JPH04128326A - Method for purifying rare earth element and its alloy - Google Patents
Method for purifying rare earth element and its alloyInfo
- Publication number
- JPH04128326A JPH04128326A JP24635590A JP24635590A JPH04128326A JP H04128326 A JPH04128326 A JP H04128326A JP 24635590 A JP24635590 A JP 24635590A JP 24635590 A JP24635590 A JP 24635590A JP H04128326 A JPH04128326 A JP H04128326A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- container
- alloy
- alloys
- earth metal
- 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.)
- Pending
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 55
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000011109 contamination Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- -1 rare earth halide Chemical class 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 10
- 239000002893 slag Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 229910052715 tantalum Inorganic materials 0.000 description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 14
- 229910001297 Zn alloy Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 4
- XQHFYYLMNCPIHT-UHFFFAOYSA-N scandium zinc Chemical compound [Sc].[Zn].[Zn].[Zn].[Zn].[Zn].[Zn] XQHFYYLMNCPIHT-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 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
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、希土類金属またはその合金の清浄化方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for cleaning rare earth metals or alloys thereof.
［従来の技術］
希土類金属またはその合金の製造する方法は、溶融塩電
解法と金属還元方法の二つの方法がある。[Prior Art] There are two methods for producing rare earth metals or their alloys: molten salt electrolysis and metal reduction.
溶融塩電解法
（１）無水希土類塩化物または希土類フッ化物を溶融塩
の電解浴中で電解採取する方法。Molten salt electrolysis method (1) A method of electrowinning anhydrous rare earth chloride or rare earth fluoride in an electrolytic bath of molten salt.
（２）希土類酸化物を溶融塩の電解浴中で電解採取する
方法。(2) A method of electrowinning rare earth oxides in a molten salt electrolytic bath.
金属還元法
（１）無水希土類塩化物または希土類フッ化物を、アル
カリ、アルカリ土類金属により熱還元する方法。Metal reduction method (1) A method of thermally reducing an anhydrous rare earth chloride or rare earth fluoride with an alkali or alkaline earth metal.
（２）希土類フッ化物を熱１元する際に、ＭｇまたはＺ
ｎ等を加えて低融点合金として採取し、これを蒸留して
Ｍｇ、Ｚｎを除去する方法。(2) When heating rare earth fluorides, Mg or Z
A method in which a low melting point alloy is collected by adding n, etc., and then distilled to remove Mg and Zn.
（３）希土類酸化物をＬａ、Ｃｅなどで熱還元する方法
。(3) A method of thermally reducing rare earth oxides with La, Ce, etc.
しかし、これらの方法では副原料や装置からの不純物の
汚染があり、高純度金属を得ることは困難であった。However, with these methods, it has been difficult to obtain highly pure metals due to contamination with impurities from auxiliary raw materials and equipment.
これらの方法で得られた希土類金属をさらに高純度化す
るためには、通常は、蒸留精製法、エレクトロ・トラン
スポート法、ゾーン精製法等を用いて精製するなど高度
な設備や技術を必要としている。In order to further purify the rare earth metals obtained by these methods, advanced equipment and technology are usually required, such as purification using distillation refining methods, electro-transport methods, zone refining methods, etc. There is.
〔発明が解決しようとする問題点］
希土類金属は、非常に活性であり、高純度なものを得る
ためには、蒸留精製法、ゾーン精製法等を用いることが
必要とされている。しかし、これらの方法で、希土類金
属と同じ挙動をする不純物成分は除去することはできな
い。[Problems to be Solved by the Invention] Rare earth metals are very active, and in order to obtain highly pure metals, it is necessary to use a distillation refining method, a zone refining method, or the like. However, these methods cannot remove impurity components that behave in the same way as rare earth metals.
以上に鑑み、本発明は、高純度希土類金属及びその合金
に関して工業的に採算のとれる高純度希土類金属製造に
関する製造法を確立することにある。In view of the above, an object of the present invention is to establish an industrially profitable manufacturing method for producing high-purity rare earth metals and alloys thereof.
［問題点を解決するための手段及び作用１本発明は、希
土類金属またはその合金を製造する装置において、反応
生成物である溶融状態の希土類金属またはその合金を、
製造容器の底部からガス等の流体等で冷却し、希土類金
属製造装置の製造容器の軸方向の温度をコントロールし
ながら軸方向に結晶を晶出させることにより、分相の良
好な不純分の少ない希土類金属またはその合金を得るこ
とができることが判明したものである。[Means and effects for solving the problems 1] The present invention provides an apparatus for producing a rare earth metal or its alloy, in which a molten rare earth metal or its alloy, which is a reaction product, is
By cooling the manufacturing container with a fluid such as gas from the bottom and crystallizing the crystals in the axial direction while controlling the temperature in the axial direction of the manufacturing container of the rare earth metal manufacturing equipment, the product has good phase separation and low impurity content. It has been found that rare earth metals or alloys thereof can be obtained.
斯くして、本発明は、
（１）希土類金属またはその合金を製造する工程におい
て、溶解還元後に製造容器の底部のヒーターを切り、他
の側壁部に配置したヒーター加熱については、４℃／分
より遅い温度傾斜をもってゆるやかに降温させ、非金属
物等が製品中に混入することを防止することを特徴とす
る希土類金属及びその合金の清浄化方法。Thus, the present invention provides the following features: (1) In the process of manufacturing rare earth metals or their alloys, after melting and reduction, the heater at the bottom of the manufacturing container is turned off, and the heaters placed on the other side walls are heated at 4°C/min. A method for cleaning rare earth metals and alloys thereof, characterized by gently lowering the temperature with a slower temperature gradient to prevent non-metallic substances from being mixed into the product.
（２）希土類金属またはその合金を製造する製造容器の
底部のヒーターのない炉において、側壁部に配置したヒ
ーター加熱を４℃／分より遅い温度傾斜をもってゆるや
かに降温させ、非金属物等が製品中に混入することを防
止することを特徴とする希土類金属及びその合金の清浄
化方法。(2) In a furnace without a heater at the bottom of a production container for producing rare earth metals or their alloys, the heater placed on the side wall is heated slowly with a temperature gradient slower than 4°C/min, so that non-metallic materials, etc. 1. A method for cleaning rare earth metals and their alloys, characterized by preventing their contamination.
（３）希土類金属またはその合金を製造する工程におい
て、反応生成物を製造容器の底部から冷却することによ
り、反応生成物である希土類金属またはその合金への非
金属介在物やガスによる汚染を防止することを特徴とす
る希土類金属及びその合金清浄化方法。(3) In the process of manufacturing rare earth metals or their alloys, cooling the reaction products from the bottom of the manufacturing container prevents contamination of the reaction products, rare earth metals or their alloys, with nonmetallic inclusions and gases. A method for cleaning rare earth metals and alloys thereof.
を提供するものである。It provides:
本発明でいう希土類金属とはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、
Ｙ、Ｇｄ、Ｔｂ％Ｌｕ％Ｓｃ、Ｄｙ、Ｈｏ。The rare earth metals referred to in the present invention include La, Ce, Pr, Nd,
Y, Gd, Tb%Lu%Sc, Dy, Ho.
Ｅｒをさすものである。上に述べた様に、これらの希土
類金属をさらに高純度化するためには、通常は、蒸留精
製法、エレクトロ・トランスボート法、ゾーン精製法等
を用いて精製する。しかしながら、これらの方法で高純
度化するためには、限界があるために精製する前に、予
め不純物濃度を少なくしておく必要がある。It refers to Er. As mentioned above, in order to further purify these rare earth metals, distillation refining methods, electrotransfer methods, zone refining methods, etc. are generally used. However, in order to achieve high purity using these methods, it is necessary to reduce the impurity concentration in advance before purification due to limitations.
希土類金属製造装置は、第１図に示すごとく製造容器（
９）、タンタル坩堝（５）、真空排気系（１４）、電気
炉（７）、炉底冷却部（１６）から主に構成されている
。まず製造容器（９）は電気炉内（７）にセットされ、
その製造容器（９）内にタンタル類等からなる容器（６
）を挿入し、さらにタンタル類等からなる坩堝（５）に
希土類ハロゲン化物、還元材、造滓材又はその合金を充
填し、上部横倒に開孔部を設けた蓋を取り付けてタンタ
ル容器（６）内にセットする。The rare earth metal manufacturing equipment consists of a manufacturing container (
9), a tantalum crucible (5), a vacuum exhaust system (14), an electric furnace (7), and a furnace bottom cooling section (16). First, the production container (9) is set in the electric furnace (7),
A container (6) made of tantalum etc. is placed in the manufacturing container (9).
), then fill the crucible (5) made of tantalum, etc. with rare earth halides, reducing agents, slag-making materials, or their alloys, attach a lid with an opening on the side of the top, and place the tantalum container ( 6) Set within.
製造容器（９）の上端には、蓋がＯリング等のシルを介
して装着される。製造容器（９）の蓋には、ジャケット
（１８）、Ａｒ封入口（１）、熱電対温度計（炉内）（
２）の取付口が設けられており、熱電対温度計は、０リ
ング等のシールを介して装着される。A lid is attached to the upper end of the manufacturing container (9) via a sill such as an O-ring. The lid of the production container (9) has a jacket (18), an Ar sealing port (1), and a thermocouple thermometer (inside the furnace) (
2) is provided, and a thermocouple thermometer is attached via a seal such as an O-ring.
希土類金属は、活性であるため熱電対温度計のアルミナ
製絶縁管は、ステンレス製のパイプで保護している。ま
た、ジャケット（１８）は、揮発成分等の不純物を凝縮
するために水冷構造とし、ジャケット（１８）の冷却水
は、入口（３）から出口（４）へと排出される。さらに
、真空排気系（１４）と製造容器（９）との間は％Ｏリ
ング等のシーフレを介して接続される。以上が、希土類
金属およびその合金の製造装置の概要である。Because rare earth metals are active, the alumina insulation tube of the thermocouple thermometer is protected by a stainless steel pipe. Further, the jacket (18) has a water-cooled structure in order to condense impurities such as volatile components, and the cooling water of the jacket (18) is discharged from the inlet (3) to the outlet (4). Further, the vacuum evacuation system (14) and the manufacturing container (9) are connected via a seal such as an O-ring. The above is an overview of the apparatus for producing rare earth metals and their alloys.
本発明は、希土類ハロゲン化物を不活性ガス雰囲気中で
加熱し、活性金属等で還元して希土類金属およびその合
金を製造し、その凝固を製造容器（９）の軸方向に行う
ことにより、清浄な希土類金属およびその合金を得る製
造装置ならびにその方法である。The present invention produces rare earth metals and their alloys by heating rare earth halides in an inert gas atmosphere, reducing them with active metals, etc., and solidifying them in the axial direction of the production container (9). The present invention provides a manufacturing apparatus and method for obtaining rare earth metals and their alloys.
第１図の装置に基づいて希土類金属およびその合金の操
業例を説明する。先ず最初に、タンタル製等の坩堝（５
）の中に希土類ハロゲン化物、還元材等及び又は希土類
合金添加元素等を所定量充填し、その上部にタンタル製
等の蓋（１１）を取り付ける。これを予め製造容器（９
）に挿入しておいたタンタル製等の容器（６）の中に入
れ、タンタル製等の足桁の上に載せる。そして製造容器
（９）に蓋ならびに不活性ガス封入口（１）、熱電対温
度計（炉内）（２）を取り付けて密閉状態とする。そし
て製造容器（９）内を真空ポンプで真空排気系（１４）
を介して十分排気する６その後、製造容器（９）を２０
０〜４００℃位に昇温しで付着ガス成分、水分を取り除
き、不活性ガスを導入しＯ６１〜０．５ｋｇ＃ｎｌの圧
力に保つ。この不活性ガス雰囲気中で希土類金属および
その合金の融点の少なくとも５０℃以上高い温度として
希土類金属およびその合金とスラグに分離させ、保持後
冷却する。この工程において製造容器（９）内の圧力を
０．１〜０．５ｋｇ／ｃｒＡに保つために圧力調整弁（
１５）により自動的に調整される。その冷却方法は、製
造容器（９）の底部のをヒーターを切り、他の側壁部に
配置したヒーター加熱については、４℃／分より遅い温
度傾斜をもってゆるやかに降温し、製造容器（９）の軸
方向に結晶を晶出させる。底部にヒーターのないものも
同様な温度傾斜をもって降温させる。この手法により、
意外にも溶融状態にある希土類金属およびその合金に含
まれれるスラグ等の不純分、ガス成分を除去することを
容易ならしめた。An example of operation of rare earth metals and their alloys will be explained based on the apparatus shown in FIG. First of all, a crucible made of tantalum (5
) is filled with a predetermined amount of rare earth halide, reducing agent, etc., and/or rare earth alloy additive elements, etc., and a lid (11) made of tantalum or the like is attached to the top. This is prepared in advance in a container (9
) and place it in a container (6) made of tantalum, etc., which has been inserted into the container (6), and place it on a foot frame made of tantalum, etc. Then, a lid, an inert gas inlet (1), and a thermocouple thermometer (inside the furnace) (2) are attached to the production container (9) to seal it. Then, the inside of the manufacturing container (9) is evacuated using a vacuum pump (14).
The production vessel (9) is then thoroughly evacuated through 6
The temperature is raised to about 0 to 400°C to remove adhering gas components and moisture, and an inert gas is introduced to maintain the pressure at O61 to 0.5 kg#nl. In this inert gas atmosphere, the rare earth metal and its alloy are heated to a temperature that is at least 50° C. higher than the melting point of the rare earth metal and its alloy, and the rare earth metal and its alloy are separated into slag, which is held and then cooled. In this process, a pressure regulating valve (
15) is automatically adjusted. The cooling method is to turn off the heater at the bottom of the production container (9), and use the heaters placed on the other side walls to slowly lower the temperature with a temperature gradient slower than 4°C/min. Crystals are crystallized in the axial direction. For those without a heater at the bottom, the temperature is lowered with a similar temperature gradient. With this method,
Surprisingly, it has become easier to remove impurities such as slag and gas components contained in molten rare earth metals and their alloys.
一方より好ましい方法としては、製造容器（９）の底部
を冷却することである。底部から先に凝固が行われ、好
ましいからである。底部の冷却方法としては、空気、不
活性ガス等のガス体で行う方法、水等の液体で行う強制
冷却方法等である。On the other hand, a more preferred method is to cool the bottom of the production container (9). This is because coagulation is performed from the bottom first, which is preferable. Methods for cooling the bottom include a method using a gas such as air or an inert gas, and a forced cooling method using a liquid such as water.
第１図の装置を用いて、スカンジウム−亜鉛合金を製造
する場合の実施例を示す。An example will be shown in which a scandium-zinc alloy is produced using the apparatus shown in FIG.
２００Ｍφのタンタル製坩堝（５）にフッ化スカンジウ
ム、還元材である粒状もしくは柱状の金属カルシウム、
造滓材としてのフッ化リチウム、合金化材として蒸留亜
鉛を不活性ガス雰囲気中で層状に充填する。そしてその
上部には、ガス及び蒸気抜きの開孔部の付いたタンタル
製の蓋（ＩＩ）を取り付け、さらに大きなタンタル製容
器（６）に挿入して製造容器（９）にセットした。In a 200Mφ tantalum crucible (5), scandium fluoride, granular or columnar metallic calcium as a reducing agent,
Lithium fluoride as a slag material and distilled zinc as an alloying material are packed in layers in an inert gas atmosphere. A tantalum lid (II) with openings for gas and steam venting was attached to the top, and the lid was inserted into a larger tantalum container (6) and set in the production container (9).
電気炉（７）は、加熱部がいくつかのゾーンにわかれて
おり、炉内温度が一定となるように熱電対温度計（炉体
） （１０）で制御した。また炉底部（１６）は、空気
等の流体で冷却するための装置を備え付けている。The electric furnace (7) had a heating section divided into several zones, and was controlled by a thermocouple thermometer (furnace body) (10) so that the temperature inside the furnace was constant. The furnace bottom (16) is also equipped with a device for cooling with a fluid such as air.
前操作として真空ポンプで製造容器（９）内を十分に排
気して昇温し３５０℃前後の温度で十分脱ガスを行った
のち、Ａｒを製造容器（９）内に導入し０．１〜０．５
Ｋ ｇ／ｃＴＩｔの圧力にセットした。モしてフッ化
スカンジウムを還元してスカンジウム−亜鉛合金（Ｓ
ｃ−Ｚ ｎ合金）を得る温度１０００〜１１００℃まで
徐々に加熱し１〜２時間保持した。その間、製造容器（
９）内の圧力は圧力調整装置（１５）により自動的に調
節した。As a pre-operation, the inside of the manufacturing container (9) was sufficiently evacuated with a vacuum pump to raise the temperature, and after sufficient degassing was performed at a temperature of around 350°C, Ar was introduced into the manufacturing container (9) to a temperature of 0.1 to 0.5
The pressure was set at K g/cTIt. Scandium fluoride is reduced using a scandium-zinc alloy (S
c-Zn alloy) was gradually heated to a temperature of 1000 to 1100°C and held for 1 to 2 hours. Meanwhile, the manufacturing container (
9) was automatically regulated by a pressure regulator (15).
１０００−１１００℃で、Ｓ ｃ−Ｚ ｎ合金（１３）
とスラグ（Ｃａ Ｆ、−４Ｌ ｉ Ｆ） （＋２）に分
相させ、セットリング後、炉底部のヒーターを切り、電
気炉（７）の加熱を弱めながら製造容器（９）内の温度
が７００〜５００℃になるまで３．５℃／分で降温させ
、冷却した。At 1000-1100 °C, S c-Z n alloy (13)
and slag (Ca F, -4L i F) (+2), and after settling, the heater at the bottom of the furnace was turned off and the temperature in the production container (9) was lowered to 700°C while weakening the heating in the electric furnace (7). The temperature was lowered at a rate of 3.5°C/min until the temperature reached ~500°C, and the mixture was cooled.
その後、電気炉（７）の加熱を停止して製造容器（９）
内にＡｒを０．５Ｋｇ／ｃｏ！の圧力になるまで封入し
て常温になるまで冷却し還元生成物である５ｃ−Ｚｎ（
１３）とスラグ（Ｃａ Ｆ、−４Ｌ ｉ Ｆ） （＋２
）を取り出した。取り出したＳ ｃ−Ｚ ｎ（１３）は
銀白色で金属光沢をしており脆く、その合金は不純分（
Ｃａ、Ｌｉ、 ＣａＦ、−４ＬｉＦ、ＣａＦ＊＋４
Ｌ ｉ Ｆ）の少ないものであった。After that, the heating of the electric furnace (7) is stopped and the manufacturing container (9) is heated.
0.5Kg/co of Ar inside! The reduction product 5c-Zn (
13) and slag (Ca F, -4L i F) (+2
) was taken out. The extracted S c-Z n (13) is silvery white, has a metallic luster, and is brittle, and its alloy is free of impurities (
Ca, Li, CaF, -4LiF, CaF*+4
L i F).
電気炉（７）の炉底部（１６）のヒーターを切り、他の
側壁部に配置したヒータ！で３８５℃／分の温度傾斜を
もって降温させて冷却した場合のＳｃ−Ｚｎ合金と、そ
うでない場合のＳ ｃ−Ｚ ｎ合金中のＣａの分析値は
第１表の通りであった。したがって５ｃ−Ｚｎ合金中の
Ｃａが、本発明の実施例では極めて低いことが言える。Turn off the heater at the bottom (16) of the electric furnace (7) and place the heater on the other side wall! Table 1 shows the analytical values of Ca in the Sc-Zn alloy when the temperature was lowered at a temperature gradient of 385° C./min and the Sc-Zn alloy when the alloy was not cooled. Therefore, it can be said that Ca in the 5c-Zn alloy is extremely low in the examples of the present invention.
より好ましくは、スカンジウム−亜鉛合金を同様な冷却
方法で冷却すると同時に、製造容器（９）の炉底部（１
６）をファン（８）等を用いてガス等の流体で冷却（冷
却速度はダンパー（１７）で調節）することにより、第
１表の実施例の値以下即ち、ＣＣａ１００ｐｐにするこ
とが出来た。More preferably, the scandium-zinc alloy is cooled by a similar cooling method, and at the same time, the furnace bottom (1) of the production vessel (9) is cooled.
By cooling 6) with a fluid such as gas using a fan (8) etc. (the cooling rate was adjusted with a damper (17)), it was possible to reduce the CCa to below the value of the example in Table 1, that is, to 100 pp. .
第１表 スカンジウム中の不純物量
（単位ｐｐｍ ）
〔比較例〕
実施例と同様なスカンジウム−亜鉛合金の製造において
、４．５℃分／の冷却スピードで側壁部を冷却したとこ
ろ、一方向にならないため第１表のごと＜Ｃａが２５３
００ｐｐｍと極めて高い値を示した。Table 1 Amount of impurities in scandium (unit: ppm) [Comparative example] In the production of a scandium-zinc alloy similar to the example, when the side wall was cooled at a cooling rate of 4.5°C/min, it did not become unidirectional. Therefore, as shown in Table 1, <Ca is 253
It showed an extremely high value of 00 ppm.
本発明を実施することにより、希土類金属（合金を含む
）とスラグの分相を良好にし、希土類金属またはその合
金中にＣａ等の不純物を極めて低い値とすることができ
る。By carrying out the present invention, it is possible to improve the phase separation between rare earth metals (including alloys) and slag, and to reduce the amount of impurities such as Ca in the rare earth metals or their alloys to extremely low values.
第１図は、本発明の希土類金属の製造装置の一例の正面
図である。
１：Ａｒ封入口
２： 熱電対温度計（炉内）
３：冷却水入口
４：冷却水出口
５： タンタル坩堝
６： タンタル容器
７：電気炉
８：フ ァ ン
９：製造容器
ｌＯ： 熱電対温度計（炉体）
１１： タンタル製蓋
１２： 反応生成物（スラグ）
１３： 反応生成物（金属又は合金）１４：
１５＝
１６＝
１７：
１８：
真空排気系
圧力調整弁
炉底冷却部
ダンパ
ジャケットFIG. 1 is a front view of an example of the rare earth metal manufacturing apparatus of the present invention. 1: Ar filling port 2: Thermocouple thermometer (in the furnace) 3: Cooling water inlet 4: Cooling water outlet 5: Tantalum crucible 6: Tantalum container 7: Electric furnace 8: Fan 9: Manufacturing container 1O: Thermocouple Thermometer (furnace body) 11: Tantalum lid 12: Reaction product (slag) 13: Reaction product (metal or alloy) 14: 15= 16= 17: 18: Vacuum exhaust system pressure regulating valve Furnace bottom cooling part damper Jacket
Claims (3)
て、溶解還元後に製造容器の底部のヒーターを切り、他
の側壁部に配置したヒーター加熱については、４℃／分
より遅い温度傾斜をもってゆるやかに降温させ、非金属
物等が製品中に混入することを防止することを特徴とす
る希土類金属及びその合金の清浄化方法。(1) In the process of manufacturing rare earth metals or their alloys, the heater at the bottom of the manufacturing container is turned off after melting and reduction, and the heater placed on the other side wall is used to slowly lower the temperature with a temperature gradient slower than 4°C/min. A method for cleaning rare earth metals and alloys thereof, characterized by preventing non-metallic substances from being mixed into the product.
底部のヒーターのない炉において、側壁部に配置したヒ
ーター加熱を４℃／分より遅い温度傾斜をもってゆるや
かに降温させ、非金属物等が製品中に混入することを防
止することを特徴とする希土類金属及びその合金の清浄
化方法。(2) In a furnace without a heater at the bottom of a production container for producing rare earth metals or their alloys, the heater placed on the side wall is heated slowly with a temperature gradient slower than 4°C/min, so that non-metallic materials, etc. 1. A method for cleaning rare earth metals and their alloys, characterized by preventing their contamination.
て、反応生成物を製造容器の底部から冷却することによ
り、反応生成物である希土類金属またはその合金への非
金属介在物やガスによる汚染を防止することを特徴とす
る希土類金属及びその合金清浄化方法。(3) In the process of manufacturing rare earth metals or their alloys, cooling the reaction products from the bottom of the manufacturing container prevents contamination of the reaction products, rare earth metals or their alloys, with nonmetallic inclusions and gases. A method for cleaning rare earth metals and alloys thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24635590A JPH04128326A (en) | 1990-09-18 | 1990-09-18 | Method for purifying rare earth element and its alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24635590A JPH04128326A (en) | 1990-09-18 | 1990-09-18 | Method for purifying rare earth element and its alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04128326A true JPH04128326A (en) | 1992-04-28 |
Family
ID=17147327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24635590A Pending JPH04128326A (en) | 1990-09-18 | 1990-09-18 | Method for purifying rare earth element and its alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04128326A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018109231A (en) * | 2016-12-29 | 2018-07-12 | 有研稀土新材料股▲フン▼有限公司 | Rare earth metal and method for purifying the same |
-
1990
- 1990-09-18 JP JP24635590A patent/JPH04128326A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018109231A (en) * | 2016-12-29 | 2018-07-12 | 有研稀土新材料股▲フン▼有限公司 | Rare earth metal and method for purifying the same |
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