I-Hafnium, i-metal Hf, inombolo ye-athomu engu-72, isisindo se-athomu 178.49, iyinsimbi ecwebezelayo empunga eshintshashintshayo.
I-Hafnium inama-isotopes ayisithupha azinzile ngokwemvelo: i-hafnium 174, 176, 177, 178, 179, kanye ne-180. I-Hafnium ayiphenduli nge-dilute hydrochloric acid, i-dilute sulfuric acid, nezisombululo ze-alkaline ezinamandla, kodwa iyancibilika ku-hydrofluoric acid kanye ne-aquareic acid. Igama lesici livela egameni lesiLatini leCopenhagen City.
Ngo-1925, usokhemisi waseSweden u-Hervey kanye nesazi sefiziksi sase-Dutch u-Koster bathola usawoti ohlanzekile we-hafnium nge-fractional crystallization of fluorinated complex salts, futhi bawunciphisa nge-metallic sodium ukuze bathole i-hafnium yensimbi ehlanzekile. I-Hafnium iqukethe u-0.00045% woqweqwe lomhlaba futhi ivame ukuhlotshaniswa ne-zirconium ngokwemvelo.
Igama lomkhiqizo: hafnium
Uphawu lwe-elementi: Hf
Isisindo se-athomu: 178.49
Uhlobo lwe-elementi: i-metallic element
Izinto ezibonakalayo:
I-Hafniumiyinsimbi empunga esiliva ene-metallic luster; Kunezinhlobo ezimbili ze-hafnium yensimbi: i-α Hafnium iyi-hexagonal ehlanganiswe eduze kakhulu (1750 ℃) enezinga lokushisa eliphakeme lokuguqulwa kune-zirconium. I-Metal hafnium inezinhlobonhlobo ze-allotrope emazingeni okushisa aphezulu. I-Metal hafnium ine-cross-section ephezulu yokumuncwa kwe-neutron futhi ingasetshenziswa njengento yokulawula yama-reactors.
Kunezinhlobo ezimbili zezinhlaka zekristalu: ukupakisha okuminyene okuyi-hexagonal emazingeni okushisa angaphansi kuka-1300 ℃ (α- Equation); Emazingeni okushisa angaphezu kuka-1300 ℃, iyi-cubic egxile emzimbeni (β- Equation). Insimbi enepulasitiki eba lukhuni futhi iba brittle lapho kukhona ukungcola. Izinzile emoyeni, iba mnyama ebusweni kuphela lapho ishile. Imicu ingavuthwa ilangabi lomentshisi. Izakhiwo ezifana ne-zirconium. Ayiphenduli ngamanzi, i-dilute acid, noma izisekelo eziqinile, kodwa incibilika kalula ku-aqua regia ne-hydrofluoric acid. Ikakhulukazi kumakhompiyutha ane-+4 valence. I-Hafnium alloy (Ta4HfC5) yaziwa ngokuba nephuzu lokuncibilika eliphakeme kakhulu (cishe 4215 ℃).
Isakhiwo sekristalu: Ingqamuzana lekristalu linamahexagonal
Inombolo ye-CAS: 7440-58-6
Indawo encibilikayo: 2227 ℃
Indawo yokubilisa: 4602 ℃
Izakhiwo zamakhemikhali:
Amakhemikhali e-hafnium afana kakhulu nalawo e-zirconium, futhi inokumelana nokugqwala okuhle futhi ayigqwali kalula yi-asidi ejwayelekile ye-alkali aqueous solutions; Incibilika kalula ku-hydrofluoric acid ukuze yakhe ama-fluorinated complexes. Emazingeni okushisa aphezulu, i-hafnium ingaphinde ihlangane ngokuqondile namagesi afana ne-oxygen ne-nitrogen ukuze yakhe ama-oxide nama-nitride.
I-Hafnium ivamise ukuba ne-+4 valence kumakhomponi. Inhlanganisela eyinhloko yii-hafnium oxideHfO2. Kunezinhlobo ezintathu ezahlukene ze-hafnium oxide:i-hafnium oxideetholwe ngokubala okuqhubekayo kwe-hafnium sulfate kanye ne-chloride oxide iyinhlobonhlobo ye-monoclinic; I-hafnium oxide etholwe ngokushisisa i-hydroxide ye-hafnium cishe ku-400 ℃ iwuhlobo lwe-tetragonal; Uma kubalwa ngaphezu kuka-1000 ℃, okuhlukile kwe-cubic kungatholakala. Enye inhlanganiselai-hafnium tetrachloride, okuyizinto ezingavuthiwe zokulungiselela i-hafnium yensimbi futhi ingalungiswa ngokusabela igesi ye-chlorine engxubeni ye-hafnium oxide ne-carbon. I-Hafnium tetrachloride ihlangana namanzi futhi ngokushesha i-hydrolyzes ibe yi-HfO (4H2O) ezinzile kakhulu 2+ion. Ama-HfO2+ion akhona kumakhompiyutha amaningi e-hafnium, futhi angacwebezela njengenaliti emise okwe-hydrated hafnium oxychloride HfOCl2 · Amakristalu angu-8H2O kusixazululo se-hydrochloric acidified hafnium tetrachloride.
I-4-valent hafnium ijwayele ukwenza izingxube ezine-fluoride, ehlanganisa i-K2HfF6, K3HfF7, (NH4) 2HfF6, kanye (NH4) 3HfF7. Lezi zinkimbinkimbi zisetshenziselwe ukuhlukaniswa kwe-zirconium ne-hafnium.
Izinhlanganisela ezijwayelekile:
I-Hafnium dioxide: igama elithi Hafnium dioxide; I-hafnium dioxide; Ifomula yemolekyuli: HfO2 [4]; Isakhiwo: Impushana emhlophe enezinhlaka ezintathu zekristalu: i-monoclinic, i-tetragonal, ne-cubic. Ukuminyana kungu-10.3, 10.1, kanye no-10.43g/cm3, ngokulandelana. Iphoyinti lokuncibilika 2780-2920K. Iphoyinti lokubilisa 5400K. I-coefficient yokwandisa okushisayo 5.8 × 10-6/℃. Ayincibiliki emanzini, i-hydrochloric acid, ne-nitric acid, kodwa incibilika ku-concentrated sulfuric acid ne-hydrofluoric acid. Ikhiqizwe ukubola okushisayo noma i-hydrolysis yamakhompiyutha afana ne-hafnium sulfate ne-hafnium oxychloride. Izinto zokusetshenziswa zokukhiqiza i-metal hafnium ne-hafnium alloys. Isetshenziswa njengezinto eziphikisayo, ama-anti radioactive coatings, nama-catalysts. [5] Ileveli yamandla e-athomu i-HfO iwumkhiqizo otholakala ngesikhathi esisodwa lapho kukhiqizwa ileveli yamandla e-athomu i-ZrO. Kusukela ku-chlorination yesibili, izinqubo zokuhlanzwa, ukunciphisa, kanye ne-vacuum distillation cishe zifana nalezo ze-zirconium.
I-Hafnium tetrachloride: I-Hafnium (IV) chloride, i-Hafnium tetrachloride Ifomula yemolekyuli HfCl4 Isisindo semolekyuli 320.30 Uhlamvu: Ibhulokhi yekristalu emhlophe. Izwela umswakama. Incibilika ku-acetone ne-methanol. I-Hydrolyze emanzini ukukhiqiza i-hafnium oxychloride (HfOCl2). Shisisa ufike ku-250 ℃ bese uyahwamuka. Ukucasula emehlweni, isimiso sokuphefumula, nesikhumba.
I-Hafnium hydroxide: I-Hafnium hydroxide (H4HfO4), ivamise ukuba khona njenge-hydrated oxide HfO2 · nH2O, ayincibiliki emanzini, ayincibiliki kalula kuma-asidi angaphili, ayincibiliki ku-ammonia, futhi ayincibiliki ku-sodium hydroxide. Ukushisa ku-100 ℃ ukukhiqiza i-hafnium hydroxide HfO (OH) 2. Imvula ye-hafnium hydroxide emhlophe ingatholwa ngokusabela usawoti we-hafnium (IV) ngamanzi ammonia. Ingasetshenziselwa ukukhiqiza amanye ama-hafnium compounds.
Umlando Wocwaningo
Umlando Wokuthola:
Ngo-1923, usokhemisi waseSweden u-Hervey kanye nesazi sefiziksi sase-Dutch u-D. Koster bathola i-hafnium ku-zircon ekhiqizwa eNorway naseGreenland, futhi bayiqamba ngokuthi i-hafnium, esuselwa egameni lesiLatini elithi Hafnia of Copenhagen. Ngo-1925, u-Hervey no-Coster bahlukanisa i-zirconium ne-titanium besebenzisa indlela ye-crystallization ye-fractional ye-fluorinated complex salts ukuze bathole usawoti ohlanzekile we-hafnium; Futhi unciphise usawoti we-hafnium nge-metallic sodium ukuze uthole i-hafnium yensimbi ehlanzekile. U-Hervey ulungiselele isampula lamamiligremu amaningana e-hafnium emsulwa.
Ukuhlolwa kwamakhemikhali ku-zirconium ne-hafnium:
Ocwaningweni olwenziwa uProfessor Carl Collins eNyuvesi yaseTexas ngo-1998, kwathiwa i-gamma irradiated hafnium 178m2 (i-isomer hafnium-178m2 [7]) ingakhulula amandla amakhulu, okungama-oda amahlanu obukhulu ngaphezu kokusebenza kwamakhemikhali kodwa. ama-oda amathathu obukhulu aphansi kune-nuclear reactions. [8] I-Hf178m2 (hafnium 178m2) inesikhathi eside sokuphila phakathi kwama-isotopi ahlala isikhathi eside afanayo: I-Hf178m2 (hafnium 178m2) inohhafu wempilo yeminyaka engama-31, okuholela emisebeni yemvelo elinganiselwa ku-1.6 trillion Becquerels. Umbiko kaCollins uthi igremu elilodwa le-Hf178m2 (hafnium 178m2) elimsulwa liqukethe cishe ama-megajoule angu-1330, alingana namandla akhishwe ukuqhuma kwamakhilogremu angu-300 eziqhumane ze-TNT. Umbiko ka-Collins ubonisa ukuthi wonke amandla kulokhu kusabela akhululwa ngendlela yama-X-ray noma imisebe ye-gamma, ekhulula amandla ngenani elishesha kakhulu, futhi i-Hf178m2 (hafnium 178m2) isengasabela ekugxiliseni okuphansi kakhulu. [9] I-Pentagon inikeze imali yocwaningo. Esivivinyweni, isilinganiso sesignali-kuya-nomsindo sasiphansi kakhulu (namaphutha abalulekile), futhi kusukela lapho, naphezu kokuhlolwa okuningi kososayensi abavela ezinhlanganweni eziningi ezihlanganisa i-United States Department of Defence Advanced Projects Research Agency (DARPA) kanye ne-JASON Defense Advisory. Iqembu [13], akekho usosayensi okwazile ukufeza lokhu kusabela ngaphansi kwezimo ezishiwo nguCollins, futhi uCollins akazange anikeze ubufakazi obuqinile bokufakazela ukuba khona kwalokhu kusabela, uCollins uhlongoze indlela yokusebenzisa i-gamma eyenziwe. ukukhishwa kwe-ray ukukhulula amandla ku-Hf178m2 (hafnium 178m2) [15], kodwa abanye ososayensi baye bafakazela ngokombono ukuthi lokhu kusabela ngeke kuzuzwe. [16] I-Hf178m2 (hafnium 178m2) ikholelwa kabanzi emphakathini wezemfundo ukuthi akuwona umthombo wamandla.
Inkambu yohlelo lokusebenza:
I-Hafnium iwusizo kakhulu ngenxa yekhono layo lokukhipha ama-electron, njengalapho esetshenziswa njengefilament kumalambu e-incandescent. Isetshenziswa njenge-cathode yamashubhu e-X-ray, nama-alloys e-hafnium ne-tungsten noma i-molybdenum asetshenziswa njengama-electrodes kumashubhu okukhipha amandla aphezulu. Okuvame ukusetshenziswa embonini yokukhiqiza i-cathode ne-tungsten wire kuma-X-ray. I-hafnium ehlanzekile iyinto ebalulekile embonini yamandla e-athomu ngenxa yepulasitiki yayo, ukucubungula kalula, ukumelana nokushisa okuphezulu, nokumelana nokugqwala. I-Hafnium inengxenye enqamulayo yokubamba i-neutron eshisayo futhi iyisidonsa se-neutron esikahle, esingasetshenziswa njengenduku yokulawula kanye nedivayisi yokuvikela yama-reactors e-athomu. I-Hafnium powder ingasetshenziswa njenge-propellant yamarokhethi. I-cathode yamashubhu e-X-ray ingakhiqizwa embonini kagesi. Ingxubevange ye-Hafnium ingasebenza njengongqimba oluvikelayo oluya phambili lwamarokhethi kanye nendiza egxumayo engena kabusha, kuyilapho ingxubevange ye-Hf Ta ingase isetshenziselwe ukwenza insimbi yamathuluzi nezinto zokumelana. I-Hafnium isetshenziswa njengesengezo kuma-alloys amelana nokushisa, njenge-tungsten, i-molybdenum, ne-tantalum. I-HfC ingasetshenziswa njengesengezo sama-alloys aqinile ngenxa yokuqina kwayo okuphezulu nendawo yokuncibilika. Iphuzu lokuncibilika le-4TaCHfC lilinganiselwa ku-4215 ℃, okuyenza ibe inhlanganisela enephuzu lokuncibilika eliphakeme kakhulu elaziwayo. I-Hafnium ingasetshenziswa njenge-getter ezinhlelweni eziningi zokwehla kwamandla emali. Ama-hafnium getters angasusa amagesi angadingekile afana ne-oxygen ne-nitrogen ekhona ohlelweni. I-Hafnium ivame ukusetshenziswa njengesengezo kuwoyela we-hydraulic ukuvimbela ukuvuvukala kwamafutha we-hydraulic ngesikhathi sokusebenza okunobungozi obukhulu, futhi inezindawo eziqinile zokulwa nokuguquguquka. Ngakho-ke, ngokuvamile isetshenziswa kuwoyela wezimboni we-hydraulic. Amafutha e-hydraulic yezokwelapha.
I-Hafnium element iphinde isetshenziswe kuma-Intel 45 nanoprocessors akamuva. Ngenxa yokwenziwa kwe-silicon dioxide (SiO2) kanye nekhono layo lokunciphisa ukujiya ukuze kuthuthukiswe ngokuqhubekayo ukusebenza kwe-transistor, abakhiqizi bamaphrosesa basebenzisa i-silicon dioxide njengomsebenzi wama-dielectrics wesango. Ngenkathi i-Intel yethula inqubo yokukhiqiza i-nanometer engu-65, nakuba yayenze yonke imizamo yokunciphisa ukujiya kwe-silicon dioxide gate dielectric ibe ama-nanometer angu-1.2, okulingana nezingqimba ezi-5 zama-athomu, ubunzima bokusetshenziswa kwamandla kanye nokuchithwa kokushisa nakho kuzokwanda lapho i-transistor. yehliswa yaba usayizi we-athomu, okwaholela ekumoshweni kwamanje namandla okushisa angadingekile. Ngakho-ke, uma izinto zamanje ziqhubeka nokusetshenziswa futhi ubukhulu buncishiswa ngokwengeziwe, ukuvuza kwe-dielectric yesango kuzokwanda kakhulu, Kwehlisela phansi ubuchwepheshe be-transistor emikhawulweni yayo. Ukubhekana nalolu daba olubucayi, i-Intel ihlela ukusebenzisa izinto eziqinile ze-K (izinto ezisekelwe ku-hafnium) njengama-dielectrics wamasango esikhundleni se-silicon dioxide, eyehlise ngempumelelo ukuvuza izikhathi ezingaphezu kwe-10. Uma kuqhathaniswa nesizukulwane sangaphambilini sobuchwepheshe be-65nm, inqubo ye-Intel ye-45nm inyusa ukuminyana kwe-transistor cishe kabili, okuvumela ukwanda kwenani eliphelele lama-transistors noma ukuncipha kwevolumu yephrosesa. Ngaphezu kwalokho, amandla adingekayo ekushintsheni kwe-transistor aphansi, ehlisa ukusetshenziswa kwamandla cishe ngo-30%. Izixhumi zangaphakathi zenziwe ngocingo lwethusi olubhangqwe ne-low k dielectric, ngcono ngokushelelayo ukusebenza kahle nokunciphisa ukusetshenziswa kwamandla, futhi isivinini sokushintshwa sicishe sibe ngama-20% ngokushesha.
Ukusatshalaliswa kwamaminerali:
I-Hafnium inenqwaba ye-crustal ephakeme kunezinsimbi ezivame ukusetshenziswa njenge-bismuth, i-cadmium, ne-mercury, futhi ilingana nokuqukethwe kwe-beryllium, i-germanium, ne-uranium. Wonke amaminerali aqukethe i-zirconium aqukethe i-hafnium. I-Zircon esetshenziswa embonini iqukethe i-0.5-2% hafnium. I-beryllium zircon (Alvite) ku-zirconium ore yesibili ingaqukatha kufika ku-15% hafnium. Kukhona futhi uhlobo lwe-metamorphic zircon, i-cyrtolite, equkethe ngaphezu kwe-5% HfO. Izimbiwa ezimbili zokugcina zincane futhi azikakamukelwa embonini. I-Hafnium itholakala ikakhulukazi ngesikhathi sokukhiqizwa kwe-zirconium.
Itholakala kuma-ore amaningi e-zirconium. [18] [19] Ngoba kuncane kakhulu okuqukethwe kuqweqwe. Ivame ukuhlangana ne-zirconium futhi ayinayo insimbi ehlukile.
Indlela yokulungiselela:
1. Ingalungiswa ngokuncishiswa kwe-magnesium ye-hafnium tetrachloride noma ukubola okushisayo kwe-hafnium iodide. I-HfCl4 kanye ne-K2HfF6 nayo ingasetshenziswa njengezinto zokusetshenziswa. Inqubo yokukhiqiza i-electrolytic ku-NaCl KCl HfCl4 noma i-K2HfF6 melt ifana naleyo yokukhiqizwa kwe-electrolytic ye-zirconium.
2. I-Hafnium ihlangana ne-zirconium, futhi ayikho impahla eluhlaza ehlukile ye-hafnium. Izinto ezisetshenziswayo zokukhiqiza i-hafnium yi-hafnium oxide engahluziwe ehlukaniswe ngesikhathi sokwenza i-zirconium. Khipha i-hafnium oxide usebenzisa i-ion exchange resin, bese usebenzisa indlela efanayo ne-zirconium ukuze ulungise i-hafnium yensimbi kule hafnium oxide.
3. Ingalungiswa ngokushisa i-hafnium tetrachloride (HfCl4) nge-sodium ngokunciphisa.
Izindlela zakuqala zokuhlukanisa i-zirconium ne-hafnium kwakuyi-fractional crystallization yama-fluorinated complex salts kanye ne-fractional precipitation yama-phosphates. Lezi zindlela zinzima ukusebenza futhi zinqunyelwe ukusetshenziswa kwaselabhorethri. Ubuchwepheshe obusha bokuhlukanisa i-zirconium ne-hafnium, njenge-fractionation distillation, i-solvent extraction, i-ion exchange, ne-fractionation adsorption, iye yavela ngokulandelana, nokukhipha i-solvent kusebenza kakhulu. Amasistimu wokuhlukanisa asetshenziswa kakhulu yi-thiocyanate cyclohexanone kanye ne-tributyl phosphate nitric acid system. Imikhiqizo etholwe ngezindlela ezingenhla yonke i-hafnium hydroxide, futhi i-hafnium oxide ehlanzekile ingatholwa ngokubala. Ukuhlanzeka okuphezulu kwe-hafnium kungatholwa ngendlela yokushintshanisa i-ion.
Embonini, ukukhiqizwa kwe-hafnium yensimbi kuvame ukubandakanya kokubili inqubo ye-Kroll kanye nenqubo ye-Debor Aker. Inqubo ye-Kroll ibandakanya ukuncishiswa kwe-hafnium tetrachloride kusetshenziswa i-metallic magnesium:
2Mg+HfCl4- → 2MgCl2+Hf
Indlela ye-Debor Aker, eyaziwa nangokuthi indlela ye-iodization, isetshenziselwa ukuhlanza isipontshi njenge-hafnium nokuthola i-hafnium yensimbi ethambile.
5. Ukuncibilikiswa kwe-hafnium ngokuyisisekelo kuyafana nalokho kwe-zirconium:
Isinyathelo sokuqala ukubola kwe-ore, okubandakanya izindlela ezintathu: i-chlorination ye-zircon ukuthola (Zr, Hf) Cl. Ukuncibilika kwe-alkali kwe-zircon. I-Zircon incibilika nge-NaOH cishe ku-600, futhi ngaphezu kuka-90% we-(Zr, Hf) O iguqulela ku-Na (Zr, Hf) O, ne-SiO iguqulelwe ku-NaSiO, encibilika emanzini ukuze isuswe. I-Na (Zr, Hf) O ingasetshenziswa njengesixazululo sokuqala sokuhlukanisa i-zirconium ne-hafnium ngemva kokuncibilika ku-HNO. Kodwa-ke, ukuba khona kwe-SiO colloids kwenza ukuhlukaniswa kwe-solvent extraction kube nzima. I-Sinter ene-KSiF bese ucwilisa emanzini ukuze uthole isixazululo se-K (Zr, Hf) F. Isixazululo singahlukanisa i-zirconium ne-hafnium ngokusebenzisa i-crystallization ye-fractional;
Isinyathelo sesibili ukuhlukaniswa kwe-zirconium ne-hafnium, engafinyelelwa ngokusebenzisa izindlela zokuhlukanisa i-solvent extraction usebenzisa i-hydrochloric acid MIBK (i-methyl isobutyl ketone) uhlelo kanye ne-HNO-TBP (tributyl phosphate) uhlelo. Ubuchwepheshe bokuhlukaniswa kwezigaba eziningi kusetshenziswa umehluko wokucindezelwa komhwamuko phakathi kwe-HfCl ne-ZrCl encibilika ngaphansi kwengcindezi ephezulu (ngaphezu kwama-atmospheres angama-20) sekuyisikhathi eside kuhlolisiswa, okungasindisa inqubo yesibili ye-chlorination futhi kunciphise izindleko. Kodwa-ke, ngenxa yenkinga yokugqwala ye-(Zr, Hf) Cl ne-HCl, akulula ukuthola izinto ezifanelekile zekholomu yokuhlukaniswa, futhi kuzonciphisa ikhwalithi ye-ZrCl ne-HfCl, kukhuphule izindleko zokuhlanza. Ngeminyaka yawo-1970, yayisesesigabeni esimaphakathi sokuhlolwa kwezitshalo;
Isinyathelo sesithathu ukucwiliswa kwesibili kwe-HfO ukuze kutholwe i-HfCl engahluziwe ukuze yehliswe;
Isinyathelo sesine ukuhlanzwa kwe-HfCl nokunciphisa i-magnesium. Le nqubo iyafana nokuhlanzwa kanye nokwehliswa kwe-ZrCl, futhi umphumela owumphumela wokuphela komkhiqizo uyi-hafnium yesiponji esimahhadla;
Isinyathelo sesihlanu ukuhlanza isiponji esingahluziwe se-distill ukususa i-MgCl futhi kubuyiselwe i-magnesium yensimbi eyeqile, okuholela kumkhiqizo oqediwe we-sponge metal hafnium. Uma i-ejenti yokunciphisa isebenzisa i-sodium esikhundleni se-magnesium, isinyathelo sesihlanu kufanele siguqulwe sibe ukucwiliswa emanzini
Indlela yokugcina:
Gcina endaweni epholile nengena umoya. Gwema izinhlansi nemithombo yokushisa. Kufanele igcinwe ngokuhlukana nama-oxidants, ama-asidi, ama-halogen, njll., futhi ugweme ukuxuba isitoreji. Ukusebenzisa izibani ezingaqhumi kanye nezindawo zokungenisa umoya. Vimbela ukusetshenziswa kwezinto eziwumshini namathuluzi ajwayele ukuba nezinhlansi. Indawo yokugcina kufanele ifakwe izinto ezifanele ukuqukatha ukuvuza.
Isikhathi sokuthumela: Sep-25-2023