Hafnium, simbi Hf, nhamba yeatomu 72, huremu hweatomu 178.49, isimbi inopenya yesirivha yegrey.
Hafnium ine nhanhatu dzakagadzika isotopes: hafnium 174, 176, 177, 178, 179, uye 180. Hafnium haina kuita ne dilute hydrochloric acid, dilute sulfuric acid, uye yakasimba alkaline mhinduro, asi inonyungudika muhydrofluoric acid uye aquare acid. Iro zita rekutanga rinobva pazita rechiLatin reCopenhagen City.
Muna 1925, nyanzvi yekemisitiri yeSweden Hervey neDutch physicist Koster vakawana pure hafnium salt nefractional crystallization yefluorinated complex salts, ndokuideredza nesimbi yesodium kuti vawane simbi yakachena hafnium. Hafnium ine 0.00045% yepasi pevhu uye inowanzobatanidzwa ne zirconium mumasikirwo.
Zita rechigadzirwa: hafnium
Element chiratidzo: Hf
Uremu hweatomu: 178.49
Element type: metallic element
Zvinhu zvenyama:
Hafniumisirivha pfumbu simbi ine simbi inopenya; Kune maviri akasiyana esimbi hafnium: α Hafnium ndeye hexagonal yakanyatso kurongedzerwa musiyano (1750 ℃) ine yakakwirira shanduko tembiricha kupfuura zirconium. Metal hafnium ine allotrope akasiyana pakupisa kwakanyanya. Metal hafnium ine yakakwira neutron absorption muchinjiko-chikamu uye inogona kushandiswa sechinhu chekudzora mareactor.
Kune mhando mbiri dzekristaro zvimiro: hexagonal dense kurongedza patembiricha iri pasi pe 1300 ℃（ α- Equation); Patembiricha iri pamusoro pe1300 ℃, ine body centered cubic (β-Equation). Simbi ine plastiki inoomesa uye inova brittle pamberi pehutsvina. Yakagadzikana mumhepo, inongosviba pamusoro kana yapiswa. Mitsara inogona kubatidzwa nemurazvo wemachisi. Zvivakwa zvakafanana ne zirconium. Haina kuita nemvura, dilute acids, kana mabhesi akasimba, asi inonyungudika nyore mu aqua regia uye hydrofluoric acid. Kunyanya mumakomboni ane +4 valence. Hafnium alloy (Ta4HfC5) inozivikanwa kuve ine yakanyanya kunyungudika (inoda kusvika 4215 ℃).
Crystal chimiro: Sero rekristaro rine hexagonal
Nhamba yeCAS: 7440-58-6
Nzvimbo yakanyungudika: 2227 ℃
Nzvimbo yekubikira: 4602 ℃
Chemical properties:
Mishonga yemakemikari yehafnium yakafanana zvikuru neiyo zirconium, uye ine yakanaka corrosion resistance uye haisi nyore kusvibiswa ne general acid alkali aqueous solutions; Zviri nyore soluble mu hydrofluoric acid kugadzira fluorinated complexes. Pakupisa kwakanyanya, hafnium inogonawo kusanganisa zvakananga nemagasi akadai seokisijeni nenitrogen kugadzira maokisijeni nemanitrides.
Hafnium inowanzova ne+4 valence mumakomponi. Mushonga mukuru ndiwohafnium oxideHfO2. Kune matatu akasiyana akasiyana ehafnium oxide:hafnium oxideinowanikwa nekuenderera mberi calcination ye hafnium sulfate uye chloride oxide inosiyana monoclinic; Iyo hafnium oxide inowanikwa nekudziisa iyo hydroxide yehafnium kutenderera 400 ℃ iri tetragonal musiyano; Kana yakaverengerwa pamusoro pe1000 ℃, cubic musiyano inogona kuwanikwa. Imwe musanganiswa ndeyehafnium tetrachloride, inova iyo mbishi yekugadzira simbi hafnium uye inogona kugadzirwa nekuita chlorine gasi pamusanganiswa wehafnium oxide uye kabhoni. Hafnium tetrachloride inosangana nemvura uye pakarepo inogadzika muHfO (4H2O) yakagadzikana zvakanyanya 2+ion. HfO2 + ions iripo mumisanganiswa yakawanda yehafnium, uye inogona kuchenesa tsono yakaita hydrated hafnium oxychloride HfOCl2 · 8H2O makristasi muhydrochloric acid acidified hafnium tetrachloride solution.
4-valent hafnium inowanzoitawo kugadzira macomplexes ane fluoride, anosanganisira K2HfF6, K3HfF7, (NH4) 2HfF6, uye (NH4) 3HfF7. Aya macomplexes akashandiswa kuparadzanisa zirconium uye hafnium.
Common compounds:
Hafnium dioxide: zita Hafnium dioxide; Hafnium dioxide; Molecular formula: HfO2 [4]; Property: Hupfu chena ine matatu makristasi zvimiro: monoclinic, tetragonal, uye cubic. Densities i10.3, 10.1, uye 10.43g/cm3, zvichiteerana. Melting point 2780-2920K. Boiling point 5400K. Thermal yekuwedzera coefficient 5.8 × 10-6/℃. Insoluble mumvura, hydrochloric acid, uye nitric acid, asi inonyungudika mune concentrated sulfuric acid uye hydrofluoric acid. Inogadzirwa nekuora kwekupisa kana hydrolysis yemakomponi akadai sehafnium sulfate uye hafnium oxychloride. Raw zvinhu zvekugadzira simbi hafnium uye hafnium alloys. Inoshandiswa senge refractory zvinhu, anti radioactive coatings, uye catalysts. [5] Atomic simba level HfO chigadzirwa chinowanikwa panguva imwe chete pakugadzira atomic energy level ZrO. Kutanga kubva kune yechipiri chlorination, maitiro ekucheneswa, kuderedza, uye vacuum distillation anenge akafanana neaya e zirconium.
Hafnium tetrachloride: Hafnium (IV) chloride, Hafnium tetrachloride Molecular formula HfCl4 Molecular weight 320.30 Character: White crystalline block. Sensitive kune unyoro. Soluble muacetone uye methanol. Hydrolyze mumvura kugadzira hafnium oxychloride (HfOCl2). Kupisa kusvika 250 ℃ uye shanduka. Zvinoshungurudza maziso, kufema, uye ganda.
Hafnium hydroxide: Hafnium hydroxide (H4HfO4), inowanzovapo se hydrated oxide HfO2 · nH2O, isinganyunguriki mumvura, inonyungudika nyore nyore mu inorganic acids, isingasviki muammonia, uye haiwanzonyungudika mu sodium hydroxide. Kupisa kusvika ku100 ℃ kugadzira hafnium hydroxide HfO (OH) 2. White hafnium hydroxide precipitate inogona kuwanikwa nekuita hafnium (IV) munyu nemvura yeammonia. Inogona kushandiswa kugadzira mamwe ma hafnium compounds.
Nhoroondo Yekutsvakurudza
Discovery History:
Muna 1923, nyanzvi yekemisitiri yeSweden Hervey uye chiremba wechiDutch wefizikisi D. Koster vakawana hafnium mu zircon yakagadzirwa muNorway neGreenland, ndokuitumidza kuti hafnium, yakabva pazita rechiLatin rokuti Hafnia of Copenhagen. Muna 1925, Hervey naCoster vakaparadzanisa zirconium uye titanium vachishandisa nzira yefractional crystallization ye fluorinated complex salts kuti vawane yakachena hafnium munyu; Uye kuderedza hafnium munyu nesimbi sodium kuti uwane yakachena simbi hafnium. Hervey akagadzira sampuli yemamirigiramu akati wandei e pure hafnium.
Kemikari kuedza pa zirconium uye hafnium:
Mukuedza kwakaitwa naProfessor Carl Collins paYunivhesiti yeTexas muna 1998, zvakanzi gamma irradiated hafnium 178m2 (iyo isomer hafnium-178m2 [7]) inogona kusunungura simba guru, iro mirairo mishanu yehukuru yakakwirira kudarika kushandiswa kwemakemikari asi. mirairo mitatu yehukuru yakaderera pane kuita kwenyukireya. [8] Hf178m2 (hafnium 178m2) ine hurefu hwakareba pakati pemaisotopi akareba-refu akafanana: Hf178m2 (hafnium 178m2) ine hafu yeupenyu hwemakore makumi matatu nerimwe, zvichikonzera radioactivity yechisikigo inosvika 1.6 tiririyoni Becquerels. Chirevo chaCollins chinoti giramu rimwe reiyo yakachena Hf178m2 (hafnium 178m2) ine angangoita 1330 megajoules, iyo yakaenzana nesimba rakaburitswa nekuputika kwemazana matatu makirogiramu eTNT zvinoputika. Chirevo chaCollins chinoratidza kuti simba rese mukuita uku rinoburitswa muchimiro cheX-rays kana gamma rays, iyo inoburitsa simba nekukurumidza zvakanyanya, uye Hf178m2 (hafnium 178m2) inogona kuramba ichiita pakadzika zvakanyanya. [9] Pentagon yakapa mari yekutsvagisa. Mukuyedza, chiratidzo-ku-ruzha reshiyo yaive yakadzikira kwazvo (ine zvikanganiso zvakakura), uye kubva ipapo, zvisinei nekuedzwa kwakawanda nemasayendisiti kubva kumasangano mazhinji anosanganisira United States Dhipatimendi reDziviriro Advanced Projects Research Agency (DARPA) uye JASON Defense Advisory. Boka [13], hapana musayendisiti akakwanisa kuita izvi pasi pemamiriro akataurwa naCollins, uye Collins haana kupa humbowo hwakasimba hunoratidza kuvepo kwekuita uku, Collins akaronga nzira yekushandisa induced gamma. ray emission kuburitsa simba kubva kuHf178m2 (hafnium 178m2) [15], asi mamwe masayendisiti akatsigira nedzidziso kuti kuita uku hakugone kuwanikwa. [16] Hf178m2 (hafnium 178m2) inotendwa zvakanyanya munharaunda yezvidzidzo kuti ive tsime resimba.
Nzvimbo yekushandisa:
Hafnium inobatsira zvikuru nekuda kwekugona kwayo kuburitsa maerekitironi, seanoshandiswa senge filament mumarambi eincandescent. Inoshandiswa se cathode ye X-ray machubhu, uye alloys e hafnium uye tungsten kana molybdenum anoshandiswa semagetsi e-high-voltage discharge tubes. Inowanzo shandiswa mucathode uye tungsten waya yekugadzira indasitiri yeX-rays. Pure hafnium chinhu chakakosha muindasitiri yesimba reatomu nekuda kwepurasitiki yayo, kugadzirwa kuri nyore, kukwira kwekushisa kwekushisa, uye kusagadzikana kwekuora. Hafnium ine hombe yekupisa neutron inobata cross-section uye yakanaka neutron absorber, iyo inogona kushandiswa seyekudzora tsvimbo uye mudziyo unodzivirira wemaatomu reactor. Hafnium powder inogona kushandiswa sepropellant yemaroketi. Iyo cathode yeX-ray machubhu inogona kugadzirwa muindasitiri yemagetsi. Hafnium alloy inogona kushanda seyekumberi inodzivirira yeroketi nozzles uye glide-yekupindazve ndege, nepo Hf Ta alloy inogona kushandiswa kugadzira simbi yemidziyo uye yekupikisa zvinhu. Hafnium inoshandiswa sechinhu chinowedzera mumagetsi asingadziviriri kupisa, senge tungsten, molybdenum, uye tantalum. HfC inogona kushandiswa sekuwedzera kune yakaoma alloys nekuda kwekuoma kwayo kwakanyanya uye nzvimbo yekunyungudika. Kunyungudika kwe4TaCHfC kunosvika 4215 ℃, zvichiita kuti ive mukomboni une nzvimbo yepamusoro inozivikanwa yekunyungudika. Hafnium inogona kushandiswa senge getter mune dzakawanda inflation system. Hafnium getters inogona kubvisa magasi asina kufanira akadai seokisijeni uye nitrogen iripo muhurongwa. Hafnium inowanzoshandiswa sechinhu chinowedzera mu hydraulic mafuta kudzivirira kupisa kwemafuta e hydraulic panguva yekushanda kwepamusoro-ngozi, uye ine yakasimba anti volatility properties. Naizvozvo, inowanzoshandiswa muindasitiri hydraulic oiri. Medical hydraulic mafuta.
Hafnium element inoshandiswawo mune yazvino Intel 45 nanoprocessors. Nekuda kwekugadzirwa kwesilicon dioxide (SiO2) uye kugona kwayo kuderedza ukobvu kuti irambe ichivandudza transistor performance, vagadziri ve processor vanoshandisa silicon dioxide sechinhu chegedhi dielectrics. Intel payakaunza iyo 65 nanometer yekugadzira maitiro, kunyangwe yaive yaedza nese kudzikisa ukobvu hwesilicon dioxide gedhi dielectric kusvika 1.2 nanometers, yakaenzana nezvikamu zvishanu zveatomu, kuoma kwekushandisa simba uye kupisa kupisa kwaizowedzerawo kana transistor. yakaderedzwa kusvika pakukura kweatomu, zvichiita kuti pave nemarara aripo uye simba risingadiwi rekupisa. Naizvozvo, kana zvinhu zvazvino zvikaramba zvichishandiswa uye ukobvu huchiwedzera kuderedzwa, kubuda kwegedhi dielectric kuchawedzera zvakanyanya, Kuunza pasi transistor tekinoroji kumiganhu yayo. Kugadzirisa nyaya iyi yakaoma, Intel iri kuronga kushandisa yakakora yakakwira K zvinhu (hafnium based materials) segedhi dielectrics pachinzvimbo chesilicon dioxide, iyo yakabudirira kudzikisa kuvuza nekanopfuura kagumi. Kuenzaniswa nechizvarwa chakapfuura che65nm tekinoroji, Intel's 45nm process inowedzera transistor density nekanenge kaviri, zvichibvumira kuwedzera kwehuwandu hwehuwandu hwema transistors kana kudzikiswa kwevhoriyamu processor. Mukuwedzera, simba rinodiwa pakushandura transistor rakaderera, kuderedza kushandiswa kwesimba neinenge 30%. Iyo yemukati yekubatanidza inogadzirwa newaya yemhangura yakapetwa neyakaderera k dielectric, zvakanaka kuvandudza kushanda uye kuderedza mashandisiro emagetsi, uye kumhanya kwekuchinja kunenge 20% nekukurumidza.
Mineral distribution:
Hafnium ine yakakwira crustal kuwanda kupfuura simbi inowanzo shandiswa senge bismuth, cadmium, uye mercury, uye yakaenzana mune zvirimo neberyllium, germanium, uye uranium. Zvese zvicherwa zvine zirconium zvine hafnium. Zircon inoshandiswa muindasitiri ine 0.5-2% hafnium. Iyo beryllium zircon (Alvite) mune yechipiri zirconium ore inogona kuva ne15% hafnium. Kune zvakare mhando ye metamorphic zircon, cyrtolite, ine pamusoro pe5% HfO. Matura emaminerari maviri ekupedzisira madiki uye haasati agamuchirwa mumaindasitiri. Hafnium inonyanya kuwanikwa panguva yekugadzirwa kwe zirconium.
Inowanikwa mune dzakawanda zirconium ores. [18] [19] Nekuti pane zvishoma zviri mukati mucrust. Inowanzogara pamwe chete ne zirconium uye haina ore yakasiyana.
Kugadzirira nzira:
1. Inogona kugadzirirwa ne magnesium kuderedzwa kwehafnium tetrachloride kana kupisa kwekuparara kwehafnium iodide. HfCl4 uye K2HfF6 inogona zvakare kushandiswa seyakagadzirwa. Maitiro ekugadzirwa kwe electrolytic muNaCl KCl HfCl4 kana K2HfF6 melt yakafanana neye electrolytic kugadzirwa kwe zirconium.
2. Hafnium inogarisana ne zirconium, uye hapana yakaparadzana mbishi yehafnium. Iyo mbishi yekugadzira hafnium ine crude hafnium oxide yakaparadzaniswa panguva yekugadzira zirconium. Bvisa hafnium oxide uchishandisa ion exchange resin, uye wozoshandisa nzira imwechete se zirconium kugadzira simbi hafnium kubva kune iyi hafnium oxide.
3. Inogona kugadzirirwa nekupisa hafnium tetrachloride (HfCl4) ne sodium kuburikidza nekuderedza.
Nzira dzekutanga dzekuparadzanisa zirconium uye hafnium dzaive dzefractional crystallization yefluorinated complex salts uye fractional precipitation yephosphates. Nzira idzi dzinonetsa kushanda uye dzinongoperera pakushandisa marabhoritari. Tekinoroji nyowani dzekuparadzanisa zirconium nehafnium, dzakaita senge fractionation distillation, solvent extraction, ion exchange, uye fractionation adsorption, yabuda imwe neimwe, nekubvisa solvent kunonyanya kushanda. Iwo maviri anowanzo shandiswa kupatsanura masisitimu ndeye thiocyanate cyclohexanone system uye tributyl phosphate nitric acid system. Zvigadzirwa zvakawanikwa nenzira dziri pamusoro apa zvese hafnium hydroxide, uye yakachena hafnium oxide inogona kuwanikwa necalcination. High kuchena hafnium inogona kuwanikwa neion exchange nzira.
Muindasitiri, kugadzirwa kwesimbi hafnium kunowanzo kusanganisa zvese Kroll process uye Debor Aker process. Iyo Kroll process inosanganisira kudzikiswa kwehafnium tetrachloride uchishandisa metallic magnesium:
2Mg+HfCl4- → 2MgCl2+Hf
Iyo nzira yeDebor Aker, inozivikanwawo seyo iodization nzira, inoshandiswa kuchenesa chipanje sehafnium uye kuwana simbi inogoneka hafnium.
5. Kunyungudutswa kwehafnium kwakangofanana nekwezirconium:
Nhanho yekutanga ndeyekuparara kwesimbi, iyo inosanganisira nzira nhatu: chlorination ye zircon kuwana (Zr, Hf) Cl. Alkali kunyunguduka kwe zircon. Zircon inonyunguduka neNaOH kumativi mazana matanhatu, uye pamusoro pe90% ye (Zr, Hf) O inoshandura kuita Na (Zr, Hf) O, neSiO inoshandurwa kuita NaSiO, iyo inonyungudutswa mumvura kuti ibvise. Na (Zr, Hf) O inogona kushandiswa semhinduro yekutanga yekuparadzanisa zirconium uye hafnium mushure mekunyungudutswa muHNO. Nekudaro, kuvepo kweSiO colloids kunoita kuti kupatsanurwa kwe solvent kuome. Sinter neKSiF wonyura mumvura kuti uwane mhinduro yeK (Zr, Hf) F. Mhinduro yacho inogona kuparadzanisa zirconium uye hafnium kuburikidza nefractional crystallization;
Nhanho yechipiri ndeyekuparadzaniswa kwe zirconium uye hafnium, iyo inogona kuwanikwa uchishandisa solvent extraction kupatsanurwa nzira uchishandisa hydrochloric acid MIBK (methyl isobutyl ketone) system uye HNO-TBP (tributyl phosphate) system. Iyo tekinoroji yekuparadzanisa-matanho akawanda uchishandisa mutsauko mumhepo yekumanikidza pakati peHfCl neZrCl inonyungudika pasi pekumanikidza kwakanyanya (pamusoro pe20 atmospheres) yakagara ichidzidzwa, iyo inogona kuchengetedza yechipiri chlorination process uye kuderedza mari. Nekudaro, nekuda kwedambudziko rekuora kwe (Zr, Hf) Cl neHCl, hazvisi nyore kuwana akakodzera kupatsanurwa column zvinhu, uye zvakare inoderedza kunaka kweZrCl neHfCl, ichiwedzera mari yekuchenesa. Muma1970, yakanga ichiri muchikamu chepakati chekuongorora chirimwa;
Nhanho yechitatu ndeyechipiri chlorination yeHfO kuwana crude HfCl yekuderedza;
Nhanho yechina ndeyekucheneswa kweHfCl uye kuderedza magnesium. Iyi nzira yakafanana nekucheneswa uye kuderedzwa kweZrCl, uye inoguma semi-yakapedza chigadzirwa ndeye coarse sponge hafnium;
Nhanho yechishanu ndeyekutsvaira distill crude sponge hafnium kubvisa MgCl uye kudzoreredza yakawandisa simbi magnesium, zvichikonzera chigadzirwa chakapedzwa chesiponji simbi hafnium. Kana iyo inoderedza inoshandisa sodium panzvimbo ye magnesium, danho rechishanu rinofanira kuchinjwa kuva kunyudzwa mumvura
Nzira yekuchengetedza:
Chengetedza muimba yekuchengetera inotonhorera uye ine mhepo. Ramba kure nepfarivari uye kunopisa kupisa. Inofanira kuchengetwa zvakasiyana kubva kune oxidants, acids, halogens, nezvimwewo, uye kudzivisa kusanganisa kuchengetedza. Kushandisa chiedza chinoputika-chisingapindi chiedza uye nzvimbo dzekupinza mhepo. Rambidza kushandiswa kwemichina uye maturusi ari nyore kupfuta. Nzvimbo yekuchengetera inofanirwa kunge yakashongedzerwa nemidziyo yakakodzera kuti ive neinodonha.
Nguva yekutumira: Sep-25-2023