JPH06173065A - Method for refining ti - Google Patents
Method for refining tiInfo
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- JPH06173065A JPH06173065A JP35154292A JP35154292A JPH06173065A JP H06173065 A JPH06173065 A JP H06173065A JP 35154292 A JP35154292 A JP 35154292A JP 35154292 A JP35154292 A JP 35154292A JP H06173065 A JPH06173065 A JP H06173065A
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- molten salt
- alkali metal
- purity
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- electrolysis
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶融塩電解法によるＴ
ｉの精製法に関する。本発明により得られる高純度Ｔｉ
は、金属不純物が極微量まで低減されており、半導体デ
バイス製造用のタ−ゲット材等として、好適である。BACKGROUND OF THE INVENTION The present invention relates to T by the molten salt electrolysis method.
i purification method. High-purity Ti obtained by the present invention
The metal impurities are reduced to an extremely small amount, and is suitable as a target material for manufacturing semiconductor devices.
【０００２】[0002]
【従来技術】溶融塩電解法によるＴｉの電解精製に用い
られる電解浴として、一般に、塩化物浴（代表例：Ｎａ
Ｃｌ−ＫＣｌ−ＴｉＣｌ2−ＴｉＣｌ3）、塩化物−弗化
物混浴（代表例：ＮａＣｌ−Ｋ2ＴｉＦ6）、弗化物浴
（代表例：ＮａＦ−Ｋ2ＴｉＦ6）等が知られている。As an electrolytic bath used for electrolytic refining of Ti by a molten salt electrolysis method, a chloride bath (typical example: Na) is generally used.
Cl-KCl-TiCl 2 -TiCl 3 ), chloride - fluoride mixed bathing (typical example: NaCl-K 2 TiF 6) , fluoride bath (typical example: NaF-K 2 TiF 6) and the like are known.
【０００３】しかしながら、塩化物浴は装置の耐食性が
高く、また取り扱い易いという利点があるものの、Ｃ
ｕ、Ｆｅ、Ｃｒ等の不純物は、塩素イオンの影響等によ
り除去されにくいのが現状である。また、弗化物浴は、
装置の耐食性、Ｔｉに付着した塩の除去が難しい等の問
題点がある。一方、塩化物−弗化物混浴にしても、弗化
物を大量に加えなければ良好な電析物を得ることが出来
ず、また、前記弗化物浴と同様の問題点がある。However, although the chloride bath has the advantages that the equipment has high corrosion resistance and is easy to handle, C
At present, it is difficult to remove impurities such as u, Fe and Cr due to the influence of chlorine ions. Also, the fluoride bath is
There are problems such as the corrosion resistance of the device and the difficulty in removing the salt adhering to Ti. On the other hand, even in a chloride-fluoride mixed bath, a good electrodeposit cannot be obtained unless a large amount of fluoride is added, and there are the same problems as in the above-mentioned fluoride bath.
【０００４】[0004]
【問題点を解決するための手段】そこで、本発明者等
が、塩化物浴を中心に鋭意検討したところ、塩化物浴に
少量のアルカリ金属弗化物を添加することにより、上記
問題点を解決できると共に高純度のＴｉを得ることがで
きることを見出した。従って、本発明の目的は、溶融塩
電解法による粗ＴｉからのＴｉの精製方法を提供するこ
とにある。Then, the inventors of the present invention have conducted intensive studies mainly on chloride baths, and found that the above problems can be solved by adding a small amount of alkali metal fluoride to the chloride baths. It was found that Ti with high purity can be obtained. Therefore, an object of the present invention is to provide a method for purifying Ti from crude Ti by a molten salt electrolysis method.
【０００５】[0005]
【発明の構成】即ち本発明は、 （１）アルカリ金属塩化物系の溶媒とチタン塩化物の溶
質を用いる溶融塩電解法で粗Ｔｉを電解精製する方法に
おいて、溶融塩中にアルカリ金属弗化物を添加して電解
を行なうことを特徴とするＴｉの精製方法。 （２）アルカリ金属弗化物の添加量が、溶融塩に対して
０．３〜１０ｗｔ％であることを特徴とする前記（１）
記載の方法。 を提供する。The present invention comprises: (1) In a method for electrolytically refining crude Ti by a molten salt electrolysis method using an alkali metal chloride solvent and a solute of titanium chloride, an alkali metal fluoride is contained in the molten salt. A method for purifying Ti, comprising the step of adding electrolysis. (2) The addition amount of the alkali metal fluoride is 0.3 to 10 wt% with respect to the molten salt, (1)
The method described. I will provide a.
【０００６】[0006]
【発明の具体的説明】次に本発明の理解を容易にするた
め具体的かつ詳細に説明する。まず、本発明の対象とな
る粗Ｔｉの純度は、特に制限はないが、通常市販されて
いる純度９９〜９９．９９ｗｔ％のものである。カソ−
ドとしては、電着する高純度Ｔｉを汚染しないもの例え
ばＴｉ，Ｎｉ，Ｗ，Ｍｏ等であり、好ましくはＴｉ、よ
り好ましくは通常目的とする純度以上の高純度Ｔｉであ
る。DETAILED DESCRIPTION OF THE INVENTION Next, a specific and detailed description will be given to facilitate understanding of the present invention. First, the purity of crude Ti which is the subject of the present invention is not particularly limited, but it is usually commercially available with a purity of 99 to 99.99 wt%. Caso
As the electrode, those which do not contaminate the high-purity Ti to be electrodeposited, such as Ti, Ni, W, Mo, etc., are preferably Ti, and more preferably high-purity Ti having a purity higher than the intended purity.
【０００７】次に本発明に用いられるアルカリ金属溶融
塩の溶媒としては、例えばＮａＣｌ，ＮａＣｌ−ＫＣｌ
（モル比＝４０〜６０：６０〜４０）、ＬｉＣｌ−ＫＣ
ｌ（モル比＝４０〜６０：６０〜４０）等があり、溶質
として、ＴｉＣｌ2、ＴｉＣｌ3、ＴｉＣｌ4等がある。
以上のような塩は、通常、重金属、高融点金属、放射性
元素等の不純物の少ない純度の高いもの、具体的には、
揮発性の不純物元素除きで純度９９．９ｗｔ％以上、好
ましくは純度９９．９９ｗｔ％以上のものを使用しなけ
ればならない。９９．９ｗｔ％以下のものを用いると、
電析したＴｉが汚染を受けてしまうからである。Next, as the solvent of the molten alkali metal salt used in the present invention, for example, NaCl, NaCl-KCl
(Molar ratio = 40-60: 60-40), LiCl-KC
1 (molar ratio = 40 to 60:60 to 40), and solutes such as TiCl 2 , TiCl 3 , and TiCl 4 .
The above-mentioned salts are usually high-purity salts with few impurities such as heavy metals, refractory metals and radioactive elements, specifically,
Excluding volatile impurity elements, a purity of 99.9 wt% or more, preferably a purity of 99.99 wt% or more must be used. If less than 99.9 wt% is used,
This is because the electrodeposited Ti is contaminated.
【０００８】これらの塩化物浴に、アルカリ金属弗化
物、例えばＮａＦ，ＫＦ等を添加するのが、本発明の特
徴である。これらも同様に、揮発性の不純物元素除きで
純度９９．９ｗｔ％以上、好ましくは純度９９．９９ｗ
ｔ％以上のものを使用しなければならない。現在、添加
に用いる入手可能なアルカリ金属弗化物は、上記不純物
濃度が高い。そこで、アルカリ金属弗化物は、例えば、
市販で高純度のＮａＣｌ等を原料として、高純度のＨＦ
を添加することにより、ＮａＦ等を製造することが好ま
しい。It is a feature of the present invention that alkali metal fluorides such as NaF and KF are added to these chloride baths. Similarly, these also have a purity of 99.9 wt% or higher, preferably 99.99 w, excluding volatile impurity elements.
A t% or more must be used. Currently available alkali metal fluorides used for addition have a high concentration of the above impurities. Therefore, the alkali metal fluoride is, for example,
Commercially available high-purity NaCl, etc.
It is preferable to produce NaF and the like by adding.
【０００９】これらを添加することにより、粗Ｔｉ中に
含まれる不純物（Ｆｅ、Ｎｉ、Ｃｒ等）が電解精製中に
溶出しても、その大部分が弗化物となり、Ｔｉの弗化物
あるいは塩化物との析出電位差が、塩化物単独の場合よ
りも大きくなり、電解精製効果が従来に比べて顕著にな
り、純度９９．９９９９ｗｔ％（以下、単に６Ｎと記
す）以上の高純度のＴｉを得ることができる。By adding these, even if impurities (Fe, Ni, Cr, etc.) contained in crude Ti are eluted during electrolytic refining, most of them become fluorides, and fluorides or chlorides of Ti are obtained. The precipitation potential difference between and is larger than that of chloride alone, the electrolytic refining effect is more remarkable than before, and high purity Ti with a purity of 99.9999 wt% (hereinafter simply referred to as 6N) or higher is obtained. You can
【００１０】アルカリ金属弗化物の添加量は、ＮａＣｌ
−ＫＣｌ−ＴｉＣｌ2−ＴｉＣｌ3（モル比：ＮａＣｌ：
ＫＣｌ＝４０〜６０：６０〜４０，Ｔｉ＝１〜４ｗｔ
％）等の浴に対して、０．３ｗｔ％〜１０ｗｔ％、好ま
しくは０．５〜３．０ｗｔ％である。０．３ｗｔ％未満
の場合、析出電位に大きな変動がなく電解精製効果がほ
とんどない。また、１０ｗｔ％を超えて加えてもその効
果に顕著な向上がみられず、装置が腐食される、Ｎａが
析出する等の問題があり好ましくない。The amount of alkali metal fluoride added is NaCl
-KCl-TiCl 2 -TiCl 3 (molar ratio: NaCl:
KCl = 40-60: 60-40, Ti = 1-4 wt
%) To a bath such as 0.3 wt% to 10 wt%, preferably 0.5 to 3.0 wt%. When it is less than 0.3 wt%, there is no large variation in the deposition potential and there is almost no electrolytic refining effect. Further, even if added in excess of 10 wt%, the effect is not significantly improved, and there are problems such as corrosion of the device and precipitation of Na, which is not preferable.
【００１１】次にＴｉの溶融塩電解精製例を具体的に示
す。まず、使用する塩は、事前に十分真空乾燥脱水し、
水分等の除去を行なうことが必要である。そして、Ｎｉ
ルツボ中にＮａＣｌ−ＫＣｌ（モル比＝４０〜６０：６
０〜４０）を入れ、アノ−ドである粗ＴｉスポンジをＮ
ｉルツボの内壁に設けたバスケット中に挿入し、そして
カソ−ドとしてＴｉ棒をＮｉルツボの中心に配置する。
これらは全てＡｒ置換された密封容器中に入れられる。Next, a specific example of molten salt electrolytic refining of Ti will be specifically shown. First, the salt to be used is thoroughly vacuum dried and dehydrated in advance,
It is necessary to remove water and the like. And Ni
NaCl-KCl (molar ratio = 40-60: 6 in crucible)
0-40) and put the crude Ti sponge which is an anode into N
Insert into a basket provided on the inner wall of the i crucible, and place a Ti rod as a cathode in the center of the Ni crucible.
All of these are placed in a sealed container with Ar substitution.
【００１２】そして、加熱することにより、ＮａＣｌ−
ＫＣｌを溶融状態にした後、ＴｉＣｌ4を導入する。こ
れにより、浴中で以下の反応を進行せしめ、ＮａＣｌ−
ＫＣｌ浴中にＴｉＣｌ2、ＴｉＣｌ3を生成せしめる。
が主反応である。 ＴｉＣｌ4＋Ｔｉ→２ＴｉＣｌ2 …………… ＴｉＣｌ2＋ＴｉＣｌ4→２ＴｉＣｌ3 ……… これにより、ＮａＣｌ−ＫＣｌ−ＴｉＣｌ2−ＴｉＣｌ3
（モル比：ＮａＣｌ：ＫＣｌ＝４０〜６０：６０〜４
０，Ｔｉ＝１〜４ｗｔ％）の溶融塩電解浴ができる。そ
して、これにアルカリ金属弗化物０．３〜１０ｗｔ％添
加した後、電解を行う。Then, by heating, NaCl-
After bringing KCl into a molten state, TiCl 4 is introduced. This allows the following reactions to proceed in the bath, NaCl-
TiCl 2 and TiCl 3 are formed in the KCl bath.
Is the main reaction. TiCl 4 + Ti → 2TiCl 2 …………… TiCl 2 + TiCl 4 → 2TiCl 3 ……… As a result, NaCl-KCl-TiCl 2 -TiCl 3
(Molar ratio: NaCl: KCl = 40-60: 60-4
(0, Ti = 1 to 4 wt%) molten salt electrolytic bath can be formed. Then, after adding 0.3 to 10 wt% of alkali metal fluoride to this, electrolysis is performed.
【００１３】溶融塩電解浴中のＴｉ濃度は、添加するＴ
ｉＣｌ4により決まるが、上記、の反応を考慮に入
れＴｉ濃度として、１〜４ｗｔ％になるようにＴｉＣｌ
4を添加することが好ましく、より好ましいＴｉ濃度
は、１．５〜３ｗｔ％である。この範囲内では、電流効
率も良く、電析状態は樹枝状となり、粒の大きさも大き
い。しかし、１ｗｔ％未満であると、カソ−ド棒に電着
しなかったり、電流効率が非常に低いものとなってしま
い好ましくない。また、電着したＴｉの粒度も非常に小
さくなる。４ｗｔ％を超えると、電流効率が低くなり、
電析形態もスポンジ状となり、Ｔｉに付着した溶融塩等
の分離が不十分となり、高純度のＴｉが得にくい。The concentration of Ti in the molten salt electrolytic bath depends on the T added.
It depends on iCl 4 , but the Ti concentration should be 1 to 4 wt% in consideration of the above reaction.
4 is preferably added, and a more preferable Ti concentration is 1.5 to 3 wt%. Within this range, the current efficiency is good, the electrodeposition is dendritic, and the size of the particles is large. However, if it is less than 1 wt%, it is not preferable because the cathode rod is not electrodeposited or the current efficiency is very low. Also, the grain size of electrodeposited Ti is very small. If it exceeds 4 wt%, the current efficiency becomes low,
The electrodeposited form is also sponge-like, and the separation of molten salts and the like adhering to Ti is insufficient, and it is difficult to obtain high-purity Ti.
【００１４】初期カソ−ド電流密度は、０．０１〜２Ａ
／ｃｍ2が好ましく、より好ましくは０．１〜１．０Ａ
／ｃｍ2である。電流密度が、上記の電流密度より低い
場合は、電流効率が低く、時間もかかるため生産性が低
く、好ましくない。一方、２．０Ａ／ｃｍ2より高い場
合は、粒が小さくなるため、カソ−ドに付着することが
少なく、仮りに得られたとしても、スポンジ状であるた
め好ましくない。The initial cathode current density is 0.01 to 2 A.
/ Cm 2 is preferable, more preferably 0.1 to 1.0 A
/ Cm 2 . When the current density is lower than the above current density, the current efficiency is low and it takes time, so that the productivity is low, which is not preferable. On the other hand, if it is higher than 2.0 A / cm 2 , the particles are small and the particles are less likely to adhere to the cathode, and even if it is obtained, it is spongy, which is not preferable.
【００１５】電解温度は、６００〜９００℃が好まし
く、より好ましくは、６５０〜８５０℃である。上記の
温度より低い場合は、結晶性の良いＴｉが得られにく
く、また電流効率も低く好ましくない。電解温度が９０
０℃よりも高い場合は、浴の蒸発が多くなり、また、電
流効率も低くなるため、好ましくない。The electrolysis temperature is preferably 600 to 900 ° C, and more preferably 650 to 850 ° C. If the temperature is lower than the above temperature, Ti with good crystallinity is difficult to obtain, and the current efficiency is low, which is not preferable. Electrolysis temperature is 90
When the temperature is higher than 0 ° C., the evaporation of the bath increases and the current efficiency also decreases, which is not preferable.
【００１６】電解を終了したならば、カソ−ドに電着し
たＴｉを引き上げ、冷却後脱着し、水洗を行なう。その
後、Ｔｉの表面をフッ化水素−硝酸で洗浄し、次いでエ
タノ−ルで洗浄する。そして最後に、真空乾燥する。さ
らに精製が切望される場合は、上記の溶融塩電解精製を
繰り返す。When the electrolysis is completed, the Ti electrodeposited on the cathode is pulled up, cooled and then desorbed, and washed with water. Then, the surface of Ti is washed with hydrogen fluoride-nitric acid and then with ethanol. And finally, it is vacuum dried. When further refining is desired, the above-described molten salt electrolytic refining is repeated.
【００１７】以下、本発明の実施例及び比較例について
説明する。Examples of the present invention and comparative examples will be described below.
【００１８】[0018]
【実施例１】あらかじめ、表１に示すような純度の原料
である粗Ｔｉスポンジ１０ｋｇを含む約７５０℃で溶融
状態のＮａＣｌ−ＫＣｌ（モル比＝４５：５５）浴１５
ｋｇ中に、ＴｉＣｌ4６００ｇを導入する。これによ
り、浴中で上記、の反応が進行し、ＮａＣｌ−ＫＣ
ｌ浴中にＴｉＣｌ2、ＴｉＣｌ3が生成する。この結果、
浴中のＴｉ濃度が、約２．０ｗｔ％となった。この浴に
対してＮａＦ１ｗｔ％添加して、浴を調整した。Example 1 A NaCl-KCl (molar ratio = 45: 55) bath 15 in a molten state at about 750 ° C. containing 10 kg of crude Ti sponge as a raw material having a purity shown in Table 1 in advance.
600 kg of TiCl 4 are introduced into kg. As a result, the above reaction proceeds in the bath, and NaCl-KC
In the 1-bath, TiCl 2 and TiCl 3 are produced. As a result,
The Ti concentration in the bath became about 2.0 wt%. The bath was adjusted by adding 1 wt% of NaF to this bath.
【００１９】この浴を使用し、粗Ｔｉスポンジをアノ−
ド、Ｔｉ棒をカソ−ドにして、電解温度７２０℃，初期
カソ−ド電流密度０．３Ａ／ｃｍ2の電解条件で、カソ
−ドに高純度のＴｉを１ｋｇ電析させた。電析Ｔｉを純
水で洗浄し、フッ酸−硝酸による酸洗及びエタノ−ル洗
浄を行なった後、６０℃で真空乾燥を行った。得られた
Ｔｉの分析値を表１に示す。Using this bath, a crude Ti sponge is anodized.
1 kg of high-purity Ti was electrodeposited on the cathode under the electrolysis conditions of an electrolysis temperature of 720 ° C. and an initial cathodic current density of 0.3 A / cm 2 , using the cathode and Ti rod as the cathode. The electrodeposited Ti was washed with pure water, pickled with hydrofluoric acid-nitric acid and ethanol washed, and then vacuum dried at 60 ° C. Table 1 shows the obtained Ti analysis values.
【００２０】[0020]
【実施例２】溶融塩中のＮａＦ濃度を５ｗｔ％とした以
外は、実施例１と同様に電解を行った。結果を表１に示
す。Example 2 Electrolysis was performed in the same manner as in Example 1 except that the concentration of NaF in the molten salt was 5 wt%. The results are shown in Table 1.
【００２１】[0021]
【比較例】溶融塩中にＮａＦを添加しない以外は、実施
例１と同様に電解を行った。結果を表１に示す。Comparative Example Electrolysis was performed in the same manner as in Example 1 except that NaF was not added to the molten salt. The results are shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１から明らかなように、ＮａＦを１及び
５ｗｔ％添加した実施例１及び２ではＮａＦを添加しな
い比較例と比較して、不純物であるＦｅ、Ｃｒ、Ｃｕが
０．０５ｐｐｍ未満（分析下限以下）と極めて低くなっ
ていることが判る。As is clear from Table 1, in Examples 1 and 2 in which NaF was added at 1 and 5 wt%, Fe, Cr, and Cu as impurities were less than 0.05 ppm (compared with Comparative Example in which NaF was not added ( It can be seen that it is extremely low (below the lower limit of analysis).
【００２４】[0024]
（１）本発明により、極めて高純度のＴｉ（６Ｎレベル
以上）を容易に得ることができる。 （２）得られた高純度Ｔｉは、半導体デバイス製造用の
タ−ゲット材等として好適に用いられる。(1) According to the present invention, extremely high purity Ti (6N level or higher) can be easily obtained. (2) The obtained high-purity Ti is suitably used as a target material for manufacturing semiconductor devices.
Claims (2)
化物の溶質を用いる溶融塩電解法で粗Ｔｉを電解精製す
る方法において、溶融塩中にアルカリ金属弗化物を添加
して電解を行なうことを特徴とするＴｉの精製方法。1. In a method for electrolytically refining crude Ti by a molten salt electrolysis method using an alkali metal chloride-based solvent and a titanium chloride solute, alkali metal fluoride is added to the molten salt for electrolysis. A method for purifying Ti, comprising:
に対して０．３〜１０ｗｔ％であることを特徴とする請
求項１記載の方法。2. The method according to claim 1, wherein the addition amount of the alkali metal fluoride is 0.3 to 10 wt% with respect to the molten salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35154292A JPH06173065A (en) | 1992-12-09 | 1992-12-09 | Method for refining ti |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35154292A JPH06173065A (en) | 1992-12-09 | 1992-12-09 | Method for refining ti |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06173065A true JPH06173065A (en) | 1994-06-21 |
Family
ID=18417991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35154292A Pending JPH06173065A (en) | 1992-12-09 | 1992-12-09 | Method for refining ti |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06173065A (en) |
Cited By (8)
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|---|---|---|---|---|
| WO2004094312A1 (en) * | 2003-04-21 | 2004-11-04 | Sumitomo Titanium Corporation | Method of purifying metal salt, method of deacidifying titanium material and method of producing the same |
| CN103147096A (en) * | 2013-03-28 | 2013-06-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium |
| WO2016028009A1 (en) * | 2014-08-20 | 2016-02-25 | 서울대학교 산학협력단 | Method for preparing titanium by using electrowinning |
| WO2018216319A1 (en) * | 2017-05-22 | 2018-11-29 | 住友電気工業株式会社 | Method for producing titanium-plated member |
| WO2018216320A1 (en) * | 2017-05-22 | 2018-11-29 | 住友電気工業株式会社 | Molten salt titanium plating solution composition and method for manufacturing titanium-plated member |
| WO2020044841A1 (en) * | 2018-08-31 | 2020-03-05 | 東邦チタニウム株式会社 | Method for producing metal titanium |
| WO2022230403A1 (en) * | 2021-04-30 | 2022-11-03 | 東邦チタニウム株式会社 | Metal titanium production method and metal titanium electrodeposit |
| WO2023007918A1 (en) * | 2021-07-30 | 2023-02-02 | 東邦チタニウム株式会社 | Method for producing electrodeposit |
-
1992
- 1992-12-09 JP JP35154292A patent/JPH06173065A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004094312A1 (en) * | 2003-04-21 | 2004-11-04 | Sumitomo Titanium Corporation | Method of purifying metal salt, method of deacidifying titanium material and method of producing the same |
| CN103147096A (en) * | 2013-03-28 | 2013-06-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium |
| CN103147096B (en) * | 2013-03-28 | 2015-07-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium |
| US10465306B2 (en) | 2014-08-20 | 2019-11-05 | Snu R&Db Foundation | Method for preparing titanium by using electrowinning |
| WO2016028009A1 (en) * | 2014-08-20 | 2016-02-25 | 서울대학교 산학협력단 | Method for preparing titanium by using electrowinning |
| CN106574384B (en) * | 2014-08-20 | 2018-07-13 | 首尔大学校产学协力团 | The method for manufacturing titanium using strike |
| CN106574384A (en) * | 2014-08-20 | 2017-04-19 | 首尔大学校产学协力团 | Method for preparing titanium by using electrowinning |
| CN110582594A (en) * | 2017-05-22 | 2019-12-17 | 住友电气工业株式会社 | Molten salt titanium plating solution composition and method for producing titanium-plated member |
| WO2018216320A1 (en) * | 2017-05-22 | 2018-11-29 | 住友電気工業株式会社 | Molten salt titanium plating solution composition and method for manufacturing titanium-plated member |
| CN110475910A (en) * | 2017-05-22 | 2019-11-19 | 住友电气工业株式会社 | Plate the manufacturing method of titanium part |
| WO2018216319A1 (en) * | 2017-05-22 | 2018-11-29 | 住友電気工業株式会社 | Method for producing titanium-plated member |
| JPWO2018216319A1 (en) * | 2017-05-22 | 2020-03-19 | 住友電気工業株式会社 | Manufacturing method of titanium plated member |
| JPWO2018216320A1 (en) * | 2017-05-22 | 2020-03-19 | 住友電気工業株式会社 | Molten salt titanium plating solution composition and method for producing titanium plated member |
| WO2020044841A1 (en) * | 2018-08-31 | 2020-03-05 | 東邦チタニウム株式会社 | Method for producing metal titanium |
| JPWO2020044841A1 (en) * | 2018-08-31 | 2021-08-26 | 東邦チタニウム株式会社 | Manufacturing method of metallic titanium |
| US11649554B2 (en) | 2018-08-31 | 2023-05-16 | Toho Titanium Co., Ltd. | Method for producing metal titanium |
| WO2022230403A1 (en) * | 2021-04-30 | 2022-11-03 | 東邦チタニウム株式会社 | Metal titanium production method and metal titanium electrodeposit |
| WO2023007918A1 (en) * | 2021-07-30 | 2023-02-02 | 東邦チタニウム株式会社 | Method for producing electrodeposit |
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