JPH059028A - Production of titanium suboxide - Google Patents
Production of titanium suboxideInfo
- Publication number
- JPH059028A JPH059028A JP18547991A JP18547991A JPH059028A JP H059028 A JPH059028 A JP H059028A JP 18547991 A JP18547991 A JP 18547991A JP 18547991 A JP18547991 A JP 18547991A JP H059028 A JPH059028 A JP H059028A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- vacuum
- suboxide
- titanium dioxide
- atmosphere
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有色顔料、導電性フィ
ラー、蒸着材等に用いる亜酸化チタンの製造方法に係
り、中でも蒸着材として好適な亜酸化チタンの製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing titanium suboxide used for colored pigments, conductive fillers, vapor deposition materials and the like, and more particularly to a method for producing titanium suboxide suitable as a vapor deposition material.
【０００２】[0002]
【従来の技術】亜酸化チタンは、二酸化チタンとは異な
り還元反応によって茶褐色、灰色、黒紫色あるいは黒色
など多様な色調を現出するうえに、良好な導電性能を有
するため有色顔料や各種材料の導電性フィラーとして汎
用されているが、近時、光学系、オプトエレクトロニク
ス等の分野で基材面に二酸化チタンの薄膜を形成するた
めの蒸着材料として利用が図られている。2. Description of the Related Art Titanium suboxide, unlike titanium dioxide, exhibits various color tones such as brownish brown, gray, black purple or black due to a reduction reaction, and also has good conductivity, so that it can be used as a color pigment or various materials. Although it is widely used as a conductive filler, it has recently been used as a vapor deposition material for forming a thin film of titanium dioxide on the surface of a substrate in the fields of optical systems, optoelectronics, and the like.
【０００３】従来、亜酸化チタンを製造する手段には、
二酸化チタンを水素またはアンモニア等のガスで高温還
元する方法（特公昭59−50604 号公報、特開昭57−2053
22号公報) 、二酸化チタンと金属チタンの混合物を真空
中または還元雰囲気中で加熱する方法（特開昭49−5432
号公報) が典型的な技術として知られている。これらの
方法は固相−気相系あるいは固相−固相系の原料組成に
よる還元反応を利用するもので、得れる亜酸化チタンは
一般にＴｉＯ、Ｔｉ2 Ｏ3 、Ｔｉ3 Ｏ5 、Ｔｉ4 Ｏ 7、
Ｔｉ5 Ｏ9 の組成を有し、いずれも焼結体である。Conventionally, the means for producing titanium suboxide has been
A method of reducing titanium dioxide at a high temperature with a gas such as hydrogen or ammonia (Japanese Patent Publication No. 59-50604, JP-A No. 57-2053).
22), a method of heating a mixture of titanium dioxide and metallic titanium in a vacuum or a reducing atmosphere (JP-A-49-5432).
Is known as a typical technique. These methods solid phase - gas phase system or solid - utilizes a reduction reaction with the raw material composition of the solid phase system, titanium suboxide that is obtained is typically TiO, Ti 2 O 3, Ti 3 O 5, Ti 4 O 7 ,
It has a composition of Ti 5 O 9 and is a sintered body.
【０００４】亜酸化チタン蒸着材による二酸化チタンの
被膜は、抵抗加熱、電子ビーム加熱等で溶解したのち基
材面に真空蒸着する方法で形成されるが、この際、前記
のＴｉＯやＴｉ2 Ｏ3 はガス吸収作用を起し、またＴｉ
4 Ｏ 7やＴｉ5 Ｏ9 は逆にガス発生作用を起して真空槽
内の雰囲気を一定に保ち得ない。その点、Ｔｉ3 Ｏ5 は
減圧、高温雰囲気下で極めて安定であるが、前記の従来
技術で製造されたＴｉ3 Ｏ5 で表わされる亜酸化チタン
焼結体（以下、単に亜酸化チタンという。）を蒸着材と
した場合には、真空加熱状態でのスプラッシュ現象が著
しく多発する。スプラッシュ現象が多く発生すると、基
材面への均一な蒸着が阻害されるばかりでなく、蒸着装
置に蒸着物が付着したり、電子銃フィラメントが酸化変
質する等のトラブルを招く。この現象を避けるために、
スプラッシュが鎮静化してから膜付け操作をおこなうこ
ともできるが、この場合には時間のロスが大きくなる。
従って、二酸化チタン形成薄膜材料に求められる要件
は、ガス発生やガス吸収を起さず、かつスプラッシュ現
象を生起せず、不純物の少ないものが好ましいとされて
いる。The titanium dioxide film formed by the titanium suboxide vapor deposition material is formed by a method in which it is melted by resistance heating, electron beam heating or the like and then vacuum deposited on the surface of the substrate. At this time, the above-mentioned TiO or Ti 2 O is used. 3 causes gas absorption, and also Ti
On the contrary, 4 O 7 and Ti 5 O 9 cause a gas generating action and cannot keep the atmosphere in the vacuum chamber constant. In that respect, Ti 3 O 5 is extremely stable under a reduced pressure and high temperature atmosphere, but the titanium suboxide sintered body represented by Ti 3 O 5 produced by the above-mentioned conventional technique (hereinafter, simply referred to as titanium suboxide). When () is used as the vapor deposition material, the splash phenomenon in a vacuum heated state remarkably frequently occurs. If many splash phenomena occur, not only the uniform vapor deposition on the surface of the base material is hindered but also the vapor deposition material adheres to the vapor deposition device, and the electron gun filament is oxidized and deteriorated. To avoid this phenomenon,
It is possible to carry out the film forming operation after the splash has subsided, but in this case, the time loss becomes large.
Therefore, the requirements for the titanium dioxide-forming thin film material are preferably those that do not cause gas generation or gas absorption, do not cause a splash phenomenon, and have few impurities.
【０００５】このような問題を解消するために有効な亜
酸化チタンの製造方法として、粒度80μm 以下の水素化
チタン粉末と二酸化チタンとの混合物をペレット状に成
形し、 700〜1600℃の温度域において真空または不活性
ガス雰囲気下で加熱焼成する技術が、本出願人によって
開発されている（特開平１−290529号公報) 。As a method for producing titanium suboxide which is effective for solving such a problem, a mixture of titanium hydride powder having a particle size of 80 μm or less and titanium dioxide is formed into pellets, and the temperature range of 700 to 1600 ° C. In the above, a technique of heating and firing in a vacuum or in an inert gas atmosphere has been developed by the present applicant (Japanese Patent Laid-Open No. 1-290529).
【０００６】[0006]
【発明が解決しようとする課題】該先行技術によれば、
製造される亜酸化チタンが蒸着に好適な粒子状態を呈し
ており、またガス成分や不純物の含有量を効果的に低減
化されているため、スプラッシュやアウトガスの発生は
従来技術に比べてかなり減少させることが可能となる。
しかしながら、この製法で得られる亜酸化チタンは不純
物も少なくガス発生もないが、スプラッシュ現象に対す
る防止効果については十分とはいえない。According to the prior art,
Since the produced titanium suboxide has a particle state suitable for vapor deposition and the content of gas components and impurities is effectively reduced, the generation of splash and outgas is considerably reduced compared to the conventional technology. It becomes possible.
However, the titanium suboxide obtained by this production method has few impurities and does not generate gas, but the effect of preventing the splash phenomenon is not sufficient.
【０００７】本発明は、二酸化チタンを還元・焼結して
亜酸化チタンを得るというこれまでの製造技術とは全く
異なるプロセスによって蒸着材用亜酸化チタンを製造す
る方法を対象とするもので、その目的は蒸着時の真空加
熱段階におけるスプラッシュ現象を効果的に低減化し得
る蒸着用亜酸化チタンの製造方法を提供することにあ
る。The present invention is directed to a method for producing titanium suboxide for a vapor deposition material by a process which is completely different from the conventional production technique of reducing and sintering titanium dioxide to obtain titanium suboxide. An object of the invention is to provide a method for producing titanium suboxide for vapor deposition, which can effectively reduce the splash phenomenon in the vacuum heating stage during vapor deposition.
【０００８】[0008]
【課題を解決するための手段】上記の目的を達成するた
めの本発明による蒸着材用亜酸化チタンの製造方法は、
二酸化チタンと、水素化チタン粉末との混合物をペレッ
ト状に成形した後、該ペレットを真空雰囲気下において
加熱することにより脱水素処理を施し、次いで不活性ガ
ス雰囲気下で溶解して得られることを構成上の特徴とす
るものである。The method for producing titanium suboxide for a vapor deposition material according to the present invention for achieving the above object comprises:
After forming a mixture of titanium dioxide and titanium hydride powder into pellets, the pellets are heated in a vacuum atmosphere for dehydrogenation, and then dissolved in an inert gas atmosphere. This is a feature of the configuration.
【０００９】本発明の原料となる二酸化チタンは、硫酸
法、塩素法のいずれの方法で製造されたものでもよく、
また結晶型はアナターゼ型、ルチル型、ブルカイト型の
いずれであっても差し支えない。該二酸化チタンは粉末
として使用されるが、その粒度には特に制約はない。た
だし、二酸化チタンとしての純度が可能な限り高いもの
が好ましい。二酸化チタンと共用する他方の原料となる
水素化チタンも粉末として使用されるが、該水素化チタ
ン粉末は通常市販のものを適宜選択して用いることがで
きる。The titanium dioxide used as the raw material of the present invention may be produced by either the sulfuric acid method or the chlorine method,
The crystal type may be any of anatase type, rutile type and brookite type. The titanium dioxide is used as a powder, but its particle size is not particularly limited. However, it is preferable that the purity of titanium dioxide is as high as possible. Titanium hydride, which is the other raw material shared with titanium dioxide, is also used as a powder, and a commercially available titanium hydride powder can be appropriately selected and used.
【００１０】上記の原料は、二酸化チタンと、水素化チ
タン粉末との混合物とし、該混合物を予めペレット状に
成形したのち、真空雰囲気下において、電気炉等により
所定の温度域、好ましくは 400〜800 ℃に加熱すること
により脱水素処理を施し、次いで溶解工程にかけられ
る。ペレット成形は、通常の油圧式または機械式のプレ
ス装置を用いておこなわれるが、金型のかじり防止と離
型性を良くするため必要に応じて適宜なバインダー成分
を添加してもかまわない。水素化チタン粉末と二酸化チ
タン粉末とを混合する際には、配合割合を重量比で１：
８〜９の範囲に設定し、乾式もしくは湿式法によって混
合される。The above raw material is a mixture of titanium dioxide and titanium hydride powder, and the mixture is preliminarily formed into pellets, and then, in a vacuum atmosphere, in a predetermined temperature range by an electric furnace or the like, preferably 400 to It is subjected to a dehydrogenation treatment by heating to 800 ° C, and then subjected to a melting step. Pellet molding is carried out using an ordinary hydraulic or mechanical press machine, but an appropriate binder component may be added if necessary in order to prevent galling of the mold and improve releasability. When the titanium hydride powder and the titanium dioxide powder are mixed, the mixing ratio is 1: 1 by weight.
It is set in the range of 8 to 9 and mixed by a dry method or a wet method.
【００１１】溶解工程は、原料ペレットをアルゴンまた
はヘリウムのような不活性ガス雰囲気下に保持された溶
解炉に移し、炉内の水冷ハースに充填した後、プラズマ
アーク溶解法、非消耗アーク溶解法、エレクトロスラグ
溶解法等を適宜に選択して行われるが、本発明において
は非消耗アーク溶解法が、装置が簡略で操作も容易であ
ることから好ましい。好適な溶解条件は、炉内の雰囲気
をアルゴンによって大気との対流を防止し得る程度の加
圧状態に保ちつつ、原料の量比に応じて印加する電流や
電圧を適宜の範囲に設定した非消耗アーク溶解によって
行なわれる。In the melting step, the raw material pellets are transferred to a melting furnace kept under an atmosphere of an inert gas such as argon or helium, filled in a water-cooled hearth in the furnace, and then plasma arc melting method or non-consumable arc melting method. The electroslag melting method or the like is appropriately selected, and the non-consumable arc melting method is preferable in the present invention because the apparatus is simple and the operation is easy. Suitable melting conditions are such that the current and voltage to be applied are set in an appropriate range according to the amount ratio of the raw materials while maintaining the atmosphere in the furnace in a pressurized state to prevent convection with the atmosphere by argon. It is done by consumable arc melting.
【００１２】溶解後は、不活性ガス雰囲気中で炉冷し、
生成した亜酸化チタンを製品として取り出す。After melting, the furnace is cooled in an inert gas atmosphere,
The produced titanium suboxide is taken out as a product.
【００１３】[0013]
【作用】本発明によれば、原料となる二酸化チタンと、
水素化チタン粉末との混合物をペレット状に成形し、単
に不活性ガス雰囲気下で非消耗アーク溶解することによ
り僅か10分程度の短時間でＴｉ3 Ｏ5 を主体とする低次
酸化形態の亜酸化チタンに転化する。この際、溶解工程
がアルゴン等の不活性ガスで対流を防止し得る程度の加
圧状態でおこなわれ、しかも短時間で溶解を終了するか
ら、大気による汚染は除去され、高純度の亜酸化チタン
を効率良く製造し得る。According to the present invention, titanium dioxide as a raw material,
A mixture of titanium hydride powder is formed into pellets and melted in a non-consumable arc in an inert gas atmosphere to form a sub-oxidized form mainly composed of Ti 3 O 5 in a short time of only about 10 minutes. Converts to titanium oxide. At this time, the melting step is carried out under a pressure condition that can prevent convection with an inert gas such as argon, and the melting is completed in a short time, so that the pollution by the atmosphere is removed, and high-purity titanium suboxide is used. Can be manufactured efficiently.
【００１４】このような作用を介して、蒸着時の真空加
熱段階でスプラッシュ現象を生じない高品質の亜酸化チ
タンを安価に製造することが可能となる。Through such an action, it becomes possible to inexpensively produce high-quality titanium suboxide that does not cause a splash phenomenon in the vacuum heating stage during vapor deposition.
【００１５】[0015]
【実施例】以下、本発明の実施例を比較例と対比して説
明する。
実施例１
粒径45μm 以下の水素化チタン粉末と、二酸化チタン粉
末を１：９の重量比で配合し、乾式混合機で12時間混合
した。この混合粉末を機械式のプレス成形装置を用いて
直径10mm、厚さ４mmの錠剤形ペレットとした。得られた
ペレットを石英製のルツボに入れて電気炉に移し、炉内
を１Torr以下の真空雰囲気に保持して、700 ℃で１時間
加熱することにより脱水素処理を施した後炉冷した。次
いで、このペレットを非消耗アーク炉の銅製の水冷ハー
スに40g 充填し、炉内をアルゴンガスで完全に置換した
後、アルゴンによって大気圧より若干加圧状態で保持し
しつつ、電流200A、電圧25V を印加して10分間アーク溶
解し、その後、炉内の雰囲気をそのまま保持して炉冷し
た。EXAMPLES Examples of the present invention will be described below in comparison with comparative examples. Example 1 Titanium hydride powder having a particle size of 45 μm or less and titanium dioxide powder were mixed in a weight ratio of 1: 9, and mixed for 12 hours with a dry mixer. This mixed powder was made into a tablet-shaped pellet having a diameter of 10 mm and a thickness of 4 mm by using a mechanical press molding device. The obtained pellets were placed in a quartz crucible, transferred to an electric furnace, and the inside of the furnace was maintained in a vacuum atmosphere of 1 Torr or less and heated at 700 ° C. for 1 hour to carry out dehydrogenation treatment and then cooled in the furnace. Next, 40 g of this pellet was charged into a copper water-cooled hearth in a non-consumable arc furnace, and after completely replacing the inside of the furnace with argon gas, while maintaining a pressure slightly higher than atmospheric pressure with argon, a current of 200 A, voltage was applied. 25 V was applied and arc melting was performed for 10 minutes, and then the furnace atmosphere was maintained as it was and the furnace was cooled.
【００１６】得られた生成物を粉末Ｘ線回折法で測定し
た結果、その化学組成はＴｉ3 Ｏ5 であることが確認さ
れた。この亜酸化チタン試料をＥＢ溶解炉で溶解し、真
空下におけるスプラッシュの状況を観察したところ、ス
プラッシュ現象は見られなかった。As a result of measuring the obtained product by powder X-ray diffractometry, it was confirmed that its chemical composition was Ti 3 O 5 . When this titanium suboxide sample was melted in an EB melting furnace and the state of splash under vacuum was observed, no splash phenomenon was observed.
【００１７】実施例２
錠剤形ペレットの量を140gとし、電流400A、電圧35V と
した以外は実施例１と同様にして実験を行なった結果、
実施例１と同様の成果が得られた。Example 2 An experiment was conducted in the same manner as in Example 1 except that the amount of tablet pellets was 140 g, the current was 400 A and the voltage was 35 V.
The same result as in Example 1 was obtained.
【００１８】比較例１
粒度45μm 以下の水素化チタン粉末555gと二酸化チタン
粉末4445g を配合し、乾式混合機で12時間混合したの
ち、機械式成形プレスを用いて直径10mm、厚さ４mmの錠
剤形ペレットに成形した。ついで、このペレットを真空
雰囲気炉に入れ、1220℃の温度で８時間加熱して還元焼
成した。得られた焼結体は黒紫色を呈しており、その化
合物組成を粉末Ｘ線回折法で測定した結果、Ｔｉ3 Ｏ5
であることが確認された。この亜酸化チタンをＥＢ溶解
炉で溶解し、真空下でスプラッシュの状況を観察したと
ころ、スプラッシュ現象が多く発生した。Comparative Example 1 555 g of titanium hydride powder having a particle size of 45 μm or less and 4445 g of titanium dioxide powder were blended and mixed in a dry mixer for 12 hours, and then a tablet form having a diameter of 10 mm and a thickness of 4 mm was formed using a mechanical molding press. Molded into pellets. Then, the pellets were put into a vacuum atmosphere furnace and heated at a temperature of 1220 ° C. for 8 hours for reduction firing. The obtained sintered body has a blackish purple color, and its compound composition was measured by powder X-ray diffractometry to find that Ti 3 O 5
Was confirmed. When this titanium suboxide was melted in an EB melting furnace and the state of splash was observed under vacuum, many splash phenomena occurred.
【００１９】比較例２
粒径45μm 以下の水素化チタン粉末と二酸化チタン粉末
とを１：９の重量比で配合し、乾式混合機で12時間混合
した。この混合粉末を油圧式成形プレスを用いて直径10
mm、厚さ４mmの錠剤形ペレットに成形した。次いで該ペ
レットを真空雰囲気炉に充填し、炉内を１Torr以下の真
空度に保持しながら、1300℃で３時間の加熱焼成を行っ
た後、炉冷した。得られた生成物を粉末Ｘ線回折法で測
定したところ、Ｔｉ3 Ｏ5 の組成を有する亜酸化チタン
であることが確認された。この亜酸化チタン試料をＥＢ
溶解炉で溶解し、真空雰囲気下におけるスプラッシュ現
象を観察したところ、多数のスプラッシュ現象が見られ
た。Comparative Example 2 Titanium hydride powder having a particle size of 45 μm or less and titanium dioxide powder were mixed in a weight ratio of 1: 9 and mixed for 12 hours with a dry mixer. This mixed powder was compressed to a diameter of 10 using a hydraulic molding press.
mm into a tablet-shaped pellet having a thickness of 4 mm. Next, the pellets were filled in a vacuum atmosphere furnace, heated and baked at 1300 ° C. for 3 hours while keeping the inside of the furnace at a vacuum degree of 1 Torr or less, and then cooled in the furnace. When the obtained product was measured by a powder X-ray diffraction method, it was confirmed to be titanium suboxide having a composition of Ti 3 O 5 . This titanium suboxide sample is EB
When it was melted in a melting furnace and the splash phenomenon was observed in a vacuum atmosphere, many splash phenomena were observed.
【００２０】[0020]
【発明の効果】本発明によれば、従来の還元焼成法とは
異なり、二酸化チタンと、水素化チタン粉末とを特定の
割合で混合したのちペレット状に成形し、該ペレットを
真空雰囲気下で加熱することにより脱水素処理を施した
ものを、不活性ガス雰囲気下で溶解することにより、Ｔ
ｉ3 Ｏ5 の組成を有する亜酸化チタンが得られる。この
亜酸化チタンは、従来の亜酸化チタンに見られる様な、
蒸着時の真空加熱下で発生するスプラッシュ現象が生起
せず、常に円滑な高品質のチタン系蒸着薄膜を形成し得
る蒸着材を提供することが可能となった。また、本発明
方法は、その工程が簡略であり、装置上とも特段の配慮
を要さず、かつ単時間の処理で所期の製品を製造し得る
為、コスト面でも大巾に改善される。According to the present invention, unlike the conventional reduction calcination method, titanium dioxide and titanium hydride powder are mixed at a specific ratio and then molded into pellets, and the pellets are placed in a vacuum atmosphere. By melting the dehydrogenated product by heating it under an inert gas atmosphere, T
Titanium suboxide having a composition of i 3 O 5 is obtained. This titanium suboxide is similar to that found in conventional titanium suboxide,
It has become possible to provide a vapor deposition material capable of forming a smooth and high quality titanium-based vapor deposition thin film without causing a splash phenomenon that occurs under vacuum heating during vapor deposition. In addition, the method of the present invention is simple in process, does not require special consideration on the apparatus, and can produce a desired product by a single-hour treatment, so that the cost is greatly improved. .
Claims (2)
混合物をペレット状に成形した後、該ペレットを真空雰
囲気下において、加熱することにより脱水素処理を施
し、次いで不活性ガス雰囲気下で溶解して得られること
を特徴とする亜酸化チタンの製造方法。1. A mixture of titanium dioxide and titanium hydride powder is molded into pellets, and the pellets are heated in a vacuum atmosphere for dehydrogenation, and then dissolved in an inert gas atmosphere. A method for producing titanium suboxide, which is obtained by
に保持し、非消耗アーク溶解法によって溶解する請求項
１記載の亜酸化チタンの製造方法。2. The method for producing titanium suboxide according to claim 1, wherein the atmosphere at the time of melting is maintained under an argon gas atmosphere and the melting is carried out by a non-consumable arc melting method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3185479A JP3069403B2 (en) | 1991-06-27 | 1991-06-27 | Method for producing titanium suboxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3185479A JP3069403B2 (en) | 1991-06-27 | 1991-06-27 | Method for producing titanium suboxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH059028A true JPH059028A (en) | 1993-01-19 |
| JP3069403B2 JP3069403B2 (en) | 2000-07-24 |
Family
ID=16171488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3185479A Expired - Fee Related JP3069403B2 (en) | 1991-06-27 | 1991-06-27 | Method for producing titanium suboxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3069403B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6699303B2 (en) | 2000-03-28 | 2004-03-02 | Dja Dodane Jean Et Associes Dja Cristel | Non-stick ceramo-metallic coating for cooking utensils |
| JP2008500939A (en) * | 2004-06-01 | 2008-01-17 | アトラバーダ リミテッド | Chemical reaction with reduced moisture |
| JP2010024111A (en) * | 2008-07-23 | 2010-02-04 | Toho Titanium Co Ltd | Method for producing titanium suboxide |
| WO2010064575A1 (en) * | 2008-12-04 | 2010-06-10 | 国立大学法人東京大学 | Titanium oxide particles, manufacturing method thereof, magnetic memory, and charge storage type memory |
| US8535816B2 (en) | 2008-12-25 | 2013-09-17 | The University Of Tokyo | Fine structural body, method for manufacturing fine structural body, magnetic memory, charge storage memory and optical information recording medium |
| JP2014144884A (en) * | 2013-01-28 | 2014-08-14 | Nisshin Seifun Group Inc | Nonstoichiometric oxide particle, and manufacturing method thereof |
| CN105887182A (en) * | 2014-12-15 | 2016-08-24 | 盱眙新远光学科技有限公司 | Preparation technology of trititanium pentoxide crystal |
| CN109110804A (en) * | 2018-11-09 | 2019-01-01 | 攀枝花学院 | Sub- titanium oxide of high-purity Magn é li phase and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5296619B2 (en) * | 2009-07-03 | 2013-09-25 | 東邦チタニウム株式会社 | Method for producing titanium suboxide |
-
1991
- 1991-06-27 JP JP3185479A patent/JP3069403B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6699303B2 (en) | 2000-03-28 | 2004-03-02 | Dja Dodane Jean Et Associes Dja Cristel | Non-stick ceramo-metallic coating for cooking utensils |
| JP2008500939A (en) * | 2004-06-01 | 2008-01-17 | アトラバーダ リミテッド | Chemical reaction with reduced moisture |
| JP2010024111A (en) * | 2008-07-23 | 2010-02-04 | Toho Titanium Co Ltd | Method for producing titanium suboxide |
| WO2010064575A1 (en) * | 2008-12-04 | 2010-06-10 | 国立大学法人東京大学 | Titanium oxide particles, manufacturing method thereof, magnetic memory, and charge storage type memory |
| US8609261B2 (en) | 2008-12-04 | 2013-12-17 | The University Of Tokyo | Titanium oxide particles, manufacturing method thereof, magnetic memory, and charge storage type memory |
| JP5549939B2 (en) * | 2008-12-04 | 2014-07-16 | 国立大学法人 東京大学 | Titanium oxide particles, manufacturing method thereof, magnetic memory and charge storage type memory |
| US8535816B2 (en) | 2008-12-25 | 2013-09-17 | The University Of Tokyo | Fine structural body, method for manufacturing fine structural body, magnetic memory, charge storage memory and optical information recording medium |
| JP2014144884A (en) * | 2013-01-28 | 2014-08-14 | Nisshin Seifun Group Inc | Nonstoichiometric oxide particle, and manufacturing method thereof |
| CN105887182A (en) * | 2014-12-15 | 2016-08-24 | 盱眙新远光学科技有限公司 | Preparation technology of trititanium pentoxide crystal |
| CN109110804A (en) * | 2018-11-09 | 2019-01-01 | 攀枝花学院 | Sub- titanium oxide of high-purity Magn é li phase and preparation method thereof |
| CN109110804B (en) * | 2018-11-09 | 2021-01-12 | 攀枝花学院 | High-purity magneli phase titanium suboxide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3069403B2 (en) | 2000-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7585486B2 (en) | Production of high-purity niobium monoxide and capacitor production therefrom | |
| KR101774319B1 (en) | Manufacturemethod for titanium powder | |
| JP2010180449A (en) | Target material of composite tungsten oxide, and method for manufacturing the same | |
| US9346715B2 (en) | Lanthanum hexaboride sintered body, target and lanthanum hexaboride film each comprising same, and process for production of the sintered body | |
| JPH059028A (en) | Production of titanium suboxide | |
| JP4060187B2 (en) | Method for producing ITO powder in which tin is dissolved in indium oxide and method for producing ITO target | |
| JP5296619B2 (en) | Method for producing titanium suboxide | |
| JP3186793B2 (en) | Method for producing titanium suboxide | |
| CN112250080B (en) | Method for preparing refractory metal boride in two steps | |
| JP5301211B2 (en) | Method for producing titanium suboxide | |
| JP3186788B2 (en) | Method for producing titanium suboxide | |
| KR102028184B1 (en) | Method for preparing titanium metal powder or titanium alloy powder | |
| JP2939359B2 (en) | Method for producing titanium suboxide | |
| JPH04224113A (en) | Production of titanium oxide for vapor deposition | |
| JPH0280318A (en) | Synthesis of refractory metal boride having predetermined particle dimension | |
| JP2008013396A (en) | Complex metal oxide and method for manufacturing electroconductive complex metal oxide | |
| JP3186789B2 (en) | Method for producing titanium suboxide | |
| JP2007045670A (en) | Manufacturing method of metal carbide | |
| US5011798A (en) | Chromium additive and method for producing chromium alloy using the same | |
| JPH04317413A (en) | Production of titanium suboxide | |
| JPH01290529A (en) | Production of high purity titanium suboxide | |
| JP4269830B2 (en) | Vapor deposition material | |
| KR100274094B1 (en) | Target for cathodic sputtering and method for producing the target | |
| JPH0525812B2 (en) | ||
| JP5426137B2 (en) | Tantalum oxide vapor deposition material, production method thereof, and production method of tantalum oxide vapor deposition film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 9 Free format text: PAYMENT UNTIL: 20090519 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090519 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090519 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100519 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100519 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 11 Free format text: PAYMENT UNTIL: 20110519 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110519 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |