JP2939359B2 - Method for producing titanium suboxide - Google Patents
Method for producing titanium suboxideInfo
- Publication number
- JP2939359B2 JP2939359B2 JP12469391A JP12469391A JP2939359B2 JP 2939359 B2 JP2939359 B2 JP 2939359B2 JP 12469391 A JP12469391 A JP 12469391A JP 12469391 A JP12469391 A JP 12469391A JP 2939359 B2 JP2939359 B2 JP 2939359B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- powder
- titanium dioxide
- suboxide
- titanium suboxide
- 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.)
- Expired - Lifetime
Links
- 239000010936 titanium Substances 0.000 title claims description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052719 titanium Inorganic materials 0.000 title description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000004408 titanium dioxide Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000008188 pellet Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- -1 titanium hydride Chemical compound 0.000 claims description 11
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000011978 dissolution method Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000007740 vapor deposition Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RKPRRHKPZCIEDP-UHFFFAOYSA-N [Ti].N#[N+][O-] Chemical compound [Ti].N#[N+][O-] RKPRRHKPZCIEDP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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 as a colored pigment, a conductive filler, a vapor deposition material 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 Unlike titanium dioxide, titanium suboxide produces various colors such as brown, gray, black-purple or black by a reduction reaction, and has good conductive properties. It is widely used as a conductive filler, but has recently been used as a vapor deposition material for forming a titanium dioxide thin film on a substrate surface in fields such as optical systems and optoelectronics.
【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, means for producing titanium suboxide include:
A method in which titanium dioxide is reduced at a high temperature with a gas such as hydrogen or ammonia (Japanese Patent Publication No. 59-50604, Japanese Patent Application Laid-Open No. 57-2053).
No. 22), a method of heating a mixture of titanium dioxide and metallic titanium in a vacuum or in a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432).
Is known as a typical technique. These methods utilize a reduction reaction based on the solid-phase or gas-phase or solid-solid system raw material composition, and the obtained titanium suboxide is generally TiO, Ti 2 O 3 , Ti 3 O 5 , Ti 4 O 7 ,
Has the composition Ti 5 O 9, each 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。[0004] coating of titanium dioxide with nitrous oxide titanium deposition material, resistance heating, are formed by a method of vacuum deposition on a substrate surface after dissolved in an electron beam heating or the like, this time, said TiO and Ti 2 O 3 causes gas absorption and 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 reduced pressure and high temperature atmosphere, but the titanium suboxide sintered body represented by Ti 3 O 5 manufactured by the above-mentioned conventional technique (hereinafter simply referred to as titanium suboxide). ) Is a vapor deposition material, splash phenomena in a vacuum heating state occur remarkably frequently. When a large number of splash phenomena occur, not only does uniform deposition on the substrate surface be hindered, but also problems such as deposition of deposits on the deposition apparatus and oxidation deterioration of the electron gun filament are caused. To avoid this phenomenon,
It is possible to perform the filming operation after the splash has subsided, but in this case, time loss is increased.
Therefore, it is considered that the requirements for a titanium dioxide-forming thin film material are those which do not generate gas or absorb gas, 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) 。[0005] As a method for producing titanium suboxide effective to solve 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 a temperature range of 700 to 1600 ° C. Has been developed by the present applicant (JP-A-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,
Splashes and outgassing are significantly reduced compared to the conventional technology because the manufactured titanium suboxide has a particle state suitable for vapor deposition and the content of gas components and impurities is effectively reduced. It is possible to do.
However, the titanium suboxide obtained by this method has few impurities and no gas generation, but its 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。[0007] The present invention is directed to a method for producing titanium suboxide for a vapor deposition material by a process completely different from the conventional production technology of reducing and sintering titanium dioxide to obtain titanium suboxide. It is an object of the present invention to provide a method for producing titanium oxide for vapor deposition, which can effectively reduce a splash phenomenon in a 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（Ｔｉ 3 Ｏ 5 ）
の製造方法は、二酸化チタンと、金属チタン粉末および
／または水素化チタン粉末とを、重量比で８〜９：１の
割合で混合して得られる混合物をペレット状に成形し、
大気圧より加圧状態の不活性ガス雰囲気下で非消耗アー
ク溶解法によって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。In order to achieve the above object, the present invention provides a titanium oxide (Ti 3 O 5 ) for a vapor deposition material according to the present invention.
Is produced by mixing titanium dioxide and metal titanium powder and / or titanium hydride powder in a weight ratio of 8 to 9: 1.
The mixture obtained by mixing at a ratio is formed into a pellet,
It is characterized in that it is obtained by melting by a non-consumable arc melting method in an inert gas atmosphere at a pressure higher than atmospheric pressure .
【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
金属チタンおよび／または水素化チタンも粉末として使
用されるが、該金属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 as a raw material of the present invention may be produced by any of a sulfuric acid method and a chlorine method.
The crystal type may be any of anatase type, rutile type and brookite type. Although the titanium dioxide is used as a powder, its particle size is not particularly limited. However, it is preferable that the purity as titanium dioxide is as high as possible. Titanium dioxide and / or titanium hydride, which is the other raw material used in common with titanium dioxide, is also used as a powder, and a commercially available metal powder can be usually appropriately selected and used.
【００１０】上記の原料は、二酸化チタンと、金属チタ
ン粉末および／または水素化チタン粉末との混合物と
し、予めペレット状に成形したのち非消耗アーク溶解工
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。金属チタン粉末
および／または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-mentioned raw material is made into a mixture of titanium dioxide, metal titanium powder and / or titanium hydride powder, and is formed into pellets in advance, and then subjected to a non-consumable arc melting step. Pellet molding is performed using a usual hydraulic or mechanical press machine, but an appropriate binder component may be added as needed to prevent galling of the mold and improve the releasability. When mixing the titanium metal powder and / or the titanium hydride powder with the titanium dioxide powder, the mixing ratio is set in a range of 1: 8 to 9 by weight and mixed by a dry or 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が大気圧より加圧
状態で保持された非消耗アーク溶解炉に移し、炉内の水
冷ハースに充填した後、所定の電圧を印加することによ
っておこなわれる。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に大気
圧より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
によって行われる。In the melting step, the raw material pellets are pressurized in an atmosphere of an inert gas such as argon or helium.
It is carried out by transferring to a non-consumable arc melting furnace maintained in a state, filling a water-cooled hearth in the furnace, and applying a predetermined voltage. Suitable dissolution conditions, the air atmosphere in the furnace to the extent capable of preventing convection between the atmosphere by argon
This is performed by non-consumable arc melting in which a current and a voltage to be applied are set in an appropriate range in accordance with the amount ratio of the raw materials while maintaining a pressure state from a pressure.
【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（Ｔｉ 3 Ｏ 5 ）を製品として取り
出す。After melting, the furnace is cooled in an inert gas atmosphere.
The generated titanium suboxide (Ti 3 O 5 ) 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、
金属チタン粉末および／または水素化チタン粉末とを、
重量比で８〜９：１の割合で混合して得られる混合物を
ペレット状に成形し、単に大気圧より加圧状態の不活性
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に大気圧より
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Ｔｉ 3 Ｏ 5
を主体とする亜酸化チタンを効率良く製造し得る。According to the present invention, there is provided titanium dioxide as a raw material,
Metal titanium powder and / or titanium hydride powder ,
The mixture obtained by mixing at a weight ratio of 8 to 9: 1 is formed into pellets, and is simply melted by non-consumable arc melting under an inert gas atmosphere under a pressure of atmospheric pressure.
It is converted into titanium oxide in a low oxidation form mainly composed of Ti 3 O 5 in a short time of about one minute. At this time, since the dissolving step is performed under a pressure higher than the atmospheric pressure to the extent that convection can be prevented by an inert gas such as argon, and the dissolution is completed in a short time, contamination by the air is removed. , High purity Ti 3 O 5
It can efficiently produce the titanium suboxide mainly composed of.
【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（Ｔｉ 3 Ｏ 5 ）を製造することが可能となる。Through such an operation, it is possible to produce high-quality titanium suboxide (Ti 3 O 5 ) which does not cause a splash phenomenon in a 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。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20
g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20V 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。Hereinafter, examples of the present invention will be described in comparison with comparative examples. Example 1 A titanium hydride powder having a particle size of 45 μm or less and a titanium dioxide powder were mixed at a weight ratio of 1: 9, and mixed with a dry mixer for 12 hours. This mixed powder was formed into tablet-shaped pellets having a diameter of 10 mm and a thickness of 4 mm using a mechanical press forming apparatus. Then
Transfer the pellets to a copper water-cooled hearth of a non-consumable arc furnace for 20 minutes.
After filling the furnace and completely replacing the inside of the furnace with argon gas, applying a current of 200 A and a voltage of 20 V for 10 minutes while applying a pressure of 20 A to the arc while maintaining the pressure slightly higher than the atmospheric pressure with argon. The atmosphere was kept 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。The obtained product was measured by a powder X-ray diffraction method. As a result, it was confirmed that the 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75g 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 the tablet-shaped pellets was changed to 75 g. As a result, the same results as in Example 1 were obtained.
【００１８】実施例３ 水酸化チタン粉末に代えて金属チタン粉末を用い、錠剤
形ペレットの大きさを直径20mm、厚さ10mmとして140g充
填し、電流400A、電圧30V を印加した以外は実施例１と
同様にして、Ｔｉ3 Ｏ5 の組成を有する亜酸化チタンを
得た。この亜酸化チタン試料を用いて実施例１と同様に
して観察を行なった結果、スプラッシュ現象はみられな
かった。Example 3 Example 1 was repeated except that a titanium pellet was used in place of the titanium hydroxide powder, and the tablet-shaped pellet was filled with 140 g with a diameter of 20 mm and a thickness of 10 mm, and a current of 400 A and a voltage of 30 V were applied. In the same manner as in the above, titanium suboxide having a composition of Ti 3 O 5 was obtained. As a result of observation using the titanium suboxide sample in the same manner as in Example 1, no splash phenomenon was observed.
【００１９】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, mixed for 12 hours by a dry mixer, and then formed into a tablet having a diameter of 10 mm and a thickness of 4 mm using a mechanical molding press. It was formed into pellets. Then, the pellets were placed in a vacuum atmosphere furnace, and heated at a temperature of 1220 ° C. for 8 hours for reduction firing. The obtained sintered body had a black-purple color, and the compound composition was measured by powder X-ray diffraction. As a result, 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.
【００２０】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10m
m、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 A titanium hydride powder having a particle size of 45 μm or less and a titanium dioxide powder were blended at a weight ratio of 1: 9 and mixed in a dry mixer for 12 hours. This mixed powder is 10m in diameter using a hydraulic molding press
m, formed into 4 mm thick tablet-shaped pellets. Next, the pellets were filled in a vacuum atmosphere furnace, and heated and fired at 1300 ° C. for 3 hours while maintaining the inside of the furnace at a degree of vacuum 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 that the product was titanium suboxide having a composition of Ti 3 O 5 . This titanium suboxide sample was EB
Melting was performed in a melting furnace, and a number of splash phenomena were observed under a vacuum atmosphere.
【００２１】[0021]
【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、金属チタン粉末および／また
は水素化チタン粉末とを、重量比で８〜９：１の割合で
混合したのちペレット状に成形し、大気圧より加圧状態
の不活性ガス雰囲気下、非消耗アーク溶解法により溶解
することにより、Ｔｉ3 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、かつ短時間の処理で所期
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 firing method, titanium dioxide and titanium metal powder and / or titanium hydride powder are mixed at a weight ratio of 8 to 9: 1 . After that, it is formed into a pellet and pressurized from atmospheric pressure
An inert gas atmosphere, by dissolving the non-consumable arc melting method, titanium suboxides having a composition of Ti 3 O 5 is obtained. This titanium suboxide does not cause a splash phenomenon that occurs under vacuum heating at the time of vapor deposition as seen in conventional titanium suboxide, and is a vapor deposition material that can always form a smooth high quality titanium-based vapor deposition thin film. It became possible to provide. Further, the method of the present invention, the process is simplified, without requiring special considerations with the device, and since that can produce a desired product in the processing of short time, is improved by a large margin in terms of cost .
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 23/04 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) C01G 23/04
Claims (2)
／または水素化チタン粉末とを、重量比で８〜９：１の
割合で混合して得られる混合物をペレット状に成形し、
大気圧より加圧状態の不活性ガス雰囲気下で非消耗アー
ク溶解法によって溶解して得られることを特徴とするＴ
ｉ 3 Ｏ 5 の製造方法。1. A titanium dioxide and a metal titanium powder and / or a titanium hydride powder in a weight ratio of 8 to 9: 1.
The mixture obtained by mixing at a ratio is formed into a pellet,
T, characterized in that it is obtained by dissolving the non-consumable earth <br/> click dissolution method in an inert gas atmosphere under pressure above atmospheric pressure
A method for producing i 3 O 5 .
とを特徴とする請求項１記載のＴｉ 3 Ｏ 5 の製造方法。2. The method according to claim 1, wherein the inert gas is an argon gas.
The method for producing Ti 3 O 5 according to claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12469391A JP2939359B2 (en) | 1991-04-26 | 1991-04-26 | Method for producing titanium suboxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12469391A JP2939359B2 (en) | 1991-04-26 | 1991-04-26 | Method for producing titanium suboxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04325416A JPH04325416A (en) | 1992-11-13 |
| JP2939359B2 true JP2939359B2 (en) | 1999-08-25 |
Family
ID=14891757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12469391A Expired - Lifetime JP2939359B2 (en) | 1991-04-26 | 1991-04-26 | Method for producing titanium suboxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2939359B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011011954A (en) * | 2009-07-03 | 2011-01-20 | Toho Titanium Co Ltd | Method for producing titanium suboxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5301211B2 (en) * | 2008-07-23 | 2013-09-25 | 東邦チタニウム株式会社 | Method for producing titanium suboxide |
-
1991
- 1991-04-26 JP JP12469391A patent/JP2939359B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011011954A (en) * | 2009-07-03 | 2011-01-20 | Toho Titanium Co Ltd | Method for producing titanium suboxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04325416A (en) | 1992-11-13 |
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