Hafnium, chitsulo Hf, nambala ya atomiki 72, kulemera kwa atomiki 178.49, ndi chitsulo chonyezimira cha siliva wotuwa.
Hafnium ili ndi ma isotopu asanu ndi limodzi okhazikika mwachilengedwe: hafnium 174, 176, 177, 178, 179, ndi 180. Hafnium samachita ndi dilute hydrochloric acid, dilute sulfuric acid, ndi njira zamphamvu zamchere zamchere, koma zimasungunuka mu hydrofluoric acid ndi aqua. Dzinali limachokera ku dzina lachilatini la Copenhagen City.
Mu 1925, katswiri wa zamankhwala wa ku Sweden Hervey ndi katswiri wa sayansi ya ku Dutch Koster adapeza mchere wa hafnium wonyezimira pogwiritsa ntchito mchere wambiri wa fluorinated, ndipo anauchepetsa ndi zitsulo za sodium kuti apeze chitsulo choyera hafnium. Hafnium ili ndi 0.00045% ya kutumphuka kwa dziko lapansi ndipo nthawi zambiri imagwirizanitsidwa ndi zirconium m'chilengedwe.
Dzina la malonda: hafnium
Chizindikiro cha chinthu: Hf
Kulemera kwa atomiki: 178.49
Mtundu wa chinthu: metallic element
Zakuthupi:
Hafniumndi siliva imvi chitsulo ndi zitsulo zonyezimira; Pali mitundu iwiri yachitsulo hafnium: α Hafnium ndi hexagonal yodzaza kwambiri (1750 ℃) yokhala ndi kutentha kwapamwamba kuposa zirconium. Metal hafnium ili ndi mitundu yosiyanasiyana ya allotrope pa kutentha kwakukulu. Chitsulo hafnium ali mkulu neutroni mayamwidwe mtanda gawo ndipo angagwiritsidwe ntchito ngati zinthu kulamulira kwa reactors.
Pali mitundu iwiri ya mapangidwe a kristalo: kulongedza kwa hexagonal wandiweyani pa kutentha pansipa 1300 ℃（ α- Equation); Pa kutentha pamwamba pa 1300 ℃, imakhala ndi thupi la cubic (β-Equation). Chitsulo chokhala ndi pulasitiki chomwe chimalimba ndikukhala chophwanyika pamaso pa zonyansa. Kukhazikika mumlengalenga, kumangodetsa pamwamba powotchedwa. Ulusiwo ukhoza kuyatsidwa ndi lawi la machesi. Zofanana ndi zirconium. Sichichita ndi madzi, ma asidi osungunuka, kapena maziko amphamvu, koma amasungunuka mosavuta mu aqua regia ndi hydrofluoric acid. Makamaka mumagulu okhala ndi +4 valence. Hafnium alloy (Ta4HfC5) amadziwika kuti ali ndi malo osungunuka kwambiri (pafupifupi 4215 ℃).
Kapangidwe ka kristalo: Selo la crystal ndi hexagonal
Nambala ya CAS: 7440-58-6
Malo osungunuka: 2227 ℃
Malo otentha: 4602 ℃
Chemical katundu:
Mankhwala a hafnium ndi ofanana kwambiri ndi a zirconium, ndipo ali ndi kukana bwino kwa dzimbiri ndipo sawonongeka mosavuta ndi ma acid ambiri amchere amchere; Mosavuta kusungunuka mu hydrofluoric acid kupanga fluorinated complexes. Pa kutentha kwambiri, hafnium imathanso kuphatikizana mwachindunji ndi mpweya monga oxygen ndi nitrogen kupanga ma oxides ndi nitrides.
Hafnium nthawi zambiri imakhala ndi +4 valence mumagulu. Chophatikiza chachikulu ndihafnium oxideHfO2. Pali mitundu itatu yosiyanasiyana ya hafnium oxide:hafnium oxideanapezedwa mosalekeza calcination wa hafnium sulfate ndi kolorayidi okusayidi ndi monoclinic zosinthika; The hafnium oxide yomwe imapezeka potenthetsa hydroxide ya hafnium pafupifupi 400 ℃ ndi mtundu wa tetragonal; Ngati calcined pamwamba 1000 ℃, zosinthika kiyubiki angapezeke. Pagulu lina ndihafnium tetrachloride, zomwe ndi zopangira pokonzekera zitsulo za hafnium ndipo zimatha kukonzedwa pochita mpweya wa chlorine pa osakaniza a hafnium oxide ndi carbon. Hafnium tetrachloride imakumana ndi madzi ndipo nthawi yomweyo imasungunuka kukhala HfO (4H2O) 2+ yokhazikika kwambiri. HfO2+ion ilipo mumagulu ambiri a hafnium, ndipo imatha kuyeretsa singano ngati hydrated hafnium oxychloride HfOCl2 · 8H2O makhiristo mu hydrochloric acid acidified hafnium tetrachloride solution.
4-valent hafnium imakondanso kupanga ma complexes okhala ndi fluoride, opangidwa ndi K2HfF6, K3HfF7, (NH4) 2HfF6, ndi (NH4) 3HfF7. Ma complex awa akhala akugwiritsidwa ntchito pakulekanitsa zirconium ndi hafnium.
Common compounds:
Hafnium dioxide: dzina lakuti Hafnium dioxide; Hafnium dioxide; Mapangidwe a maselo: HfO2 [4]; Katundu: ufa woyera wokhala ndi makristalo atatu: monoclinic, tetragonal, ndi cubic. Kachulukidwe ndi 10.3, 10.1, ndi 10.43g/cm3, motero. Malo osungunuka 2780-2920K. Malo otentha 5400K. Kukula kokwanira kwamafuta 5.8 × 10-6/℃. Insoluble m'madzi, hydrochloric acid, ndi nitric acid, koma imasungunuka mu sulfuric acid ndi hydrofluoric acid. Amapangidwa ndi kuwonongeka kwamafuta kapena hydrolysis ya mankhwala monga hafnium sulfate ndi hafnium oxychloride. Zida zopangira zitsulo za hafnium ndi hafnium alloys. Amagwiritsidwa ntchito ngati zida zodziwikiratu, zokutira zotsutsa ma radioactive, ndi zothandizira. [5] Atomic energy level HfO ndi chinthu chomwe chimapezeka nthawi imodzi popanga mulingo wa mphamvu ya atomiki ZrO. Kuyambira ku chlorination yachiwiri, njira zoyeretsera, kuchepetsa, ndi kutsekemera kwa vacuum zimakhala zofanana ndi za zirconium.
Hafnium tetrachloride: Hafnium (IV) chloride, Hafnium tetrachloride Molecular formula HfCl4 Molecular weight 320.30 Khalidwe: White crystalline block. Kumva chinyezi. Kusungunuka mu acetone ndi methanol. Hydrolyze m'madzi kuti mupange hafnium oxychloride (HfOCl2). Kutenthetsa mpaka 250 ℃ ndikusungunula. Zowawa m'maso, kupuma, ndi khungu.
Hafnium hydroxide: Hafnium hydroxide (H4HfO4), nthawi zambiri imapezeka ngati hydrated oxide HfO2 · nH2O, imasungunuka m'madzi, imasungunuka mosavuta mu ma inorganic acid, osasungunuka mu ammonia, ndipo kawirikawiri imasungunuka mu sodium hydroxide. Kutentha mpaka 100 ℃ kupanga hafnium hydroxide HfO (OH) 2. White hafnium hydroxide precipitate imapezeka pochita mchere wa hafnium (IV) ndi madzi ammonia. Itha kugwiritsidwa ntchito popanga mankhwala ena a hafnium.
Mbiri Yofufuza
Mbiri Yakale:
Mu 1923, katswiri wa zamankhwala wa ku Sweden Hervey ndi katswiri wa sayansi ya ku Dutch D. Koster anapeza hafnium mu zircon yopangidwa ku Norway ndi Greenland, ndipo anaitcha kuti hafnium, yomwe inachokera ku dzina lachilatini Hafnia of Copenhagen. Mu 1925, Hervey ndi Coster analekanitsa zirconium ndi titaniyamu pogwiritsa ntchito njira ya fractional crystallization ya fluorinated complex salt kupeza mchere wa hafnium; Ndipo kuchepetsa mchere wa hafnium ndi zitsulo zachitsulo kuti mupeze chitsulo choyera hafnium. Hervey anakonza chitsanzo cha ma milligrams angapo a pure hafnium.
Kuyesera kwamankhwala pa zirconium ndi hafnium:
Pakuyesa kochitidwa ndi Pulofesa Carl Collins ku Yunivesite ya Texas mu 1998, akuti gamma irradiated hafnium 178m2 (isomer hafnium-178m2 [7]) imatha kutulutsa mphamvu zazikulu, zomwe ndi maulamuliro asanu apamwamba kuposa momwe amachitira ndi mankhwala. maulalo atatu otsika kwambiri kuposa machitidwe a nyukiliya. [8] Hf178m2 (hafnium 178m2) ili ndi moyo wautali kwambiri pakati pa ma isotopu omwe akhalapo nthawi yayitali: Hf178m2 (hafnium 178m2) imakhala ndi theka la moyo wa zaka 31, zomwe zimapangitsa kuti ma radioactivity achilengedwe a Becquerels pafupifupi 1.6 thililiyoni. Lipoti la Collins likuti gilamu imodzi ya Hf178m2 yoyera (hafnium 178m2) ili ndi pafupifupi ma megajoules 1330, omwe ndi ofanana ndi mphamvu yotulutsidwa ndi kuphulika kwa ma kilogalamu 300 a zophulika za TNT. Lipoti la Collins likuwonetsa kuti mphamvu zonse munjira iyi zimatulutsidwa mu mawonekedwe a X-ray kapena gamma ray, yomwe imatulutsa mphamvu mwachangu kwambiri, ndipo Hf178m2 (hafnium 178m2) imathabe kuchitapo kanthu pakatsika kwambiri. [9] Pentagon yapereka ndalama zofufuzira. Pakuyesaku, chiŵerengero cha signal-to-noise chinali chochepa kwambiri (ndi zolakwika zazikulu), ndipo kuyambira pamenepo, ngakhale asayansi akuyesa kangapo m'mabungwe angapo kuphatikizapo United States Department of Defense Advanced Projects Research Agency (DARPA) ndi JASON Defense Advisory. Gulu [13], palibe wasayansi yemwe wakwanitsa kuchita izi malinga ndi zomwe Collins ananena, ndipo Collins sanapereke umboni wamphamvu wotsimikizira kukhalapo kwa izi, Collins adapereka njira yogwiritsira ntchito gamma yopangidwa. ray kutulutsa mphamvu kuchokera ku Hf178m2 (hafnium 178m2) [15], koma asayansi ena atsimikizira kuti izi sizingachitike. [16] Hf178m2 (hafnium 178m2) amakhulupirira kwambiri kuti ophunzira sangakhale gwero lamphamvu.
Munda wa ntchito:
Hafnium ndi yothandiza kwambiri chifukwa cha kuthekera kwake kutulutsa ma electron, monga momwe amagwiritsidwira ntchito ngati filament mu nyali za incandescent. Amagwiritsidwa ntchito ngati cathode ya machubu a X-ray, ndipo ma alloys a hafnium ndi tungsten kapena molybdenum amagwiritsidwa ntchito ngati ma elekitirodi a machubu otulutsa mphamvu kwambiri. Amagwiritsidwa ntchito kwambiri mumakampani opanga ma cathode ndi tungsten mawaya a X-ray. Pure hafnium ndi chinthu chofunikira kwambiri pamakampani opanga mphamvu za atomiki chifukwa cha pulasitiki yake, kukonza kosavuta, kukana kutentha kwambiri, komanso kukana dzimbiri. Hafnium ili ndi gawo lalikulu la matenthedwe a nyutroni ndipo ndi chotengera chabwino cha nyutroni, chomwe chitha kugwiritsidwa ntchito ngati ndodo yowongolera ndi chida choteteza cha ma atomiki. Ufa wa Hafnium ukhoza kugwiritsidwa ntchito ngati chopangira ma roketi. Cathode ya machubu a X-ray imatha kupangidwa m'makampani amagetsi. Hafnium alloy imatha kukhala ngati gawo loteteza kutsogolo kwa ma rocket nozzles ndi ndege zoloweranso, pomwe aloyi a Hf Ta angagwiritsidwe ntchito kupanga zida zachitsulo ndi zokana. Hafnium imagwiritsidwa ntchito ngati chowonjezera pazitsulo zosagwira kutentha, monga tungsten, molybdenum, ndi tantalum. HfC itha kugwiritsidwa ntchito ngati chowonjezera cha ma aloyi olimba chifukwa cha kuuma kwake kwakukulu komanso malo osungunuka. Malo osungunuka a 4TaCHfC ndi pafupifupi 4215 ℃, zomwe zimapangitsa kuti pakhale malo omwe amadziwika bwino kwambiri. Hafnium ingagwiritsidwe ntchito ngati getter muzinthu zambiri za inflation. Ma Hafnium getters amatha kuchotsa mpweya wosafunikira monga mpweya ndi nayitrogeni womwe ulipo mu dongosolo. Hafnium nthawi zambiri imagwiritsidwa ntchito ngati chowonjezera mumafuta a hydraulic kuti ateteze kuphulika kwamafuta a hydraulic panthawi yomwe ali pachiwopsezo chachikulu, ndipo amakhala ndi mphamvu zotsutsana ndi kugwedezeka. Chifukwa chake, nthawi zambiri amagwiritsidwa ntchito m'mafakitale hydraulic mafuta. Medical hydraulic mafuta.
Hafnium element imagwiritsidwanso ntchito mu Intel 45 nanoprocessors aposachedwa. Chifukwa cha kupangidwa kwa silicon dioxide (SiO2) komanso kuthekera kwake kuchepetsa makulidwe kuti apititse patsogolo magwiridwe antchito a transistor, opanga ma processor amagwiritsa ntchito silicon dioxide ngati zinthu zopangira ma dielectric pachipata. Intel itayambitsa njira yopangira ma nanometer 65, ngakhale idayesetsa kuchepetsa makulidwe a silicon dioxide gate dielectric kukhala ma nanometer 1.2, ofanana ndi zigawo 5 za maatomu, zovuta zogwiritsa ntchito mphamvu ndi kutayika kwa kutentha zimachulukiranso pamene transistor. idachepetsedwa kukhala kukula kwa atomu, zomwe zimapangitsa kuti pakhale zinyalala zapano komanso mphamvu ya kutentha yosafunikira. Choncho, ngati zipangizo zamakono zikupitilizidwa kugwiritsidwa ntchito ndipo makulidwe akucheperachepera, kutuluka kwa dielectric pachipata kudzawonjezeka kwambiri, Kubweretsa teknoloji ya transistor mpaka malire ake. Kuti athane ndi vutoli, Intel ikukonzekera kugwiritsa ntchito zida zokulirapo za K (zochokera ku hafnium) ngati ma dielectric pachipata m'malo mwa silicon dioxide, zomwe zachepetsa bwino kutayikira nthawi zopitilira 10. Poyerekeza ndi m'badwo wam'mbuyomu waukadaulo wa 65nm, njira ya Intel's 45nm imachulukitsa kachulukidwe wa transistor pafupifupi kawiri, zomwe zimapangitsa kuchuluka kwa ma transistors kapena kuchepetsa kuchuluka kwa purosesa. Kuphatikiza apo, mphamvu yofunikira pakusintha kwa transistor ndiyotsika, kumachepetsa kugwiritsa ntchito mphamvu pafupifupi 30%. Maulumikizidwe amkati amapangidwa ndi waya wamkuwa wophatikizidwa ndi dielectric otsika k, kuwongolera bwino komanso kuchepetsa kugwiritsa ntchito mphamvu, ndipo liwiro losinthira lili pafupifupi 20% mwachangu.
Kugawa kwa mchere:
Hafnium ili ndi crustal yochuluka kuposa zitsulo zomwe zimagwiritsidwa ntchito nthawi zambiri monga bismuth, cadmium, ndi mercury, ndipo ndizofanana ndi beryllium, germanium, ndi uranium. Mchere uliwonse wokhala ndi zirconium uli ndi hafnium. Zircon zomwe zimagwiritsidwa ntchito m'makampani zimakhala ndi 0.5-2% hafnium. Beryllium zircon (Alvite) mu ore yachiwiri ya zirconium imatha kukhala ndi 15% hafnium. Palinso mtundu wa metamorphic zircon, cyrtolite, yomwe ili ndi 5% HfO. Zosungirako za mchere ziwiri zomalizazi ndizochepa ndipo sizinagwiritsidwebe ntchito m'makampani. Hafnium imapezedwa makamaka popanga zirconium.
Imapezeka m'mafuta ambiri a zirconium. [18] [19] Chifukwa pali zochepa zomwe zili mu kutumphuka. Nthawi zambiri amakhala limodzi ndi zirconium ndipo alibe ore osiyana.
Njira yokonzekera:
1. Ikhoza kukonzedwa ndi magnesium kuchepetsa hafnium tetrachloride kapena kuwola matenthedwe a hafnium iodide. HfCl4 ndi K2HfF6 zitha kugwiritsidwanso ntchito ngati zopangira. Njira yopanga ma electrolytic mu NaCl KCl HfCl4 kapena K2HfF6 melt ndi yofanana ndi ya electrolytic kupanga zirconium.
2. Hafnium imakhala pamodzi ndi zirconium, ndipo palibe zopangira zosiyana za hafnium. Zopangira zopangira hafnium ndi crude hafnium oxide yomwe imapatulidwa panthawi yopanga zirconium. Chotsani hafnium oxide pogwiritsa ntchito ion exchange resin, ndiyeno gwiritsani ntchito njira yofanana ndi zirconium pokonzekera zitsulo za hafnium kuchokera ku hafnium oxide iyi.
3. Ikhoza kukonzedwa ndi co heat hafnium tetrachloride (HfCl4) ndi sodium kupyolera mu kuchepetsa.
Njira zoyambirira zolekanitsira zirconium ndi hafnium zinali crystallization ya mchere wovuta wa fluorinated ndi mpweya wochepa wa phosphates. Njirazi ndizovuta kuzigwira ndipo zimangogwiritsidwa ntchito ku labotale. Tekinoloje zatsopano zolekanitsa zirconium ndi hafnium, monga kuphatikizika kwa magawo, kutulutsa zosungunulira, kusinthana kwa ion, ndi kuphatikizika kwa magawo, zatulukira chimodzi pambuyo pa chimzake, ndikuchotsa zosungunulira kukhala zothandiza kwambiri. Njira ziwiri zolekanitsa zomwe zimagwiritsidwa ntchito kwambiri ndi thiocyanate cyclohexanone system ndi tributyl phosphate nitric acid system. Zogulitsa zomwe zapezedwa ndi njira zomwe zili pamwambazi zonse ndi hafnium hydroxide, ndipo hafnium oxide yoyera imatha kupezedwa ndi calcination. High purity hafnium imatha kupezeka ndi njira yosinthira ion.
M'makampani, kupanga chitsulo hafnium nthawi zambiri kumaphatikizapo ndondomeko ya Kroll ndi ndondomeko ya Debor Aker. Njira ya Kroll imaphatikizapo kuchepetsa hafnium tetrachloride pogwiritsa ntchito zitsulo zachitsulo:
2Mg+HfCl4- → 2MgCl2+Hf
Njira ya Debor Aker, yomwe imadziwikanso kuti iodization, imagwiritsidwa ntchito kuyeretsa siponji ngati hafnium ndikupeza chitsulo chosungunuka.
5. Kusungunuka kwa hafnium ndikofanana kwenikweni ndi zirconium:
Gawo loyamba ndi kuwonongeka kwa ore, komwe kumaphatikizapo njira zitatu: chlorination ya zircon kuti ipeze (Zr, Hf) Cl. Kusungunuka kwa alkali kwa zircon. Zircon imasungunuka ndi NaOH pafupifupi 600, ndipo kuposa 90% ya (Zr, Hf) O imasintha kukhala Na (Zr, Hf) O, ndi SiO yosinthidwa kukhala NaSiO, yomwe imasungunuka m'madzi kuti ichotsedwe. Na (Zr, Hf) O itha kugwiritsidwa ntchito ngati njira yoyambira yolekanitsira zirconium ndi hafnium pambuyo pakusungunuka mu HNO. Komabe, kukhalapo kwa SiO colloids kumapangitsa kulekanitsa zosungunulira m'zigawo kukhala zovuta. Sinter ndi KSiF ndikuviika m'madzi kuti mupeze yankho la K (Zr, Hf) F. Yankho likhoza kulekanitsa zirconium ndi hafnium kupyolera mu crystallization fractional;
Gawo lachiwiri ndi kulekanitsa zirconium ndi hafnium, zomwe zingatheke pogwiritsa ntchito njira zolekanitsa zosungunulira pogwiritsa ntchito hydrochloric acid MIBK (methyl isobutyl ketone) dongosolo ndi HNO-TBP (tributyl phosphate) dongosolo. Ukadaulo wogawika magawo ambiri pogwiritsira ntchito kusiyana kwa mpweya pakati pa HfCl ndi ZrCl umasungunuka pansi pa kupanikizika kwakukulu (pamwamba pa 20 atmospheres) wakhala akuphunzira kale, zomwe zingapulumutse njira yachiwiri ya chlorination ndi kuchepetsa ndalama. Komabe, chifukwa cha vuto la dzimbiri la (Zr, Hf) Cl ndi HCl, sikophweka kupeza zipangizo zoyenera zogawa magawo, komanso kuchepetsa ubwino wa ZrCl ndi HfCl, kuonjezera ndalama zoyeretsera. M'zaka za m'ma 1970, inali idakali pakatikati yoyesera zomera;
Gawo lachitatu ndi chlorination yachiwiri ya HfO kuti mupeze HfCl yaiwisi kuti muchepetse;
Gawo lachinayi ndikuyeretsedwa kwa HfCl ndi kuchepetsa magnesium. Njirayi ndi yofanana ndi kuyeretsedwa ndi kuchepetsedwa kwa ZrCl, ndipo zotsatira zomwe zimatsirizidwa ndi coarse sponge hafnium;
Gawo lachisanu ndikupukuta siponji yakuda ya hafnium kuti muchotse MgCl ndikubwezeretsanso chitsulo chowonjezera cha magnesium, zomwe zimapangitsa kuti pakhale siponji yachitsulo. Ngati wochepetsera akugwiritsa ntchito sodium m'malo mwa magnesium, gawo lachisanu liyenera kusinthidwa kukhala kumizidwa m'madzi
Njira yosungira:
Kusunga m'nyumba yozizira komanso mpweya wokwanira. Khalani kutali ndi zoyaka ndi kutentha. Iyenera kusungidwa mosiyana ndi okosijeni, zidulo, halogens, etc., ndi kupewa kusakaniza yosungirako. Kugwiritsa ntchito magetsi osaphulika komanso mpweya wabwino. Letsani kugwiritsa ntchito zida zamakina ndi zida zomwe zimakonda kuphulika. Malo osungiramo ayenera kukhala ndi zipangizo zoyenera kuti pakhale zotayikira.
Nthawi yotumiza: Sep-25-2023