JPS62224692A - Method and apparatus for producing terbium alloy - Google Patents
Method and apparatus for producing terbium alloyInfo
- Publication number
- JPS62224692A JPS62224692A JP6793486A JP6793486A JPS62224692A JP S62224692 A JPS62224692 A JP S62224692A JP 6793486 A JP6793486 A JP 6793486A JP 6793486 A JP6793486 A JP 6793486A JP S62224692 A JPS62224692 A JP S62224692A
- Authority
- JP
- Japan
- Prior art keywords
- terbium
- alloy
- cathode
- electrolytic
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001117 Tb alloy Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- LKNRQYTYDPPUOX-UHFFFAOYSA-K trifluoroterbium Chemical compound F[Tb](F)F LKNRQYTYDPPUOX-UHFFFAOYSA-K 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229910001632 barium fluoride Inorganic materials 0.000 claims abstract description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 85
- 239000000956 alloy Substances 0.000 claims description 85
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 37
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 31
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 31
- 229910052771 Terbium Inorganic materials 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 26
- JSUSQWYDLONJAX-UHFFFAOYSA-N iron terbium Chemical compound [Fe].[Tb] JSUSQWYDLONJAX-UHFFFAOYSA-N 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 18
- 229910000531 Co alloy Inorganic materials 0.000 claims description 16
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 9
- 150000003502 terbium compounds Chemical class 0.000 claims description 8
- 238000003780 insertion Methods 0.000 claims description 7
- 230000037431 insertion Effects 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 8
- 229910004299 TbF3 Inorganic materials 0.000 abstract 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 43
- SDVIPADSGIIEHD-UHFFFAOYSA-N cobalt terbium Chemical compound [Co].[Tb] SDVIPADSGIIEHD-UHFFFAOYSA-N 0.000 description 13
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 150000002910 rare earth metals Chemical class 0.000 description 13
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 8
- 229910003451 terbium oxide Inorganic materials 0.000 description 8
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000002909 rare earth metal compounds Chemical class 0.000 description 4
- 239000003870 refractory metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- -1 calcium Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 206010065687 Bone loss Diseases 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910000982 rare earth metal group alloy Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- OTBIRTREDHPGJA-UHFFFAOYSA-N terbium Chemical compound [Tb].[Tb] OTBIRTREDHPGJA-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（技術分野）
本発明は、テルビウム−鉄合金、テルビウム−コバルト
合金等のテルビウム合金の製造方法並びにその製造装置
に係り、特に希土類系光磁気ディスク用合金等へ添加す
るのに適した、テルビウムの含有量が高く、不純物や介
在物の含有量の低い母合金を連続的に製造することの出
来る方法並びにその装置に関するものである。Detailed Description of the Invention (Technical Field) The present invention relates to a method for manufacturing terbium alloys such as terbium-iron alloys and terbium-cobalt alloys, and an apparatus for manufacturing the same. The present invention relates to a method and an apparatus for continuously producing a master alloy having a high terbium content and a low content of impurities and inclusions, which is suitable for use in the present invention.
（背景技術）
テルビウムは、最近、研究開発・実用化が進められてい
る光磁気ディスク材料、例えばＴｂＦｅ。(Background Art) Terbium is a magneto-optical disk material, such as TbFe, which has been recently researched, developed and put into practical use.
ＴｂＣｏ、ＴｂＧｄＦｅ、ＴｂＦｅＣｏ等として、更に
は他の材料系への添加元素として、その需要の増大が期
待されている。而して、テルビウムの所定の用途に供さ
れる合金への添加は、テルビウム金属の形でも可能であ
るが、テルビウム金属の融点が１３６５℃と高温である
ところから、むしろ取扱い上、鉄、コバルト等の金属と
の母合金の方が有利と考えられる。Demand for TbCo, TbGdFe, TbFeCo, etc., and as an additive element to other material systems is expected to increase. Terbium can be added to alloys used for specific purposes in the form of terbium metal, but because terbium metal has a high melting point of 1,365°C, it is difficult to add terbium to alloys used for specific purposes, such as iron or cobalt. It is considered that a master alloy with metals such as
ところで、希土類金属と高融点金属との合金の製造方法
としては、一般的に、次の４つの方法が知られている。By the way, the following four methods are generally known as methods for producing alloys of rare earth metals and high melting point metals.
まず、第一は、希土類金属を溶融塩電解法或いは活性金
属による還元法等により製造しく希土類金属或いはそれ
らの合金として取り出す）、他金属と混合溶解し、合金
化する方法である。しかして、この方法のうち、電解に
より希土類金属或いはそれらの合金を形成せしめる工程
を経由する方・法にあっては、その電解原料として塩化
物を用いる場合、原料の取扱いが難しく、また操業がバ
ッチ式であるところに問題がある。また、フッ化物電解
浴を用いて希土類金属の酸化物を電解する場合には、か
かる酸化物原料の電解浴への溶解度が小さく、そのため
に連続操業が難しく、電解槽底部にスラッジが形成され
る問題が内在している。First, there is a method in which rare earth metals are produced by molten salt electrolysis or reduction with active metals (removed as rare earth metals or alloys thereof), mixed with other metals, melted, and alloyed. However, among these methods, when using chloride as the raw material for electrolysis, handling of the raw material is difficult and operation is difficult. The problem is that it is a batch method. Furthermore, when oxides of rare earth metals are electrolyzed using a fluoride electrolytic bath, the solubility of such oxide raw materials in the electrolytic bath is low, which makes continuous operation difficult, and sludge is formed at the bottom of the electrolytic bath. There is an inherent problem.
特に、大量生産、連続操業を達成するには、生成メタル
は液体状態であることが好ましいが、高融点希土類金属
の場合においては、そのために電解温度を高くする必要
があり、炉材等の不純物が生成メタル中に混入し易く、
現実的ではないのである。In particular, in order to achieve mass production and continuous operation, it is preferable that the metal produced be in a liquid state, but in the case of high melting point rare earth metals, it is necessary to raise the electrolysis temperature to achieve this, and impurities such as furnace materials is easily mixed into the generated metal,
It's not realistic.
一方、活性金属を用いて希土類金属原料を還元する工程
を含む上記方法にあっては、操業がバッチ式であり、連
続的な大規模生産には適していない問題がある他、高価
な還元剤の使用、還元装置に高価な材料が必要であり、
また、残留還元剤成分の除去工程が必要である等の工程
が複雑となる問題を内在している。On the other hand, the above method, which includes the step of reducing rare earth metal raw materials using active metals, has problems in that the operation is batch-type and is not suitable for continuous large-scale production. use, requires expensive materials for reduction equipment,
Further, there are inherent problems in that the process is complicated, such as the need for a process to remove residual reducing agent components.
また、第二は、希土類金属の化合物と合金化すべき金属
の化合物を混合し、適当な化合物（例えばＳ ｍ −Ｃ
ｏ合金製造の場合では、水素化カルシウム）で還元する
方法であるが、この方法では、高価な還元剤を用いるこ
と、操業がバッチ式であって、連続的な大規模生産には
適していないこと等の問題がある。In the second method, a rare earth metal compound and a metal compound to be alloyed are mixed, and an appropriate compound (for example, S m -C
o In the case of alloy production, the method is to reduce with calcium hydride), but this method uses an expensive reducing agent and is a batch-type operation, which is not suitable for continuous large-scale production. There are other problems.
さらに、第三に、溶融塩電解法で希土類金属の化合物と
合金化すべき金属の化合物を電解浴中に溶融せしめ、再
化合物を電解還元して、陰極上に合金として析出させる
方法（例えば、米国特許第３２９８９３５号）があるが
、この方法にも、次のような問題が内在しているのであ
る。すなわち、陰極上に析出する合金の組成を、電解工
程中長期間にわたって安定化させることが難しく、また
酸化物を原料とする場合には、電解浴への原料の溶解度
が小さいために、連続操業が難しい等の問題が内在して
いるのである。Furthermore, thirdly, a method in which a metal compound to be alloyed with a rare earth metal compound is melted in an electrolytic bath by molten salt electrolysis, and the compound is electrolytically reduced and deposited as an alloy on the cathode (for example, Japanese Patent No. 3298935), but this method also has the following problems. In other words, it is difficult to stabilize the composition of the alloy deposited on the cathode over a long period of time during the electrolytic process, and when oxides are used as raw materials, the solubility of the raw materials in the electrolytic bath is low, making continuous operation difficult. There are inherent problems such as difficulty in
そしてまた、第四の方法は、所謂消耗電極法と称される
ものであって、合金化すべき金属を固体の陰極とする一
方、希土類金属の化合物を適当な溶融塩の電解浴中に溶
解させて電解還元せしめ、目的とする希土類金属を陰極
上に析出させ、陰極金属と合金化させる方法（Ｕ、Ｓ、
ビューロー・オプ・マインズ、レポート・オブ・インベ
スティゲーションズ、１ｔｈ７１４６ （１９６８）
、特許第８３７４０１号、特許第９６７３８９号など参
照〕である。The fourth method is the so-called consumable electrode method, in which the metal to be alloyed is used as a solid cathode, while the rare earth metal compound is dissolved in an electrolytic bath of a suitable molten salt. A method (U, S,
Bureau of Mines, Report of Investigations, 1th7146 (1968)
, Patent No. 837401, Patent No. 967389, etc.].
しかしながら、この方法にあっても、次のような欠点が
内在している。すなわち、電解還元されるべき希土類金
属の化合物として酸化物原料が用いられた場合にあって
は、先に述べた如く、電解浴中への酸化物の溶解度が低
いことやスラッジが生成する等の問題があり、そしてこ
の問題の回避のためには、高温操業が必要となるのであ
る。しかして、この高温操業を行なうと、炉材等からの
不純物の混入が多くなって、生成合金の品質を低下せし
める、新たな問題を惹起することとなる。However, even this method has the following drawbacks. In other words, when an oxide raw material is used as a rare earth metal compound to be electrolytically reduced, as mentioned above, there are problems such as low solubility of the oxide in the electrolytic bath and the formation of sludge. There is a problem, and high temperature operation is required to avoid this problem. However, when this high-temperature operation is performed, a new problem arises in that impurities from the furnace materials and the like increase, degrading the quality of the produced alloy.
しかも、この消耗電極法では、生成合金の回収は、バッ
チ式等で行なわれ、連続化されておらず、大量生産には
不適当である問題も内在している。Moreover, in this consumable electrode method, the produced alloy is collected in a batch manner, and is not continuous, which has the inherent problem of being unsuitable for mass production.
かかる状況下、テルビウム金属は、これまで殆ど用途が
なく、その少量の製造方法としては、上述の第一の方法
における還元法が考えられるが、還元剤のカルシウムの
残存や酸素等の不純物が、ターゲット材料としては有害
であり、それを連続的に製造する工業的な方法は充分に
確立されていない。Under such circumstances, terbium metal has had almost no use so far, and the reduction method in the first method mentioned above is considered as a method for producing small quantities of terbium metal, but the residual calcium of the reducing agent and impurities such as oxygen It is harmful as a target material, and an industrial method for continuously producing it is not well established.
（発明の目的）
ここにおいて、本発明は、かかる事情を背景にして為さ
れたものであって、その目的とするところは、テルビウ
ム−鉄合金、テルビウム化合物ル１へ合金等のテルビウ
ム合金を、連続的に製造し得る方法並びにそのだめの装
置を提供することにあり、また他の目的とするところは
、テルビウムの含有量が高く、カルシウムや酸素等の不
純物や介在物等の含有量の低い、テルビウム合金の信頬
性のある経済的な工業的製造方法並びに装置を提供する
ことにある。(Object of the Invention) The present invention has been made against the background of the above, and its object is to produce a terbium alloy such as a terbium-iron alloy or a terbium compound 1 alloy. The purpose is to provide a method and an apparatus for continuous production, and another purpose is to provide a method that can be produced continuously, and another purpose is to provide a method that can be manufactured continuously, and another purpose is to provide a method that can produce it continuously. The object of the present invention is to provide a reliable and economical industrial manufacturing method and apparatus for terbium alloy.
（発明の構成・効果）
本発明は、かかる目的を達成するために、テルビウムと
合金化し得る金属からなる固体の陰極と炭素陽極とを用
いて、テルビウム化合物を溶融塩電解浴中において電解
還元せしめ、生成するテルビウムを前記陰極上に析出さ
せると共に、該陰極を構成する金属と合金化せしめて、
目的とするテルビウム合金を形成させるに際して、前記
テルビウム化合物としてフッ化テルビウムを用いると共
に、かかるテルビウム化合物を含む前記溶融塩電解浴が
、実質的に２０〜９５重世％のフッ化テルビウム、５〜
８０重量％のフッ化リチウム、４０重撥％までのフッ化
バリウム及び２０重泄％までのフッ化カルシウムにて構
成されるように調整する一方、前記テルビウム合金を前
記陰極上に液体状態で生成せしめ、そして該液体状態の
テルビウム合金を、液滴として該陰極下方の電解浴中に
開口部を有する受器内に滴下せしめて、液層として溜め
、更にこの受器内の液層より、テルビウム合金を液体状
態で取り出すようにしたのである。(Structure and Effects of the Invention) In order to achieve the above object, the present invention reduces a terbium compound electrolytically in a molten salt electrolytic bath using a solid cathode made of a metal that can be alloyed with terbium and a carbon anode. , depositing the generated terbium on the cathode and alloying it with the metal constituting the cathode,
In forming the desired terbium alloy, terbium fluoride is used as the terbium compound, and the molten salt electrolytic bath containing the terbium compound contains substantially 20 to 95% by weight of terbium fluoride, 5 to 95% by weight.
The terbium alloy is formed in a liquid state on the cathode while being adjusted to consist of 80% by weight of lithium fluoride, up to 40% by weight of barium fluoride and up to 20% by weight of calcium fluoride. Then, the terbium alloy in the liquid state is dropped as droplets into a receiver having an opening in the electrolytic bath below the cathode to collect it as a liquid layer, and from the liquid layer in the receiver, terbium This allowed the alloy to be extracted in a liquid state.
かくの如く、本発明に従えば、テルビウム−鉄合金、テ
ルビウム−コバルト合金などのテルビウム合金が電解還
元操作の一段階で製造でき、そして光磁気ディスク材料
などの材料特性に悪影響を与える酸素等不純物や介在物
等の含有量が低く、且つテルビウム含有量の高いテルビ
ウム合金が一段階で経済的に且つ、連続的に製造するこ
とができることとなったのである。より具体的には、固
体の陰極を使用するため、陰極の取扱が容易であること
は勿論、生成合金を電解時の液体合金のままで取り出す
ために、実質上、電解を中断することなく、連続操業が
可能であり、そして、消耗陰極法の利点である低温操業
が連続的に行ない得る結果、電解成績並びに酸素等不純
物の低減等生成合金品位が効果的に改善されるのである
。As described above, according to the present invention, terbium alloys such as terbium-iron alloys and terbium-cobalt alloys can be produced in one step of the electrolytic reduction operation, and impurities such as oxygen that adversely affect the properties of materials such as magneto-optical disk materials can be produced. It became possible to economically and continuously produce a terbium alloy with a low content of terbium and inclusions and a high terbium content in one step. More specifically, since a solid cathode is used, the cathode is not only easy to handle, but also the produced alloy can be taken out as a liquid alloy during electrolysis, so electrolysis can be carried out without interrupting the electrolysis. Continuous operation is possible, and as a result of continuous low-temperature operation, which is an advantage of the consumable cathode method, the electrolytic performance and the quality of the produced alloy, such as the reduction of impurities such as oxygen, are effectively improved.
また、かかる本発明に従えば、前述したカルシウム等の
活性金属による還元法では困難な、操業の連続化が達成
され、且つ活性金属等の不純物の混入が抑制され、更に
酸化テルビウムを原料とするフッ化物−酸化物混合溶融
塩の電解による製造方法における連ＶＥ燥業上の困難を
悉く回避することができることとなったのである。Further, according to the present invention, continuous operation, which is difficult to achieve with the above-mentioned reduction method using active metals such as calcium, is achieved, and contamination of impurities such as active metals is suppressed, and furthermore, terbium oxide is used as a raw material. It has become possible to avoid all the difficulties associated with VE drying in the electrolytic production method of fluoride-oxide mixed molten salt.
さらに、本発明に従えば、酸化テルビウムを原料とする
電解より、低い温度での操業が可能であり、これによっ
て炉材等からの生成合金への不純物、介在物の混入を効
果的に抑制することができ、また同一温度でアノード電
流密度を大きくとることができるところから、同一寸法
のアノードを用いた場合に、前記酸化物を原料とする電
解法に比して、電流を増すことができ、生産性を向上せ
しめることができる利点がある。Furthermore, according to the present invention, it is possible to operate at a lower temperature than electrolysis using terbium oxide as a raw material, which effectively suppresses the incorporation of impurities and inclusions from furnace materials etc. into the produced alloy. Furthermore, since the anode current density can be increased at the same temperature, the current can be increased when using an anode of the same size compared to the electrolytic method using the above-mentioned oxide as a raw material. , which has the advantage of improving productivity.
なお、かかる本発明において、陰極としては、目的とす
るテルビウム合金を構成する金属、例えば鉄、コバルト
、更には銅、ニッケル、マンガン、クロム、チタン等の
容易に合金化し得る金属からなるものが用いられること
となる。In the present invention, the cathode used is a metal constituting the target terbium alloy, such as iron, cobalt, or a metal that can be easily alloyed, such as copper, nickel, manganese, chromium, or titanium. It will be.
また、かくの如き本発明手法にあっては、前記溶融塩電
解浴は、例えばテルビウム−鉄合金電解の場合には８６
０〜１０００℃の温度に、またテルビウム−コバルト合
金電解の場合には７１０〜１０００℃の温度に保持され
、この温度下において前記電解還元操作が進行せしめら
れることが望ましく、またその電解還元操作においては
、陽極電流密度：０．０５〜１０．０Ａ／ｃＪ、陰極電
流密度：０．５０〜８０Ａ／ｃｊの条件が好適に採用さ
れることとなる。In addition, in such a method of the present invention, the molten salt electrolytic bath is, for example, 86°C in the case of terbium-iron alloy electrolysis.
It is desirable that the electrolytic reduction operation be carried out at a temperature of 0 to 1000°C, or 710 to 1000°C in the case of terbium-cobalt alloy electrolysis, and in the electrolytic reduction operation. The conditions of anode current density: 0.05 to 10.0 A/cJ and cathode current density: 0.50 to 80 A/cj are preferably adopted.
さらに、前記電解還元操作の実施される前記フフ化物原
料を含む溶融塩電解浴は、それが実質的にフッ化テルビ
ウムとフッ化リチウムの二元系にて構成される場合にあ
っては、該フッ化テルビウムが少なくとも２５重量％以
上、且つ該フッ化リチウムが少なくとも１５重量％以上
の割合で電解浴中に存在するように調整せしめられるこ
とが望ましいのである。Furthermore, if the molten salt electrolytic bath containing the fluoride raw material in which the electrolytic reduction operation is carried out is substantially composed of a binary system of terbium fluoride and lithium fluoride, It is desirable that the proportion of terbium fluoride is at least 25% by weight and the lithium fluoride is present in the electrolytic bath in a proportion of at least 15% by weight.
また、かかる本発明を実施するに際しては、（ａ）実質
的に、フッ化テルビウム及びフッ化リチウム、並びに必
要に応じて添加されたフッ化バリウム、フッ化カルシウ
ムからなる溶融塩電解浴を収容する、耐火性材料から構
成された電解槽と、（ｂ）該電解槽の内面の接浴部に施
されたライニングと、（Ｃ）該電解槽の溶融塩電解浴中
に挿入、浸漬される、実質的に長さ方向に形状の変化の
ない長手の炭素陽極と、（ｄ）該電解槽の溶融塩電解浴
中に挿入、浸漬される、実質的に長さ方向に形状の変化
のない、テルビウムと合金化し得る金属からなる長手の
陰極と、（ｅ）開口部が、該陰極の下方に位置するよう
に、前記電解槽の溶融塩電解浴中に配置せしめられて、
前記炭素陽極と陰極との間に印加される直流電流による
フッ化テルビウムの電解還元によって該陰極上に生じる
テルビウム合金の液滴が滴下せしめられる、生成合金液
滴を集めるための合金受器と、（「）該合金受器内の液
体状態のテルビウム合金を電解槽外に取り出すための液
状合金取出手段と、（ｇ）前記陰極を、前記テルビウム
合金の生成に伴なうその消耗に従って、前記電解槽の溶
融塩電解浴中に所定の電流密度が得られるように挿入す
るための陰極挿入手段とを、含む装置が好適に用いられ
る。In carrying out the present invention, (a) a molten salt electrolytic bath consisting essentially of terbium fluoride and lithium fluoride, and barium fluoride and calcium fluoride added as necessary; , an electrolytic cell made of a refractory material, (b) a lining applied to the inner surface of the electrolytic cell in contact with the bath, and (C) inserted and immersed in the molten salt electrolytic bath of the electrolytic cell. (d) a longitudinal carbon anode with substantially no change in shape in the longitudinal direction; an elongate cathode made of a metal that can be alloyed with terbium; and (e) positioned in the molten salt electrolytic bath of the electrolytic cell so that the opening is located below the cathode;
an alloy receiver for collecting produced alloy droplets, into which droplets of terbium alloy produced on the cathode are dropped by electrolytic reduction of terbium fluoride by a direct current applied between the carbon anode and the cathode; (“) a liquid alloy extraction means for extracting the terbium alloy in a liquid state in the alloy receiver to the outside of the electrolytic cell; Preferably, an apparatus is used which includes a cathode insertion means for insertion into the molten salt electrolytic bath of the bath so as to obtain a predetermined current density.
尤も、このようなテルビウム合金の製造装置は、更に、
前記炭素陽極を前記電解槽の溶融塩電解浴中に所定の電
流密度が得られるように挿入するための陽極挿入手段や
、原料としてのフッ化テルビウムを前記電解槽内に供給
するための原料供給手段を備えていることが望ましく、
また前記電解槽の内面に施されるライニングとしては、
モリブデン、タングステン等の難融金属材料に代えで、
安価な鉄材料が好適に用いられることとなる。Of course, such a terbium alloy manufacturing device furthermore
Anode insertion means for inserting the carbon anode into the molten salt electrolytic bath of the electrolytic cell so as to obtain a predetermined current density, and a raw material supply for supplying terbium fluoride as a raw material into the electrolytic cell. It is desirable to have the means to
In addition, the lining applied to the inner surface of the electrolytic cell includes:
Instead of refractory metal materials such as molybdenum and tungsten,
An inexpensive iron material will be suitably used.
また、本発明にあっては、電解槽内に配置された合金受
器中に集められた液体状態のテルビウム合金を、液体状
態のままにおいて電解槽外に効果的に取り出すために、
前記液状合金取出手段が該合金受器内の液状の生成合金
中に挿入されるパイプ状ノズルを有するように構成され
、該ノズルを通じて、真空吸引作用により該生成合金を
吸い上げて、電解槽外に取り出すようにすることが、工
業的な実施の観点から有利に採用されることとなる。Further, in the present invention, in order to effectively take out the liquid state of the terbium alloy collected in the alloy receiver placed in the electrolytic cell out of the electrolytic cell while keeping it in the liquid state,
The liquid alloy extraction means is configured to have a pipe-shaped nozzle that is inserted into the liquid produced alloy in the alloy receiver, and through the nozzle sucks up the produced alloy by vacuum suction to the outside of the electrolytic cell. It is advantageous to take it out from the viewpoint of industrial implementation.
（構成の具体的な説明）
まず、第１図には、本発明を実施するための電解システ
ムの模式図が示されているが、そこにおいて、その電解
システムの主要部をなす電解槽２へは、溶融塩電解浴を
構成する溶剤４が装入せしめられるようになっている。(Specific explanation of the configuration) First, FIG. 1 shows a schematic diagram of an electrolytic system for carrying out the present invention. is adapted to be charged with a solvent 4 constituting a molten salt electrolytic bath.
そして、この溶剤４としては、フッ化テルビウム（Ｔｂ
Ｆｆｆ）とフッ化リチウム（Ｌ ｉ Ｆ）が用いられる
が、これらに加えて、フッ化バリウム（ＢａＦｚ）並び
にフッ化カルシウム（ＣａＦｚ）を単独で或いは両者同
時に添加して用いることも可能である。一方、電解原料
は、原料供給装置６より電解槽２内の電解浴中に供給さ
れることとなるが、本発明では、この原料として、酸化
テルビウム（Ｔｂ４０７）ではなくて、電解浴の構成成
分の一つでもあるフッ化テルビウムが使用されるのであ
る。As this solvent 4, terbium fluoride (Tb
Fff) and lithium fluoride (L i F) are used, but in addition to these, barium fluoride (BaFz) and calcium fluoride (CaFz) can be used alone or in combination. On the other hand, the electrolytic raw material is supplied from the raw material supply device 6 into the electrolytic bath in the electrolytic cell 2, but in the present invention, this raw material is not terbium oxide (Tb407), but is a component of the electrolytic bath. Terbium fluoride, which is also one of the
また、電解槽２内の電解浴中へは、炭素陽極８と鉄、コ
バルト等の合金化金属からなる陰極１０とがそれぞれ浸
漬せしめられて、それら陽極８と陰極１０の間に直流の
電力１２が印加せしめられることにより、電解浴中のフ
ッ化テルビウムの電解還元が行なわれる。そして、この
電解還元によって陰極１０上に析出した金属テルビウム
は、直ちに陰極１０を構成する鉄或いはコバルト等の金
属と液体状態の合金を生成せしめ、陰極１０表面より滴
下して、電解槽２内の電解浴中に設置した受器に溜るよ
うになる。なお、上記所定の溶剤組成のものが溶融する
温度では、陰極１０上に生成する合金は液体状態となる
ものであり、またそのような溶融塩からなる電解浴の比
重は、生成合金のそれよりも小さくされているところか
ら、かかる液体状の合金が陰極１０上に生成されるに従
って、それは陰極１０表面より下方に落下するようにな
る。Further, a carbon anode 8 and a cathode 10 made of an alloyed metal such as iron or cobalt are respectively immersed in the electrolytic bath in the electrolytic bath 2, and between the anode 8 and the cathode 10, a DC power 12 is provided. By applying , the terbium fluoride in the electrolytic bath is electrolytically reduced. The metal terbium deposited on the cathode 10 by this electrolytic reduction immediately forms a liquid alloy with metals such as iron or cobalt constituting the cathode 10, drips from the surface of the cathode 10, and enters the electrolytic cell 2. It will accumulate in a receiver placed in the electrolytic bath. Note that at the temperature at which the above-mentioned predetermined solvent composition melts, the alloy formed on the cathode 10 is in a liquid state, and the specific gravity of the electrolytic bath made of such a molten salt is lower than that of the formed alloy. Since the liquid alloy is also made smaller, as the liquid alloy is formed on the cathode 10, it falls below the surface of the cathode 10.
従って、陰極１０から落下する液体合金を受ける、該陰
極１０の下方に位置する開口部を有する受器内に溜めら
れた液体合金は、更に適当な合金取出手段１４によって
電解槽２外へ取り出され、回収されることとなるのであ
る。Therefore, the liquid alloy collected in a receiver having an opening located below the cathode 10, which receives the liquid alloy falling from the cathode 10, is further taken out to the outside of the electrolytic cell 2 by a suitable alloy removal means 14. , and will be collected.
なお、電解槽２へは、電解浴、生成合金、電極（陽極８
と陰極１０）、電解槽の構成材料等の変質を防ぎ、生成
合金への有害不純物や介在物の混入を避けること等のた
めに、保護ガス１６が導入される。また、電解還元操作
にて電解槽２内に発生したガスは、導入された保護ガス
と共に廃ガス処理装置１８に導かれ、所定の処理が施さ
れるようになっている。In addition, the electrolytic bath, the produced alloy, and the electrode (anode 8
A protective gas 16 is introduced in order to prevent deterioration of the cathode 10), the constituent materials of the electrolytic cell, etc., and to avoid the mixing of harmful impurities and inclusions into the produced alloy. Further, the gas generated in the electrolytic cell 2 during the electrolytic reduction operation is led to the waste gas treatment device 18 together with the introduced protective gas, and is subjected to a predetermined treatment.
ところで、かくの如き本発明に従う電解システムにおい
ては、上述のように、電解原料として、酸化テルビウム
とは異なり、フッ化テルビウムが使用される。このフッ
化テルビウムを原料とする場合においては、フッ化テル
ビウム自体が電解浴の主要構成成分でもあるところから
、電解によってそれが消費される分を供給によって補う
ことが容易であり、且つ酸化物電解の場合に比較して電
解浴の遥かに広い原料濃度範囲で電解を継続することが
できるのである。By the way, in the electrolytic system according to the present invention, as described above, terbium fluoride, unlike terbium oxide, is used as the electrolytic raw material. When using terbium fluoride as a raw material, since terbium fluoride itself is the main component of the electrolytic bath, it is easy to supplement the amount consumed by electrolysis by supplying terbium fluoride. Electrolysis can be continued over a much wider range of raw material concentration in the electrolytic bath than in the case of .
なお、この原料フッ化テルビウムの供給方法としては、
粉末の状態で電解浴の表面に添加するのが一般的であり
、電解浴への溶解速度も速く、好ましいが、電解浴内に
ガスと共に導入する方法、或いは粉末の成形体を電解浴
中に浸漬する方法でも、行なうことが可能である。The method for supplying this raw material terbium fluoride is as follows:
Generally, it is added to the surface of the electrolytic bath in the form of a powder, which is preferable because it dissolves quickly into the electrolytic bath. It is also possible to carry out the method by dipping.
また、酸化テルビウムの電解の場合と比べて、フッ化テ
ルビウムの電解操作においては、電極間の電解領域にお
ける電解原料濃度の許容範囲が血かに大きく、それ故に
供給した原料のかかる領域への移動に多少の遅れがあっ
ても、電解の継続に支障を来すことが少なく、従って原
料フッ化テルビウムの供給位置並びに電解電気量光たり
の供給量に関して、酸化テルビウムを原料とする場合の
ような細かい制約を受けず、より任意に選択を行なうこ
とができる利点を有する。Furthermore, compared to the case of electrolysis of terbium oxide, in the electrolysis of terbium fluoride, the allowable range of the concentration of the electrolytic raw material in the electrolytic region between the electrodes is extremely large, so that the movement of the supplied raw material to this region is extremely large. Even if there is a slight delay in the electrolysis, it will not interfere with the continuation of electrolysis, so the supply position of the raw material terbium fluoride and the amount of electricity supplied for electrolysis should be adjusted to the same level as when terbium oxide is used as the raw material. It has the advantage of being able to make more arbitrary selections without being subject to detailed restrictions.
そして、本発明において、不純物の少ないテルビウム合
金を製造するためには、電解温度の低下が必要であり、
このために、実質的に、２０〜９５％（重量基準。以下
同じ）のフッ化テルビウム、５〜８０％のフッ化リチウ
ム、４０％までのフッ化バリウム、及び２０％までのフ
ッ化カルシウムにて構成される、実質的にフッ化物のみ
よりなる混合溶融塩が電解浴として選ばれ、そしてその
ような電解浴に、上記した原料フッ化テルビウムが添加
された場合にあっても、電解中は常にかかる組成範囲の
電解浴となるように調整されることとなる。In the present invention, in order to produce a terbium alloy with few impurities, it is necessary to lower the electrolysis temperature,
For this purpose, substantially terbium fluoride of 20 to 95% (by weight, the same applies hereinafter), 5 to 80% of lithium fluoride, up to 40% of barium fluoride, and up to 20% of calcium fluoride. A mixed molten salt consisting essentially of only fluoride is selected as the electrolytic bath, and even if the above raw material terbium fluoride is added to such an electrolytic bath, during electrolysis The electrolyte bath will always be adjusted to have such a composition range.
なお、かかる本発明に従う電解浴組成におけるフッ化テ
ルビウム濃度が下限未満、即ち２０％に満たない場合に
は、電解成績が悪化し、またその上限濃度（９５％）を
越えるようになると、電解浴の融点が上がり過ぎる等の
問題を惹起する。また、フッ化リチウムは、その濃度が
余りにも低い場合には電解浴の融点が上がり過ぎ、一方
その濃度が余りにも高い場合には生成合金との反応が激
しくなって、電解成績が悪化する等の問題を惹起するた
め、その濃度としては５〜８０％に調節する必要がある
。Note that if the terbium fluoride concentration in the electrolytic bath composition according to the present invention is less than the lower limit, that is, less than 20%, the electrolytic performance will deteriorate, and if it exceeds the upper limit concentration (95%), the electrolytic bath This causes problems such as the melting point of the material becoming too high. In addition, if the concentration of lithium fluoride is too low, the melting point of the electrolytic bath will rise too much, while if the concentration is too high, the reaction with the formed alloy will be intense, resulting in poor electrolytic results, etc. Since this problem occurs, it is necessary to adjust the concentration to 5 to 80%.
さらに、フッ化バリウムやフッ化カルシウムは、高価な
フッ化リチウムの使用量を減少させ、また形成される混
合溶融塩の溶融温度を調節する等の目的をもって加えら
れるものであり、それらの添加量があまりにも多い場合
には、電解浴の融点が上がり過ぎるところから、前者の
フッ化バリウムは４０％までの割合で、また後者のフッ
化カルシウムは２０％までの割合で、それぞれ単独に或
いは共に用いられることとなる。そして、これら４成分
、即ちフッ化テルビウム、フッ化リチウム、フッ化バリ
ウム及びフッ化カルシウムの合計量が実質的に１００％
となるようにして、電解浴が形成されるのである。Furthermore, barium fluoride and calcium fluoride are added for the purpose of reducing the amount of expensive lithium fluoride used and adjusting the melting temperature of the mixed molten salt that is formed. If there is too much fluoride, the melting point of the electrolytic bath will rise too much, so the former barium fluoride should be used at a proportion of up to 40%, and the latter calcium fluoride at a proportion of up to 20%, each alone or together. It will be used. The total amount of these four components, namely terbium fluoride, lithium fluoride, barium fluoride and calcium fluoride, is substantially 100%.
In this way, an electrolytic bath is formed.
尤も、このような電解浴組成に関して、かかる電解浴が
フッ化テルビウムとフッ化リチウムの二つの成分のみに
て構成される二元系の場合においては、フッ化テルビウ
ムは電解浴中において少なくとも２５％以上、フッ化リ
チウムは少なくとも１５％以上、それぞれ存在するよう
に調整されることが望ましい。なお、電解浴の組成は、
生成せしめられるテルビウム−鉄合金、テルビウム−コ
バルト合金等の生成合金の比重より小さな比重を電解浴
が有するように選ばれるものであるところから、電解時
には、生成されたテルビウム−鉄合金、テルビウム−コ
バルト合金等のテルビウム合金が、陰極より比重差によ
って電解浴中を落下し、陰極の下方に位置する開口部を
有する生成合金の受器に容易に到達し得るのである。However, regarding such an electrolytic bath composition, if such an electrolytic bath is a binary system consisting of only two components, terbium fluoride and lithium fluoride, terbium fluoride should account for at least 25% of the electrolytic bath. As mentioned above, it is desirable that lithium fluoride is adjusted to be present in an amount of at least 15% or more. The composition of the electrolytic bath is
Since the electrolytic bath is selected to have a specific gravity smaller than the specific gravity of the produced alloy such as terbium-iron alloy or terbium-cobalt alloy, during electrolysis, the produced terbium-iron alloy or terbium-cobalt alloy is The terbium alloy, such as the alloy, falls from the cathode into the electrolytic bath due to the difference in specific gravity and can easily reach the resulting alloy receiver having an opening located below the cathode.
また、本発明にあっては、かくの如き組成の電解浴の電
解時の温度は、生成するテルビウム合金の種類によって
適宜に選択され、例えばテルビウム−鉄合金電解では８
６０℃〜１０００℃、テルビウム−コバルト合金電解で
は７１０℃〜１０００℃の範囲に調節せしめられること
となる。前述したように、電解浴温度が余りにも高くな
り過ぎると、生成合金への不純物、介在物の混入がみら
れ、一方余りにも低い電解浴温度の場合にあっては、例
えばテルビウム−鉄合金電解では、テルビウム−鉄二元
系合金の共晶温度が約８５０℃と推定されるところから
、析出する金属テルビウムと陰極の鉄が充分に合金化せ
ず、高融点の固体状の金属テルビウムの析出により、陰
極−陽極間の短絡現象が生起して、電解を継続すること
が困難となるからである。一方、テルビウム−コバルト
合金電解では、余りにも低い電解浴温度の場合にあって
は、均質な溶融塩電解浴を形成することが困難となり、
電解浴の性状が悪化し、電解をｗＥ続することが困難と
なるからである。この温度の範囲内で、出来るだけ低温
の方が、炉材等からの不純物の混入の少ないテルビウム
−鉄、テルビウム−コバルト等の母合金の製造が可能で
あることは言うまでもない。In addition, in the present invention, the temperature during electrolysis of the electrolytic bath having such a composition is appropriately selected depending on the type of terbium alloy to be produced. For example, in the case of terbium-iron alloy electrolysis,
In the case of terbium-cobalt alloy electrolysis, it is adjusted to a range of 60°C to 1000°C, and 710°C to 1000°C. As mentioned above, if the electrolytic bath temperature is too high, impurities and inclusions will be mixed into the produced alloy, while if the electrolytic bath temperature is too low, for example, terbium-iron alloy electrolysis will occur. Since the eutectic temperature of the terbium-iron binary alloy is estimated to be approximately 850°C, the precipitated metal terbium and the cathode iron are not sufficiently alloyed, and the solid metal terbium with a high melting point is precipitated. This is because a short circuit phenomenon occurs between the cathode and the anode, making it difficult to continue electrolysis. On the other hand, in terbium-cobalt alloy electrolysis, if the electrolytic bath temperature is too low, it becomes difficult to form a homogeneous molten salt electrolytic bath.
This is because the properties of the electrolytic bath deteriorate and it becomes difficult to continue electrolysis. It goes without saying that within this temperature range, it is possible to produce master alloys such as terbium-iron and terbium-cobalt with less contamination of impurities from furnace materials etc. at the lowest possible temperature.
そして、かかる温度範囲では、テルビウムを８０重量％
以上含む、高テルビウム濃度のテルビウム−鉄合金、テ
ルビウム−コバルト合金等のテルビウム合金が有利に生
成せしめられ得るのであり、またその生成合金はこの温
度範囲において受器内で液層を形成し、液体状態での取
出しに適しているのである。そして、この受器内の液状
合金は、電解槽上部より、真空吸引方式によって効果的
に取り出すことができる他、下方より流し出し方式によ
って取り出すことも可能である。しかも、この取出に際
しては、受器内の合金を特別に加熱する必要もなく、極
めて容易に液状合金として電解槽外に取り出すことがで
きるのである。In this temperature range, 80% by weight of terbium
Terbium alloys such as terbium-iron alloys and terbium-cobalt alloys containing high terbium concentrations can be advantageously produced, and the produced alloys form a liquid layer in the receiver in this temperature range and become liquid. It is suitable for taking out in a state. The liquid alloy in this receiver can be effectively taken out from the upper part of the electrolytic cell by a vacuum suction method, and can also be taken out from below by a pouring method. Furthermore, when taking out the alloy, there is no need to specially heat the alloy in the receiver, and the alloy can be taken out of the electrolytic cell very easily as a liquid alloy.
また、本発明にあっては、電解用電極として、陰極に鉄
或いはコバルト等の容易に合金化し得る金属、陽極に炭
素、特に黒鉛が好適に用いられる。Further, in the present invention, as the electrode for electrolysis, a metal that can be easily alloyed such as iron or cobalt is preferably used for the cathode, and carbon, particularly graphite, is preferably used for the anode.
陰極の鉄、コバルト等の金属は、不純物を含むと、その
まま生成合金中に不純物を持ち込むこととなるところか
ら、該陰極の金属材料としては、必要に応じて不純物の
少ないものを用いることが好ましい。また、本発明に従
えば、電解操作の進行につれて、陰極を構成する鉄、コ
バルト等の合金化金属は、テルビウム−鉄合金、テルビ
ウム−コバルト合金等の、目的とするテルビウム合金を
生成して、消費されることとなるが、かかる電解によっ
て消耗する部分の鉄、コバルト等の金属を補って、順次
、陰極を電解浴中に浸漬するようにすれば、電解操作を
中断することなく、目的とするテルビウム合金を連続的
に製造することができるのである。その際、陰極の金属
部材の端部にネジ切り加工等を行なっておいて、ネジ結
合等によって陰極を構成する金属部材を順次接続せしめ
、消耗した陰極分を補うことは、勿論可能である。If a metal such as iron or cobalt for the cathode contains impurities, the impurities will be directly introduced into the formed alloy, so it is preferable to use a metal material with low impurities as necessary as the metal material for the cathode. . Further, according to the present invention, as the electrolytic operation progresses, the alloyed metal such as iron and cobalt constituting the cathode produces the desired terbium alloy such as terbium-iron alloy, terbium-cobalt alloy, etc. However, if the metals such as iron and cobalt that are consumed by such electrolysis are replenished and the cathode is sequentially immersed in the electrolytic bath, the intended purpose can be achieved without interrupting the electrolytic operation. This makes it possible to continuously produce terbium alloys. At this time, it is of course possible to perform thread cutting or the like on the end of the metal member of the cathode, and then connect the metal members constituting the cathode one after another by screw connection or the like to compensate for the consumed cathode portion.
このように、固体の合金化金属が陰極として使用できる
ことは、溶融金属を陰極として使用する場合に比して、
取扱が容易であり、且つ電解炉を装置的にみて簡略化し
得る点で大きな利点となるものである。Thus, the ability to use solid alloyed metals as cathodes, compared to the use of molten metals as cathodes,
This is a major advantage in that it is easy to handle and the electrolytic furnace can be simplified in terms of equipment.
さらに、かかる本発明に従う炭素陽極を用いるフッ化テ
ルビウムの電解にあっては、陽極全表面にわたっての電
流密度を、０．０５〜１０．０ Ａ ／ ｃＡの範囲内
に、電解操作中学に維持していることが望ましい。けだ
し、この電流密度が低過ぎる場合には、陽極表面積が大
き過ぎるか、陽極単（丸表面積当たりの電流が小さ過ぎ
ることとなり、このために生産性が悪化し、工業的に有
利ではなくなるからであり、またかかる電流密度が高く
なり過ぎると、酸化テルビウムを原料とした場合の陽極
効果乃至はこれと類似の異常現象が発生し易くなるから
である。従って、本発明にあっては、電解条件の一つと
しての陽極電流密度を上記の範囲に保つことによって、
そのような異常現象の発生を効果的に回避することが、
推奨されるのである。なお、陽極表面における局部的な
変動を考慮に入れると、上記陽極全表面にわたっての電
流密度は、０．１〜８．０ Ａ ／ ｃｔ／＋の間に保
持することがより好ましい。さらに、フッ化テルビウム
を原料とした場合は酸化テルビウムを原料にした時より
も、同一温度では、アノード電流密度を太き（とること
ができ、実操業の点から好ましい。Furthermore, in the electrolysis of terbium fluoride using the carbon anode according to the present invention, the current density over the entire surface of the anode is maintained within the range of 0.05 to 10.0 A/cA during electrolytic operation. It is desirable that However, if this current density is too low, the anode surface area will be too large or the current per anode single surface area will be too small, resulting in poor productivity and no industrial advantage. Moreover, if the current density becomes too high, an anode effect or similar abnormal phenomena will easily occur when terbium oxide is used as a raw material.Therefore, in the present invention, the electrolytic conditions are By keeping the anode current density as one of the above ranges,
To effectively avoid the occurrence of such abnormal phenomena,
It is recommended. Note that, taking into account local fluctuations on the anode surface, it is more preferable to maintain the current density over the entire surface of the anode between 0.1 and 8.0 A/ct/+. Furthermore, when terbium fluoride is used as a raw material, the anode current density can be made thicker at the same temperature than when terbium oxide is used as a raw material, which is preferable from the point of view of actual operation.
一方、陰極の電流密度は、陰極全表面にわたっての電流
密度として０．５０〜８０Ａ／ｃｎｌの広い範囲にわた
って許容される。しかし、陰極電流密度が余りにも低過
ぎると、陰極単位表面積光たりの電流が小さ過ぎて、生
産性が悪化し、工業的ではなくなる。また、この陰極電
流密度が高くなり過ぎると、電解電圧の上昇が甚だしく
なり、電解成績を悪化させる。なお、実際の電解操業の
継続に当たっては、更に１．０〜３０ Ａ ／ ｃｎｌ
のより狭い陰極電流密度の範囲に保つことが、電解電圧
の変動幅を狭く維持し、電解操業を容易にする上におい
て、より好ましいと言える。On the other hand, the current density of the cathode is allowed over a wide range of 0.50 to 80 A/cnl as the current density over the entire surface of the cathode. However, if the cathode current density is too low, the current per unit surface area of the cathode will be too small, resulting in poor productivity and not being industrially viable. Furthermore, if this cathode current density becomes too high, the electrolytic voltage will increase significantly and the electrolytic results will deteriorate. In addition, for continuation of actual electrolytic operation, an additional 1.0 to 30 A/cnl
It can be said that it is more preferable to maintain the cathode current density within a narrower range of , in order to maintain a narrow variation range of electrolysis voltage and facilitate electrolysis operation.
さらに、本発明に従えば、電解浴の耐浴材とは別の炭素
を陽極として使用するものであるところから、電解浴の
耐浴容器（耐浴材）と陽極を兼用する場合とは異なり、
陽極の消耗によって電解を終了せしめる必要はなく、た
だその消耗分を補って、更に陽極を電解浴中に浸漬する
か、或いは複数の陽極を使用するので、順次新しい陽極
に交換するだけで良い。また、陰極も同様に、その消耗
分を補って電解浴中に浸漬するか、或いは新しい陰極に
交換するだけで良いのである。本発明では、好適に採用
される陽極と陰極の表面電流密度の比の大きな違いによ
り、各陰極の周りに複数本の陽極を配置して、陽極が陰
極と対向するようにした電極配列が好適に採用されるこ
ととなるが、そのような場合において、陽極の交換を順
次行なうようにすれば、実質上、電解操業を中断するこ
となく、テルビウム合金を連続的に製造することができ
、電解法の利点を充分に生かすことができる。Furthermore, according to the present invention, carbon, which is different from the bath-resistant material of the electrolytic bath, is used as the anode, unlike the case where the bath-resistant container (bath-resistant material) of the electrolytic bath also serves as the anode. ,
There is no need to terminate the electrolysis due to consumption of the anode; it is only necessary to compensate for the consumption and further immerse the anode in the electrolytic bath, or, since a plurality of anodes are used, to replace them with new anodes one by one. Similarly, the cathode only needs to be immersed in an electrolytic bath to compensate for its consumption, or replaced with a new cathode. In the present invention, due to the large difference in the surface current density ratio between the anode and cathode, it is preferable to use an electrode arrangement in which a plurality of anodes are arranged around each cathode so that the anode faces the cathode. In such cases, if the anodes are replaced sequentially, terbium alloy can be produced continuously without interrupting the electrolytic operation. You can take full advantage of the benefits of the law.
しかも、陽極形状、陰極形状とも、外形上は実質的に長
さ方向には変化がないものを用いることができるところ
から、それらの連続的な使用において何等の不都合が惹
起されることもないのである。Moreover, since both the anode shape and the cathode shape can be used with an external shape that does not substantially change in the length direction, there will be no inconvenience caused in their continuous use. be.
また、本発明を実施する電解槽の構造の好適な一例が、
第２図に模式的に示されている。Further, a preferred example of the structure of an electrolytic cell for carrying out the present invention is
It is schematically shown in FIG.
かかる第２図において、電解槽２０は、下部槽２２とそ
の開口部を覆蓋する蓋体２４にて構成されている。また
、これら下部槽２２及び蓋体２４の外側は、通常、鋼等
の金属よりなる槽外枠２６゜２８より構成されている。In FIG. 2, the electrolytic cell 20 is composed of a lower tank 22 and a lid 24 that covers the opening thereof. The outer sides of the lower tank 22 and the lid body 24 are usually constructed of tank outer frames 26 and 28 made of metal such as steel.
さらに、下部槽２２及び蓋体２４は、それぞれ外側にレ
ンガやキャスタブル・アルミナ等よりなる耐火断熱材層
３０，３２、及び内側に黒鉛、炭素質スタンプ材等から
なる耐浴材層３４．３６を配置して、構成されている。Further, the lower tank 22 and the lid body 24 each have fire-resistant insulation layers 30 and 32 made of brick, castable alumina, etc. on the outside, and bath-resistant material layers 34 and 36 made of graphite, carbonaceous stamp material, etc. on the inside. Arranged and configured.
そして、下部槽２２の内側耐浴材層３４の内面の接浴面
には、ライニング材３８が設けられて、かかる接浴面を
被覆している。このライニング材３８は、耐浴材層３４
からの不純物の混入を防ぐ他、それがタングステンやモ
リブデン等の難融金属にて形成されている場合には、生
成する液状テルビウム−鉄合金、テルビウム−コバルト
合金等のテルビウム合金の受器を兼ねることもできる。A lining material 38 is provided on the inner bath-contact surface of the inner bath-resistant material layer 34 of the lower tank 22 to cover the bath-contact surface. This lining material 38 is a bath-resistant material layer 34.
In addition to preventing the contamination of impurities from metals such as tungsten or molybdenum, if the metal is made of refractory metals such as tungsten or molybdenum, it also serves as a receiver for the liquid terbium alloys such as terbium-iron alloys and terbium-cobalt alloys that are formed. You can also do that.
尤も、本発明にあっては、かかるライニング材３８とし
て、難融金属より安価な鉄材料を用いることが推奨され
る。また、耐浴材層３４は、必ずしも必要ではなく、耐
火断熱材層３０上に直接にライニング材３８を適用して
も何等差支えない。However, in the present invention, it is recommended to use iron material, which is cheaper than refractory metal, as the lining material 38. Further, the bath-resistant material layer 34 is not necessarily required, and there is no problem in applying the lining material 38 directly on the fire-resistant heat insulating material layer 30.
また、蓋体２４を貫通するように、１本若しくは複数本
の、鉄、コバルト、銅、ニッケル、マンガン、クロム、
チタン等の容易に合金化し得る金属からなる陰極４０と
、この陰極４０に対向して配置された複数本の炭素陽極
４２が設けられており、またそれら両電極４０．４２は
、下部槽２２内に収容される前記所定の溶融塩からなる
電解浴４４中に、所定電流密度となる長さにわたって浸
漬されるようになっている。なお、ここでは、炭素陽極
４２．４２は、陰極４０と向かい合って配置される陽極
のうちの２本が示されており、それらの材質としては黒
鉛が好適に用いられることとなる。Moreover, one or more iron, cobalt, copper, nickel, manganese, chromium,
A cathode 40 made of a metal that can be easily alloyed such as titanium, and a plurality of carbon anodes 42 arranged opposite to this cathode 40 are provided. The electrode is immersed in an electrolytic bath 44 made of the predetermined molten salt housed in the electrolyte bath 44 over a length that provides a predetermined current density. Here, two carbon anodes 42, 42 are shown among the anodes disposed facing the cathode 40, and graphite is suitably used as the material for them.
さらに、これら炭素陽極４２．４２は、・棒状、板状、
管状等の形態で用いられ、電解浴４４への浸漬部分の陽
極表面積を大きくして陽極電流密度を下げるために、公
知のように溝付きとすることもできる。なお、第２図で
は、炭素陽極４２には、電解による陽極消耗の跡を示し
て、陽極浸漬部に僅かに傾斜が付けられている。この陽
極４２には、給電のために金属等の適当な導電体の電気
リードが取り付けられていても、何等差支えない。また
、陽極４２は、陽極挿入手段としての陽極昇降機構４６
によって上下動せしめられ得るようになっており、これ
により電解ｍ続のための適切な陽極電流密度が確保され
るように、間欠的に或いは連続的に、その浸漬部の表面
積を浸漬深さで調整し得るようになっている。なお、陽
極昇降機構４６゜４６は、陽極への電気接続機能を兼ね
備えることも出来る。Furthermore, these carbon anodes 42.42 are rod-shaped, plate-shaped,
It is used in a tubular shape or the like, and may be grooved as is known in the art in order to increase the anode surface area of the part immersed in the electrolytic bath 44 and lower the anode current density. In addition, in FIG. 2, the carbon anode 42 has a slight slope at the anode immersion part, showing traces of anode wear due to electrolysis. There is no problem even if an electric lead made of a suitable conductor such as metal is attached to the anode 42 for power supply. Further, the anode 42 is connected to an anode lifting mechanism 46 as an anode insertion means.
The surface area of the immersion part can be moved up and down by the immersion depth, either intermittently or continuously, so as to ensure a suitable anodic current density for the electrolytic series. It is adjustable. Note that the anode lifting/lowering mechanism 46° 46 can also have the function of electrically connecting to the anode.
一方、陰極４０は、電解還元作用にて析出せしめられる
金属テルビウムと合金化させるべき鉄、コバルト等の金
属にて構成されており、ここではその１本が示されてい
る。また、第２図では、テルビウム合金の液滴生成によ
る陰極消耗の跡を示して、陰極浸漬部分が円錐形状で示
しである。なお、電解温度は、陰極４０の金属材料の融
点以下に選ばれるところから、この陰極４０は固体であ
り、線状、棒状、板状、管状等の形態で用いられる。こ
の陰極４０は、また、陰極挿入手段としての陰極昇降機
構４８によって、合金生成による消耗骨を補って、電解
浴４４中へ連続的或いは間欠的に送り込まれるようにな
っている。そして、この陰極昇降機構４８は、陰極への
電気接続機能を兼ね備えることもできる。さらに、かか
る陰極４０の浸漬部以外の表面が、防食のために適当な
保護スリーブ等で保護せしめられるようにしても、何等
差支えない。On the other hand, the cathode 40 is made of a metal such as iron or cobalt to be alloyed with the metal terbium deposited by electrolytic reduction, one of which is shown here. Further, in FIG. 2, the cathode immersion portion is shown in a conical shape, showing traces of cathode consumption due to the formation of droplets of terbium alloy. Since the electrolysis temperature is selected to be below the melting point of the metal material of the cathode 40, the cathode 40 is solid and is used in the form of a wire, rod, plate, tube, or the like. The cathode 40 is also continuously or intermittently fed into the electrolytic bath 44 by a cathode lifting mechanism 48 serving as a cathode insertion means to compensate for bone loss due to alloy formation. The cathode lifting mechanism 48 can also have the function of electrically connecting to the cathode. Furthermore, there is no problem if the surface of the cathode 40 other than the immersed part is protected with a suitable protective sleeve or the like for corrosion prevention.
また、かかる陰極４０の下方に受器開口部が位置するよ
うに、電解浴４４内において、下部槽２２の底部上に生
成合金受器５０が配置せしめられており、電解還元操作
によって陰極４ｏ上に生成された液状のテルビウム−鉄
合金、テルビウム−コバルト合金等のテルビウム合金５
２は、陰極表面より滴下して、その直下において開口す
る生成合金受器５０内に溜められる。なお、この生成合
金受器５０は、生成合金５２との反応性の小さな難融金
属、例えばタングステン、タンタル、モリブデン、ニオ
ブ、或いはそれらの合金等を用いて形成される他、窒化
ホウ素等のホウ化物や酸化物等のセラミックス、或いは
サーメット等の材料を用いて形成することもできる。Further, in the electrolytic bath 44, a produced alloy receiver 50 is arranged on the bottom of the lower tank 22 so that the receiver opening is located below the cathode 40, and the produced alloy receiver 50 is placed on the cathode 4o by the electrolytic reduction operation. Terbium alloys such as liquid terbium-iron alloys and terbium-cobalt alloys produced in
2 drips from the surface of the cathode and is collected in the produced alloy receiver 50 which opens directly below it. The produced alloy receiver 50 is formed using a refractory metal that has low reactivity with the produced alloy 52, such as tungsten, tantalum, molybdenum, niobium, or an alloy thereof, or a boron such as boron nitride. It can also be formed using materials such as ceramics such as compounds and oxides, or cermets.
なお、電解浴４４は、前記した本発明に従う組成に調整
された、フッ化テルビウムを含有するフッ化物混合溶融
塩よりなるものであり、その組成は、その比重が生成さ
れるテルビウム合金の比重以下となるように選ばれる。The electrolytic bath 44 is made of a fluoride mixed molten salt containing terbium fluoride, which is adjusted to have a composition according to the present invention described above, and whose specific gravity is lower than the specific gravity of the terbium alloy to be produced. is selected so that
そして、電解によって消費される電解原料は、原料供給
装置５４から蓋体２４に設けられた原料供給孔５６を通
じて供給され、所定組成の電解浴４４が維持せしめられ
るようになっている。The electrolytic raw material consumed by electrolysis is supplied from a raw material supply device 54 through a raw material supply hole 56 provided in the lid 24, so that the electrolytic bath 44 of a predetermined composition is maintained.
また、陰極４０から滴下して受器５０内に溜められた生
成合金５２は、それが所定量溜まった時に、液体状態の
ままで所定の合金回収機構（取出手段）によって電解槽
２０外に取り出されることとなるが、本発明にあっては
、第２図に示される如く、パイプ状の真空吸引ノズル５
８を、蓋体２４に設けられた生成合金吸引孔６０を通じ
て電解浴４４内に差し入れ、該ノズル５８の先端を生成
合金受器５０内の生成合金５２中に浸漬せしめ、図示さ
れていない真空装置の真空吸引作用を利用して吸引する
ことにより生成合金５２を吸い上げて電解槽２０外に取
り出す手段が、有利に採用されることとなる。Furthermore, when a predetermined amount of generated alloy 52 drips from the cathode 40 and accumulates in the receiver 50, it is taken out of the electrolytic cell 20 in a liquid state by a predetermined alloy recovery mechanism (retrieval means). However, in the present invention, as shown in FIG.
8 is inserted into the electrolytic bath 44 through the produced alloy suction hole 60 provided in the lid body 24, and the tip of the nozzle 58 is immersed in the produced alloy 52 in the produced alloy receiver 50. Advantageously, a means for sucking up the generated alloy 52 and taking it out of the electrolytic cell 20 by suction using the vacuum suction effect of the electrolytic cell 20 is advantageously employed.
尤も、このような真空吸引による生成合金５２の吸引取
出し方式に代えて、電解槽２０（下部槽２２）の下部を
貫通する取出パイプを設け、この取出パイプの先端を更
に生成合金受器５０を貫通させて、該受器５０内に開口
せしめることにより、かかる取出パイプを通じて、生成
合金５２を炉外下方に流し出す合金回収機構を採用する
ことも可能である。However, instead of using such a vacuum suction method to take out the produced alloy 52, an extraction pipe is provided that penetrates the lower part of the electrolytic cell 20 (lower tank 22), and the tip of this extraction pipe is further connected to the produced alloy receiver 50. It is also possible to adopt an alloy recovery mechanism in which the formed alloy 52 is flowed out of the furnace and downward through the take-out pipe by penetrating the pipe and opening into the receiver 50.
なお、図示はされていないが、かかる電解炉２０内には
、保護ガスが供給されるようになっており、また電解操
作によって発生するガスは、かかる保護ガスと共に、廃
ガス出口６２を通じて外部に排出されるようになってい
る。また、このような電解槽２０には、前記した電解温
度に保持するための特別な加熱装置は設けられていない
が、所定の温度に維持するために、必要に応じて、この
電解槽２０内に或いはその外部に適当な加熱装置を設け
てもよいことは、言うまでもないところである。Although not shown, a protective gas is supplied into the electrolytic furnace 20, and the gas generated by the electrolytic operation is discharged to the outside through the waste gas outlet 62 together with the protective gas. It is designed to be ejected. Further, although such an electrolytic cell 20 is not provided with a special heating device for maintaining the electrolysis temperature described above, in order to maintain the electrolysis temperature at a predetermined temperature, the inside of this electrolytic cell 20 may be heated as necessary. It goes without saying that a suitable heating device may be provided inside or outside the heating device.
（実施例）
以下、本発明を更に具体的に明らかにするために、本発
明に従う幾つかの実施例を示すが、本発明がそのような
実施例の記載によって同等制限的に解釈されるものでな
いことは、言うまでもないところである。(Examples) In order to clarify the present invention more specifically, some examples according to the present invention will be shown below, but the present invention shall be interpreted in an equivalent and restrictive manner by the description of such examples. It goes without saying that this is not the case.
なお、本発明は、上述した本発明の詳細な説明並びに以
下の実施例の他にも、各種の態様において実施され得る
ものであり、本発明の趣旨を逸脱しない限りにおいて、
当業者の知識に基づいて種々なる態様において実施され
得るものは、何れも本発明の範晴に属するものであるこ
とが、理解されるべきである。It should be noted that the present invention can be implemented in various embodiments in addition to the above-described detailed description of the present invention and the following examples, and as long as they do not depart from the spirit of the present invention,
It should be understood that any of the various embodiments that can be implemented based on the knowledge of those skilled in the art belong to the scope of the present invention.
実施例 １
テルビウムを主とする希土類金属８９％（重量基準。以
下同じ）及び鉄１１’％の組成を有する希土類金属−鉄
（ＲＥ−Ｆｅ）合金０．４９ ｋｇが、次のようにして
得られた。Example 1 0.49 kg of a rare earth metal-iron (RE-Fe) alloy having a composition of 89% rare earth metal (by weight, the same applies hereinafter) mainly consisting of terbium and 11'% iron was obtained as follows. It was done.
すなわち、第２図に示される電解槽と同様な構成の装置
において、電解槽の耐浴材として鉄をライニングした黒
鉛るつぼを用い、生成合金受器として該黒鉛るつぼの底
部中央に設置した窒化ホウ素（Ｂ Ｎ）製容器を用いて
、実質上フッ化テルビウムとフッ化リチウムのみの二元
系フッ化物混合溶融塩よりなる電解浴を、平均９００℃
の電解温度にて不活性ガス雰囲気中で電解した。陰極と
しては、黒鉛るつぼ中央部の電解浴中に浸漬した１本の
６龍φの鉄線を用い、陽極としては、かかる陰極の周り
に同心円状に配列して（平面形態において）電解浴中に
浸漬した、４本の４０龍φの黒鉛棒を用いた。That is, in an apparatus having a configuration similar to the electrolytic cell shown in FIG. 2, a graphite crucible lined with iron is used as the bath-resistant material of the electrolytic cell, and boron nitride is placed at the center of the bottom of the graphite crucible as a receptacle for the produced alloy. Using a container made of (BN), an electrolytic bath consisting of a binary fluoride mixed molten salt consisting essentially of terbium fluoride and lithium fluoride was heated at an average temperature of 900°C.
Electrolysis was carried out in an inert gas atmosphere at an electrolysis temperature of . As the cathode, a single 6-diameter iron wire was immersed in the electrolytic bath at the center of the graphite crucible, and as the anode, the wires were arranged concentrically around the cathode (in planar form) and immersed in the electrolytic bath. Four 40-diameter graphite rods were used.
そして、フッ化テルビウムを原料として、その粉末を電
解浴に連続的に供給しつつ、下記第１表に示される範囲
内の電解条件を保持して、８時間電解を行なった。この
間、電解操業は極めて良好に４１続することができ、液
体状の希土類金属（テルビウム）−鉄合金が順次滴下し
て、電解浴内に配置された窒化ホウ素（ＢＮ）の受器内
に溜められた。この溜められた合金は、真空吸引ノズル
を有する真空吸引式合金回収装置にて電解炉の外部に取
り出された。Using terbium fluoride as a raw material, electrolysis was carried out for 8 hours while continuously supplying the powder to the electrolytic bath and maintaining the electrolytic conditions within the range shown in Table 1 below. During this period, the electrolytic operation continued very well, and the liquid rare earth metal (terbium)-iron alloy was successively dripped and collected in the boron nitride (BN) receiver placed in the electrolytic bath. It was done. This accumulated alloy was taken out of the electrolytic furnace by a vacuum suction type alloy recovery device having a vacuum suction nozzle.
かかる電解操作により得られた電解成績並びに生成合金
の分析結果を、下記第１表及び第２表に示す。なお、電
流効率は、回収した希土類金属重量（すべてテルビウム
と仮定）に基づいて求められた。The electrolytic results obtained by such electrolytic operation and the analysis results of the produced alloy are shown in Tables 1 and 2 below. Note that the current efficiency was determined based on the weight of the rare earth metal recovered (all assumed to be terbium).
実施例 ２
実質的にテルビウムからなる希土類金属８０％及びコバ
ルト２０％の組成を有する希土類金属（テルビウム）−
コバルト合金の０．５８ｋｇが、次のような電解操作に
より得られた。Example 2 A rare earth metal (terbium) having a composition of 80% rare earth metal consisting essentially of terbium and 20% cobalt.
0.58 kg of cobalt alloy was obtained by the following electrolytic operation.
まず、耐浴材としての黒鉛るつぼの内面に鉄をライニン
グしたものを、電解浴の容器として用い、更にこの底部
中央に設置したモリブデン製容器を生成合金の受器とし
て用いて、実質上フッ化テルビウムとフッ化リチウムの
みの二元系フッ化物混合溶融塩よりなる電解浴を、平均
７９０ ’Ｃの電解温度にて不活性ガス雰囲気中で電解
した。そして、陰極としては、実施例１と同様に配置し
た１本の６１脂φのコバルト棒を用い、また陽極として
は、実施例１と同様の４本の４０ｍｍφの黒鉛棒を用い
た。First, a graphite crucible lined with iron as a bath-resistant material was used as a container for the electrolytic bath, and a molybdenum container placed in the center of the bottom of the crucible was used as a receiver for the produced alloy. An electrolytic bath consisting of a binary fluoride mixed molten salt containing only terbium and lithium fluoride was electrolyzed in an inert gas atmosphere at an average electrolysis temperature of 790'C. As the cathode, one cobalt rod with a diameter of 61 mm and arranged in the same manner as in Example 1 was used, and as the anode, the same four graphite rods with a diameter of 40 mm as in Example 1 were used.
そして、フッ化テルビウムを原料として、電解浴に連続
的にその供給を行ないつつ、下記第１表に示される範囲
内に電解条件を保持したところ、８時間にわたり、良好
な電解操業が継続された。When terbium fluoride was used as a raw material and was continuously supplied to the electrolytic bath while maintaining the electrolytic conditions within the range shown in Table 1 below, good electrolytic operation continued for 8 hours. .
また、液体状の希土類金属（テルビウム）−コバルト合
金が順次滴下して、モリブデン製受器内に集められた。In addition, a liquid rare earth metal (terbium)-cobalt alloy was sequentially dropped and collected in a molybdenum receiver.
さらに、この集められた受器内の生成合金は、実施例１
と同様に液体状態で取り出すことができた。Furthermore, the generated alloy in this collected receiver was Example 1
It was also possible to extract it in liquid form.
かかる電解操作によって得られた電解成績並びに生成合
金の分析結果を、それぞれ下記第１表及び第２表に示す
。The electrolytic results obtained by such electrolytic operation and the analysis results of the produced alloy are shown in Tables 1 and 2 below, respectively.
第 １ 表
“：全希土類金属σｈんどテルビウム）第 ２
表
“：全希土類金属廓んどテルビウム）
かかる第１表及び第２表の結果から明らかなように、本
発明に従ってフッ化テルビウムを電解すとにより、テル
ビウム含有量の高いチルビラ鉄合金或いはテルビウム−
コバルト合金が一製造され得るのであり、またそのよう
な生成は、合金特性を悪化させるカルシウム、酸素、鈍
物の含有量の低いテルビウム−鉄合金或い一ルビウムー
コバルト合金であることが認められる。Table 1: Total rare earth metals σhnd terbium) Part 2
As is clear from the results in Tables 1 and 2, by electrolyzing terbium fluoride according to the present invention, terbium iron alloys with high terbium content or terbium-
It is recognized that cobalt alloys can be produced, and that such formations are terbium-iron alloys or mono-rubium-cobalt alloys with low calcium, oxygen, and obtuse contents that deteriorate the alloy properties. .
また、以上の実施例では、更に長時間にわたって継続し
て電解を行なうことが容易であり、そのような場合にあ
っても、それぞれの実施例と同様な結果が得られること
が確認されている。In addition, in the above examples, it is easy to continue electrolysis for a longer period of time, and even in such a case, it has been confirmed that the same results as in each example can be obtained. .
第１図は本発明を実施するための具体的な電解システム
を示す模式図であり、第２図は本発明を実施するための
電解槽の構造の一例を示す断面図である。
２：電解槽 ４：溶剤
６：原料供給装置 ８：炭素陽極１０：陰極
１２：電力
１４：合金取出手段 １６：保護ガス１８：廃ガス
処理装置
２０：電解槽 ２２：下部槽２４：Ｍ体
３０．３２：耐火断熱材層
３４．３６：耐浴材層
３８ニライニング材 ４０：陰極
４２：炭素陽極 ４４：電解浴４６：陽極昇降
機構 ４８：陰極昇降機構５０：生成合金受器 ５
２：生成合金５４：原料供給装置 ５８：真空吸引ノズ
ル６０：生成合金吸引孔
出願人 住友軽金属工業株式会社
第１図FIG. 1 is a schematic diagram showing a specific electrolytic system for implementing the present invention, and FIG. 2 is a sectional view showing an example of the structure of an electrolytic cell for implementing the present invention. 2: Electrolytic cell 4: Solvent 6: Raw material supply device 8: Carbon anode 10: Cathode 12: Electric power 14: Alloy extraction means 16: Protective gas 18: Waste gas treatment device 20: Electrolytic cell 22: Lower tank 24: M body 30 .32: Fireproof insulation layer 34.36: Bath-resistant layer 38 lining material 40: Cathode 42: Carbon anode 44: Electrolytic bath 46: Anode lifting mechanism 48: Cathode lifting mechanism 50: Generated alloy receiver 5
2: Produced alloy 54: Raw material supply device 58: Vacuum suction nozzle 60: Produced alloy suction hole Applicant: Sumitomo Light Metal Industries, Ltd. Figure 1
Claims (15)
極と炭素陽極とを用いて、テルビウム化合物を溶融塩電
解浴中において電解還元せしめ、生成するテルビウムを
前記陰極上に析出させると共に、該陰極を構成する金属
と合金化せしめて、目的とするテルビウム合金を形成さ
せる方法にして、 前記テルビウム化合物としてフッ化テルビウムを用いる
と共に、かかるテルビウム化合物を含む前記溶融塩電解
浴が、実質的に２０〜９５重量％のフッ化テルビウム、
５〜８０重量％のフッ化リチウム、４０重量％までのフ
ッ化バリウム及び２０重量％までのフッ化カルシウムに
て構成されるように調整する一方、前記テルビウム合金
を前記陰極上に液体状態で生成せしめ、そして該液体状
態のテルビウム合金を、液滴として該陰極下方の電解浴
中に開口部を有する受器内に滴下せしめて、液層として
溜め、更にこの受器内の液層より、テルビウム合金を液
体状態で取り出すようにしたことを特徴とするテルビウ
ム合金の製造方法。(1) Using a solid cathode made of a metal that can be alloyed with terbium and a carbon anode, a terbium compound is electrolytically reduced in a molten salt electrolytic bath, and the generated terbium is deposited on the cathode, and the cathode is A method for forming a target terbium alloy by alloying with constituent metals, wherein terbium fluoride is used as the terbium compound, and the molten salt electrolytic bath containing the terbium compound has a substantially 20 to 95 wt% terbium fluoride,
The terbium alloy is formed in a liquid state on the cathode while being adjusted to consist of 5 to 80% by weight of lithium fluoride, up to 40% by weight of barium fluoride and up to 20% by weight of calcium fluoride. Then, the terbium alloy in the liquid state is dropped as droplets into a receiver having an opening in the electrolytic bath below the cathode to collect it as a liquid layer, and from the liquid layer in the receiver, terbium A method for producing a terbium alloy, characterized in that the alloy is extracted in a liquid state.
が製造される特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the cathode is made of iron and a terbium-iron alloy is manufactured.
コバルト合金が製造される特許請求の範囲第１項記載の
製造方法。(3) The cathode is made of cobalt and terbium-
The manufacturing method according to claim 1, wherein a cobalt alloy is manufactured.
に保持され、かかる温度下に前記電解還元操作が進行せ
しめられる特許請求の範囲第２項記載の製造方法。(4) The manufacturing method according to claim 2, wherein the molten salt electrolytic bath is maintained at a temperature of 860 to 1000°C, and the electrolytic reduction operation is performed at this temperature.
に保持され、かかる温度下に前記電解還元操作が進行せ
しめられる特許請求の範囲第３項記載の製造方法。(5) The manufacturing method according to claim 3, wherein the molten salt electrolytic bath is maintained at a temperature of 710 to 1000°C, and the electrolytic reduction operation is performed at this temperature.
１０．０Ａ／ｃｍ＾２、陰極電流密度：０．５０〜８０
Ａ／ｃｍ＾２の条件下に行なわれる特許請求の範囲第１
項乃至第５項の何れかに記載の製造方法。(6) The electrolytic reduction operation has an anode current density of 0.05 to
10.0A/cm^2, cathode current density: 0.50-80
Claim 1 carried out under the condition of A/cm^2
6. The manufacturing method according to any one of items 5 to 5.
第１項乃至第６項の何れかに記載の製造方法。(7) The manufacturing method according to any one of claims 1 to 6, wherein the carbon anode is a graphite electrode.
質的にフッ化テルビウムとフッ化リチウムにて構成され
、且つ該フッ化テルビウムが少なくとも２５重量％以上
、該フッ化リチウムが少なくとも１５重量％以上、それ
ぞれ存在するように調整せしめられる特許請求の範囲第
１項乃至第７項の何れかに記載の製造方法。(8) The molten salt electrolytic bath containing the terbium compound is substantially composed of terbium fluoride and lithium fluoride, and the terbium fluoride is at least 25% by weight or more and the lithium fluoride is at least 15% by weight. The manufacturing method according to any one of claims 1 to 7, wherein the manufacturing method is adjusted so that each of the above exists.
、並びに必要に応じて添加されたフッ化バリウム、フッ
化カルシウムからなる溶融塩電解浴を収容する、耐火性
材料から構成された電解槽と、 該電解槽の内面の接浴部に施されたライニングと、 該電解槽の溶融塩電解浴中に挿入、浸漬される、実質的
に長さ方向に形状の変化のない長手の炭素陽極と、 該電解槽の溶融塩電解浴中に挿入、浸漬される、実質的
に長さ方向に形状の変化のない、テルビウムと合金化し
得る金属からなる長手の陰極と、 開口部が、該陰極の下方に位置するように、前記電解槽
の溶融塩電解浴中に配置せしめられて、前記炭素陽極と
陰極との間に印加される直流電流によるフッ化テルビウ
ムの電解還元によって該陰極上に生じるテルビウム合金
の液滴が滴下せしめられる、かかるテルビウム合金液滴
を集めるための合金受器と、 該合金受器内の液体状態のテルビウム合金を電解槽外に
取り出すための液状合金取出手段と、前記陰極を、前記
テルビウム合金の生成に伴なうその消耗に従って、前記
電解槽の溶融塩電解浴中に所定の電流密度が得られるよ
うに挿入するための陰極挿入手段とを、 含むことを特徴とするテルビウム合金の製造装置。(9) An electrolytic cell made of a refractory material and containing a molten salt electrolytic bath consisting essentially of terbium fluoride and lithium fluoride, as well as barium fluoride and calcium fluoride added as necessary. , a lining provided on the inner surface of the electrolytic cell in contact with the bath; a longitudinal carbon anode that is inserted into and immersed in the molten salt electrolytic bath of the electrolytic cell and whose shape does not substantially change in the longitudinal direction; , an elongated cathode made of a metal capable of alloying with terbium and having substantially no change in shape in the length direction and inserted into and immersed in the molten salt electrolytic bath of the electrolytic cell; terbium formed on the cathode by electrolytic reduction of terbium fluoride by a direct current applied between the carbon anode and the cathode; an alloy receiver for collecting the terbium alloy droplets into which the alloy droplets are dropped; a liquid alloy take-out means for taking out the liquid terbium alloy in the alloy receiver to the outside of the electrolytic cell; and the cathode. and a cathode insertion means for inserting the terbium alloy into the molten salt electrolytic bath of the electrolytic tank so as to obtain a predetermined current density according to its consumption as the terbium alloy is produced. Terbium alloy manufacturing equipment.
ている特許請求の範囲第９項記載の製造装置。(10) The manufacturing apparatus according to claim 9, wherein the cathode is made of iron or cobalt.
所定の電流密度が得られるように挿入するための陽極挿
入手段を備えた特許請求の範囲第９項または第１０項記
載の製造装置。(11) The production according to claim 9 or 10, comprising an anode insertion means for inserting the carbon anode into the molten salt electrolytic bath of the electrolytic cell so as to obtain a predetermined current density. Device.
に供給する原料供給手段を備えた特許請求の範囲第９項
乃至第１１項の何れかに記載の製造装置。(12) The manufacturing apparatus according to any one of claims 9 to 11, comprising a raw material supply means for supplying terbium fluoride as a raw material into the electrolytic cell.
状テルビウム合金中に挿入されるパイプ状ノズルを有し
、該ノズルを通じて真空吸引作用により該テルビウム合
金を吸い上げ、電解槽外に取り出すようにした特許請求
の範囲第９項乃至第１２項の何れかに記載の製造装置。(13) The liquid alloy extraction means has a pipe-shaped nozzle inserted into the liquid terbium alloy in the alloy receiver, and the terbium alloy is sucked up by vacuum suction through the nozzle and taken out of the electrolytic cell. A manufacturing apparatus according to any one of claims 9 to 12.
特許請求の範囲第９項乃至第１３項の何れかに記載の製
造装置。(14) The manufacturing apparatus according to any one of claims 9 to 13, wherein the lining is made of iron material.
囲第９項乃至第１４項の何れかに記載の製造装置。(15) The manufacturing apparatus according to any one of claims 9 to 14, wherein the carbon anode is a graphite electrode.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6793486A JPS62224692A (en) | 1986-03-26 | 1986-03-26 | Method and apparatus for producing terbium alloy |
| US07/025,272 US4783245A (en) | 1986-03-25 | 1987-03-12 | Process and apparatus for producing alloy containing terbium and/or gadolinium |
| AT87302468T ATE58400T1 (en) | 1986-03-25 | 1987-03-23 | METHOD AND APPARATUS FOR THE PRODUCTION OF AN ALLOY CONTAINING TERBIUM AND/OR GADOLINIUM. |
| EP87302468A EP0242995B1 (en) | 1986-03-25 | 1987-03-23 | Process and apparatus for producing alloy containing terbium and/or gadolinium |
| DE8787302468T DE3766148D1 (en) | 1986-03-25 | 1987-03-23 | METHOD AND DEVICE FOR PRODUCING AN ALLOY CONTAINING TERBIUM AND / OR GADOLINIUM. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6793486A JPS62224692A (en) | 1986-03-26 | 1986-03-26 | Method and apparatus for producing terbium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62224692A true JPS62224692A (en) | 1987-10-02 |
| JPH0569918B2 JPH0569918B2 (en) | 1993-10-04 |
Family
ID=13359253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6793486A Granted JPS62224692A (en) | 1986-03-25 | 1986-03-26 | Method and apparatus for producing terbium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62224692A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258103A (en) * | 1991-01-17 | 1993-11-02 | Mitsubishi Kasei Corporation | Process for producing terbium alloy or terbium metal |
| JP2009287119A (en) * | 2008-05-01 | 2009-12-10 | National Institute Of Advanced Industrial & Technology | Method for collecting rare earth metal |
| JP2015513604A (en) * | 2012-07-31 | 2015-05-14 | グリレム アドヴァンスド マテリアルズ カンパニー リミテッドＧｒｉｒｅｍ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． | Rare earth metal, rare earth metal alloy, and method of manufacturing rare earth metal and rare earth metal alloy by molten salt electrolysis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3383294A (en) * | 1965-01-15 | 1968-05-14 | Wood Lyle Russell | Process for production of misch metal and apparatus therefor |
-
1986
- 1986-03-26 JP JP6793486A patent/JPS62224692A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3383294A (en) * | 1965-01-15 | 1968-05-14 | Wood Lyle Russell | Process for production of misch metal and apparatus therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258103A (en) * | 1991-01-17 | 1993-11-02 | Mitsubishi Kasei Corporation | Process for producing terbium alloy or terbium metal |
| JP2009287119A (en) * | 2008-05-01 | 2009-12-10 | National Institute Of Advanced Industrial & Technology | Method for collecting rare earth metal |
| JP2015513604A (en) * | 2012-07-31 | 2015-05-14 | グリレム アドヴァンスド マテリアルズ カンパニー リミテッドＧｒｉｒｅｍ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． | Rare earth metal, rare earth metal alloy, and method of manufacturing rare earth metal and rare earth metal alloy by molten salt electrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0569918B2 (en) | 1993-10-04 |
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