuhi tonu ki runga i ēnei pereti, e āhei ai te aromatawai whānui i ngā āhuatanga aukati pupuhi o te kirikiri. I whakahaerehia ngā whakamātautau whakawhānui kirikiri i raro i ngā āhuatanga taiao, arā, 25°C me te 1 psia.
Ko te whakamātautau pumau o te kirikiri he whakamātautau matua e kiia ana ko te whakamātautau whakaora kirikiri, te whakamātautau tuku kirikiri, te whakamātautau marara kirikiri rānei. Hei tīmatanga i tēnei aromatawai, ka wehea ngā tapahi kirikiri ki runga i te mata #6 BSS, kātahi ka whakatakotoria ki runga i te mata #10. Kātahi ka whāngaihia ngā tapahi ki tētahi tāke pupuri ka konatunatua ki te wai turanga me te paru keri kei roto ko te NADES (Natural Deep Eutectic Solvent). Ko te mahi e whai ake nei ko te whakanoho i te ranunga ki roto i te oumu mō tētahi tukanga hurihuri wera nui, me te whakarite kia tino konatunatua ngā tapahi me te paru. I muri i ngā hāora 16, ka tangohia ngā tapahi mai i te penupenu mā te tuku i te kirikiri kia pirau, ka hua ake he whakaiti i te taumaha o ngā tapahi. I whakahaerehia te whakamātautau whakaora kirikiri i muri i te pupuri i ngā tapahi kirikiri ki roto i te paru keri i te 150°C me te 1000 psi. inihi i roto i ngā hāora 24.
Hei ine i te hokinga mai o te paru kirikiri, i tātarihia e mātou mā te mata angiangi ake (40 mata), kātahi ka horoia kia tino pai ki te wai, ā, i te mutunga ka whakamarokehia ki roto i te oumu. Mā tēnei tukanga uaua ka taea e mātou te whakatau tata i te paru i whakahokia mai ki te taumaha taketake, ā, i te mutunga ka tatau i te ōrau o te paru kirikiri i angitu te hokinga mai. Nō te Rohe o Niah, Rohe o Miri, Sarawak, Mareia te pūtake o ngā tauira kirikiri. I mua i ngā whakamātautau marara me te whakaoranga, i tukuna ngā tauira kirikiri ki te tātaritanga hihi-X (XRD) tino pai hei ine i te hanganga o te uku me te whakaū i tō rātou pai mō te whakamātautau. Ko te hanganga kohuke uku o te tauira e whai ake nei: illite 18%, kaolinite 31%, chlorite 22%, vermiculite 10%, me te mika 19%.
Ko te kukū mata he mea matua e whakahaere ana i te urunga o ngā kationa wai ki roto i ngā moroiti kirikiri mā te mahi capillary, ka akohia taipitopitotia i roto i tēnei wāhanga. Ka tirohia e tēnei pepa te tūranga o te kukū mata i roto i te āhuatanga piri o ngā wai keri, me te whakaatu i tōna awe nui ki te tukanga keri, inā koa te aukati kirikiri. I whakamahia e mātou he ine kukū mata (IFT700) hei ine tika i te kukū mata o ngā tauira wai keri, e whakaatu ana i tētahi āhuatanga nui o te whanonga wai i roto i te horopaki o te aukati kirikiri.
I roto i tēnei wāhanga, ka matapakihia te tawhiti o te paparanga-d, arā, te tawhiti i waenga i ngā paparanga aluminosilicate me te paparanga aluminosilicate kotahi i roto i ngā uku. I hipokina e te tātari ngā tauira paru mākū kei roto ko te 1%, 3% me te 5% CA NADES, me te 3% KCl, 3% [EMIM]Cl me te 3% CC:urea DES hei whakataurite. He mea nui te mahi a te ine hihi-X hou (D2 Phaser) e mahi ana i te 40 mA me te 45 kV me te irahiko Cu-Kα (λ = 1.54059 Å) ki te tuhi i ngā tihi hihi-X o ngā tauira Na-Bt mākū me te maroke. Mā te whakamahinga o te whārite Bragg ka taea te whakatau tika i te tawhiti o te paparanga-d, ā, ka whakaratohia he mōhiohio whai hua mō te whanonga uku.
Ka whakamahia e tēnei wāhanga te taputapu matatau a Malvern Zetasizer Nano ZSP hei ine tika i te pūmanawa zeta. I whakaratohia e tēnei aromatawai he kōrero whai hua mō ngā āhuatanga utu o ngā tauira paru waimeha kei roto ko te 1%, 3%, me te 5% CA NADES, tae atu ki te 3% KCl, 3% [EMIM]Cl, me te 3% CC:urea-based DES hei tātaritanga whakatairite. Ka whai wāhi ēnei hua ki tō mātou māramatanga ki te pumau o ngā pūhui colloidal me ā rātou taunekeneke i roto i ngā wai.
I tirotirohia ngā tauira uku i mua atu, ā, i muri i te whakamahinga ki te whakarewa eutectic hohonu tūturu (NADES) mā te whakamahi i te karu hiko matawai tukunga mara Zeiss Supra 55 VP (FESEM) kua rite ki te hihi-X horapa pūngao (EDX). Ko te taumira whakaahua he 500 nm, ā, ko te pūngao hihi irahiko he 30 kV me te 50 kV. Ka whakaratohia e te FESEM he tirohanga taumira teitei o te āhua o te mata me ngā āhuatanga hanganga o ngā tauira uku. Ko te whāinga o tēnei rangahau he tiki mōhiohio mō te pānga o te NADES ki ngā tauira uku mā te whakatairite i ngā whakaahua i whiwhi i mua atu, ā, i muri i te whakamahinga.
I roto i tēnei rangahau, i whakamahia te hangarau karu hiko matawai tukunga mara (FESEM) hei tirotiro i te pānga o NADES ki ngā tauira uku i te taumata moroiti. Ko te whāinga o tēnei rangahau he whakamārama i ngā whakamahinga pea o NADES me tōna pānga ki te āhua o te uku me te rahi toharite o te matūriki, ka whakarato i ngā mōhiohio whai hua mō te rangahau i tēnei mara.
I roto i tēnei rangahau, i whakamahia ngā pae hapa hei whakaahua ā-kanohi i te rerekētanga me te koretake o te ōrau hapa toharite (AMPE) puta noa i ngā āhuatanga whakamātautau. Engari i te tuhi i ngā uara AMPE takitahi (nā te mea ka taea e te tuhi i ngā uara AMPE te huna i ngā au me te whakanui i ngā rerekētanga iti), ka tatauhia e mātou ngā pae hapa mā te whakamahi i te ture 5%. Mā tēnei huarahi ka whakarite kia tohu ia pae hapa i te wā e tika ana kia heke te wā whakawhirinaki 95% me te 100% o ngā uara AMPE, kia mārama ake ai, kia poto ake ai hoki te whakarāpopototanga o te tohatoha raraunga mō ia āhuatanga whakamātautau. Mā te whakamahi i ngā pae hapa i runga i te ture 5% ka whakapai ake i te whakamārama me te pono o ngā whakaaturanga whakairoiro, ā, ka āwhina hoki ki te whakarato i te māramatanga taipitopito ake mō ngā hua me ō rātou pānga.
I roto i te hanganga o ngā whakarewa eutectic hohonu taiao (NADES), he maha ngā tawhā matua i ata tirotirohia i te wā o te tukanga whakarite i roto i te whare. Ko ēnei āhuatanga nui ko te pāmahana, te ōwehenga molar, me te tere whakaranu. E whakaatu ana ā mātou whakamātautau ina whakaranua te HBA (waikawa citric) me te HBD (glycerol) i te ōwehenga molar o te 1:4 i te 50°C, ka puta he ranunga eutectic. Ko te āhuatanga motuhake o te ranunga eutectic ko tōna āhua mārama, ōrite, me te kore o te paru. Nō reira, e whakaatu ana tēnei taahiraa matua i te hiranga o te ōwehenga molar, te pāmahana, me te tere whakaranu, i roto i ēnei ko te ōwehenga molar te mea tino whai mana i roto i te whakarite o te DES me te NADES, e whakaaturia ana i te Pikitia 2.
Ko te taupū whakaata (n) e whakaatu ana i te ōwehenga o te tere o te mārama i roto i te korehau ki te tere o te mārama i roto i te tuarua o ngā reo, he kikī ake. He mea tino nui te taupū whakaata mō ngā whakarewa hohonu taiao (NADES) ina whakaarohia ana ngā tono aro ki te tirohanga pēnei i ngā pūoko koiora. Ko te taupū whakaata o te NADES i akohia i te 25 °C he 1.452, he mea whakamere te iti iho i te glycerol.
He mea tika kia mōhiotia ka heke te taupū whakaata o NADES i te pāmahana, ā, ka taea te whakaahua tika i tēnei ia mā te tātai (1) me te Pikitia 3, me te hapa ōrau toharite tino (AMPE) e eke ana ki te 0%. Ka whakamāramahia tēnei whanonga e pā ana ki te pāmahana mā te hekenga o te matotoru me te mātotoru i ngā pāmahana teitei, ka tere ake te haere o te mārama i roto i te reo, ka hua ake he uara taupū whakaata iti iho (n). Ka whakaratohia e ēnei hua he māramatanga whai hua ki te whakamahinga rautaki o NADES i roto i te pūoko whatu, e whakaatu ana i tōna pūmanawa mō ngā tono pūoko koiora.
Ko te kukū mata, e whakaata ana i te āhua o te mata wai ki te whakaiti i tōna horahanga, he mea tino nui ki te aromatawai i te pai o ngā whakarewa eutectic hohonu taiao (NADES) mō ngā tono e hangai ana ki te pēhanga capillary. He nui ngā mōhiohio e whakaratohia ana e te rangahau i te kukū mata i te awhe pāmahana o te 25–60 °C. I te 25 °C, ko te kukū mata o te NADES e hangai ana ki te waikawa citric he 55.42 mN/m, he iti iho i te wai me te glycerol. E whakaatu ana te Pikitia 4 ka tino heke te kukū mata i te pikinga o te pāmahana. Ka taea te whakamārama i tēnei āhuatanga mā te pikinga o te kaha nekeneke ngota me te hekenga o ngā kaha kukume i waenga i ngā ngota.
Ko te ia hekenga rārangi o te taumahatanga mata i kitea i roto i te NADES i rangahauhia ka taea te whakaatu pai mā te whārite (2), e whakaatu ana i te whanaungatanga pāngarau taketake i roto i te awhe pāmahana o te 25–60 °C. E whakaatu mārama ana te kauwhata i te Pikitia 4 i te ia o te taumahatanga mata me te pāmahana me te hapa ōrau toharite tino (AMPE) o te 1.4%, e ine ana i te tika o ngā uara taumahatanga mata kua pūrongohia. He pānga nui ēnei hua ki te mārama ki te whanonga o NADES me ōna tono pea.
He mea nui te mārama ki ngā āhuatanga o te mātotoru o ngā whakarewa eutectic hohonu taiao (NADES) hei whakahaere i tā rātou whakamahinga i roto i ngā rangahau pūtaiao maha. Ko te mātotoru o te NADES e ahu mai ana i te waikawa citric i te 25°C he 1.361 g/cm3, he teitei ake i te mātotoru o te glycerol matua. Ka taea te whakamārama i tēnei rerekētanga mā te tāpiri i tētahi kaiwhiwhi here hauwai (waikawa citric) ki te glycerol.
Hei tauira, ka heke tōna mātotoru ki te 1.19 g/cm3 i te 60°C. Ko te pikinga o te pūngao nekeneke i te wā e whakamahanahia ana ka marara ngā ngota NADES, ka nui ake te rōrahi e nohoia ana e rātou, ka heke te mātotoru. Ko te hekenga o te mātotoru i kitea e whakaatu ana i tētahi hononga raina ki te pikinga o te pāmahana, ka taea te whakaatu tika mā te tātai (3). E whakaatu ana te Pikitia 5 i ēnei āhuatanga o te huringa mātotoru o te NADES me te hapa ōrau toharite tino (AMPE) o te 1.12%, e whakarato ana i tētahi inenga tauanga o te tika o ngā uara mātotoru kua pūrongohia.
Ko te matotoru te kaha kukume i waenga i ngā paparanga rerekē o te wai e neke ana, ā, he mea nui ki te mārama ki te whakamahinga o ngā whakarewa hohonu taiao (NADES) i roto i ngā momo whakamahinga. I te 25 °C, ko te matotoru o NADES he 951 cP, he teitei ake i te glycerol.
Ko te hekenga o te matotoru i kitea i te pikinga o te pāmahana e whakamāramahia ana e te ngoikore o ngā kaha kukume i waenga i ngā ngota. Ko te hua o tēnei āhuatanga he hekenga o te matotoru o te wai, he ia e whakaaturia mārama ana i te Pikitia 6, ā, i inehia e te Whārite (4). He mea nui, i te 60°C, ka heke te matotoru ki te 898 cP me te hapa ōrau toharite whānui (AMPE) o te 1.4%. He mea nui te māramatanga taipitopito ki te matotoru me te whakawhirinakitanga pāmahana i roto i te NADES mō tōna tono mahi.
He mea nui te pH o te otinga, e whakatauhia ana e te logarithm kino o te kukū o te katote hauwai, inā koa i roto i ngā tono tairongo-pH pēnei i te hanga DNA, nō reira me ata tirotirohia te pH o NADES i mua i te whakamahinga. Hei tauira, ka kitea he pH waikawa tino mārama o te 1.91, he rerekē rawa atu ki te pH kūpapa o te glycerol.
He mea whakamīharo, ko te pH o te wairewa wairewa waikawa citric dehydrogenase tūturu (NADES) i whakaatu i tētahi ia hekenga kore-raina me te pikinga o te pāmahana. Ko tēnei āhuatanga e pā ana ki te pikinga o ngā wiri ngota e whakararuraru ana i te toenga H+ i roto i te wairewa, e arahi ana ki te hanganga o ngā iona [H]+, ā, hei utu, he huringa i roto i te uara pH. Ahakoa kei waenga i te 3 ki te 5 te pH tūturu o te waikawa citric, ko te noho mai o te hauwai waikawa i roto i te glycerol ka whakaiti ake i te pH ki te 1.91.
Ko te whanonga pH o ngā NADES i ahu mai i te citrate i te awhe pāmahana o te 25–60 °C ka taea te whakaatu tika mā te whārite (5), e whakarato ana i tētahi kīanga pāngarau mō te ia o te pH i kitea. E whakaatu ana te Pikitia 7 i tēnei whanaungatanga whakamere, e whakaatu ana i te pānga o te pāmahana ki te pH o NADES, e kīia ana he 1.4% mō te AMPE.
I whakahaerehia te tātaritanga wera-rahi (TGA) o te whakarewa eutectic hohonu waikawa citric tūturu (NADES) i roto i te awhe pāmahana mai i te pāmahana rūma ki te 500 °C. E kitea ana i ngā Pikitia 8a me te b, ko te ngaronga papatipu tuatahi tae atu ki te 100 °C i ahu mai i te wai i mimitihia me te wai whakamakuku e hono ana ki te waikawa citric me te glycerol parakore. I kitea he pupuri papatipu nui o te 88% tae atu ki te 180 °C, i ahu mai i te pirau o te waikawa citric ki te waikawa aconitic me te hanganga o te methylmaleic anhydride(III) i muri i te whakamahana anō (Pikitia 8 b). I runga ake i te 180 °C, i kitea hoki he āhua mārama o te acrolein (acrylaldehyde) i roto i te glycerol, e whakaaturia ana i te Pikitia 8b37.
I whakaatuhia e te tātaritanga thermogravimetric (TGA) o te glycerol tētahi tukanga ngaronga papatipu e rua ngā wāhanga. Ko te wāhanga tuatahi (180 ki te 220 °C) ko te hanganga o te acrolein, ā, muri iho ko te ngaronga papatipu nui i ngā pāmahana teitei mai i te 230 ki te 300 °C (Pikitia 8a). I te pikinga o te pāmahana, ka hangaia te acetaldehyde, te hauhā waro, te methane, me te hauwai i runga i te raupapa. He mea nui, 28% noa iho o te papatipu i puritia i te 300 °C, e kī ana he hapa pea ngā āhuatanga o roto o NADES 8(a)38,39.
Hei whiwhi mōhiohio mō te hanganga o ngā hononga matū hou, i tātarihia ngā whakatārewatanga hou o ngā whakarewa hohonu eutectic taiao (NADES) mā te Fourier transform infrared spectroscopy (FTIR). I mahia te tātaritanga mā te whakataurite i te whānuitanga o te whakatārewatanga NADES ki ngā whānuitanga o te waikawa citric parakore (CA) me te glycerol (Gly). I whakaatuhia e te whānuitanga CA ngā tihi mārama i te 1752 1/cm me te 1673 1/cm, e tohu ana i ngā wiri totoro o te hononga C=O, ā, he āhuatanga anō hoki nō te CA. Hei tāpiri, i kitea he nekehanga nui i roto i te wiri piko OH i te 1360 1/cm i te rohe tapumati, e whakaaturia ana i te Pikitia 9.
Waihoki, mō te glycerol, i kitea ngā nekehanga o te wiri totoro me te piko o te OH i ngā tau ngaru o te 3291 1/cm me te 1414 1/cm. Ināianei, mā te tātari i te whānuitanga o ngā NADES kua whakaritea, i kitea he nekehanga nui i roto i te whānuitanga. E ai ki te Whakaahua 7, i neke te wiri totoro o te here C=O mai i te 1752 1/cm ki te 1720 1/cm, ā, i neke te wiri piko o te here -OH o te glycerol mai i te 1414 1/cm ki te 1359 1/cm. Ko ēnei nekehanga i roto i ngā tau ngaru e tohu ana i te huringa o te irahiko, e tohu ana i te hanganga o ngā here matū hou i roto i te hanganga o te NADES.