JPH03162584A - Thin film of titanium-containing multiple oxide and production thereof - Google Patents
Thin film of titanium-containing multiple oxide and production thereofInfo
- Publication number
- JPH03162584A JPH03162584A JP30363989A JP30363989A JPH03162584A JP H03162584 A JPH03162584 A JP H03162584A JP 30363989 A JP30363989 A JP 30363989A JP 30363989 A JP30363989 A JP 30363989A JP H03162584 A JPH03162584 A JP H03162584A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- titanium oxide
- titanium
- oxide
- plate
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 52
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 22
- 239000010936 titanium Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、複合チタン酸化物薄膜とその製遣方法に関
するものである．さらに詳しくは、この発明は、水熱反
応によって形成する複合チタン酸化物薄膜とその製造方
法に関するものである．（従来の技術）
複合チタン酸化物薄膜は、コンデンサー材料をはじめと
して、種々の電子材料の誘電体、表面弾性体、センサー
等に用いられている．
従来、この複合チタン酸化物薄膜の形戒方法としては、
スパッタリングに代表される物理蒸着法や、ＣＶＤ，Ｍ
ＯＣＶＤ等に代表される化学蒸着法、あるいは基板に塗
布した有機金属を所定の温度で焼成し熟分解して酸化物
を得るというイＩ機金属塗布法が採用されてきている．
（発明が解決しようとする課題）
しかしながら、これら従来の形成方法にはそれぞれ改暮
すべき課題があった．
すなわち、スパッタリング等の物理蒸着法による場合に
は、複合チタン酸化物薄膜の成長速度が遅く、多大なエ
ネルギーを浪費するという欠点がある．さらに、基板温
度が低い場合には非晶質になりやすく、また、高い場合
には冷却時に熟歪みが生じ、クラックや剥離が生じやす
いという問題点らある．また、この方法は低酸素分圧下
で行うので形成した薄膜が多量の酸素欠陥を有すること
となり、半導体化しやすく、また、絶縁破壊電圧も低く
なりやすい．このために成膜後には焼鈍をしなくてはな
らないが、この焼鈍により形成した薄膜が基板と無用な
反応をしたり、基板から剥離したりするという欠点もあ
る．
ＣＶＤ法による場合には、原料に非常に活性で蒸発しや
すい有機金属を使用しなくてはならないのでその取扱が
めんどうであり、また、ＷＩ膜の製造コストも高くなる
．さらに、薄膜の成長速度が遅いなどの欠点もある．
また、有機金属塗布法による場合には、基板に塗布した
有機金属の焼或工程で大きな収縮が生じ、形成した薄膜
にクラヅクが発生しやすい．また、焼戊工程中の有機金
属の蒸発や燃焼により緻密な薄膜が得にくいという欠点
もある．
この発明は、以上の通りの事情に鑑みてなされたもので
あり、従来の複合チタン酸化物薄膜の形成方法の欠点を
解消し、簡便な方法により結晶性に優れた薄膜を得られ
るようにすることを目的としている．
（課題を解決するための手段）
この発明は、上記の課題を解決するため、チタンまたは
チタン酸化物を金属溶液中で水熱反応させ、その表面に
複合チタン酸化物薄膜を形成することを特徴とする複合
チタン酸化物薄膜の製造方法を提供し、また、この方法
により形成した複合チタン酸化物薄１模を提供する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention relates to a composite titanium oxide thin film and a method for producing the same. More specifically, the present invention relates to a composite titanium oxide thin film formed by a hydrothermal reaction and a method for producing the same. (Prior Art) Composite titanium oxide thin films are used as capacitor materials, dielectrics of various electronic materials, surface elastic materials, sensors, etc. Conventionally, the method for forming this composite titanium oxide thin film was as follows:
Physical vapor deposition methods such as sputtering, CVD, M
Chemical vapor deposition methods, such as OCVD, or organic metal coating methods, in which an organic metal coated on a substrate is baked at a predetermined temperature and then fully decomposed to obtain an oxide, have been adopted. (Problems to be solved by the invention) However, each of these conventional forming methods had their own problems that needed to be changed. That is, when physical vapor deposition methods such as sputtering are used, the growth rate of the composite titanium oxide thin film is slow and a large amount of energy is wasted. Furthermore, when the substrate temperature is low, it tends to become amorphous, and when the temperature is high, ripening distortion occurs during cooling, which causes cracks and peeling. In addition, since this method is carried out under a low oxygen partial pressure, the formed thin film will have a large amount of oxygen defects, making it easier to convert into a semiconductor and also tend to have a lower dielectric breakdown voltage. For this reason, it is necessary to perform annealing after film formation, but this has the disadvantage that the thin film formed by this annealing may cause unnecessary reactions with the substrate or may peel off from the substrate. When using the CVD method, it is necessary to use organic metals as raw materials that are very active and easily evaporate, which is troublesome to handle and also increases the manufacturing cost of the WI film. Furthermore, there are other drawbacks, such as the slow growth rate of thin films. Furthermore, when using an organic metal coating method, large shrinkage occurs during the baking process of the organic metal applied to the substrate, and cracks are likely to occur in the formed thin film. Another drawback is that it is difficult to obtain a dense thin film due to the evaporation and combustion of organic metals during the firing process. This invention was made in view of the above circumstances, and aims to eliminate the drawbacks of the conventional method of forming a composite titanium oxide thin film, and to make it possible to obtain a thin film with excellent crystallinity by a simple method. The purpose is to (Means for Solving the Problems) In order to solve the above problems, the present invention is characterized by subjecting titanium or titanium oxide to a hydrothermal reaction in a metal solution to form a composite titanium oxide thin film on the surface thereof. The present invention provides a method for manufacturing a composite titanium oxide thin film, and also provides a composite titanium oxide thin film 1 formed by this method.
この発明の方法は、チタンまたはチタン酸化物を金属溶
液中で水熱反応させるだけで、チタンまたはチタン酸化
物の表面に直接的に複合金属・チタン酸化物薄膜を形成
するものである．チタンまたはチタン酸化物としては種
々のものを使用することができ、たとえば、チタン金属
板、絶縁基板上にスパッタリング等により形成したチタ
ン金属薄膜、配向したチタン薄膜、酸化チタン板、酸化
チタン薄膜、これらの単結晶品または多孔質品などを用
いることができる．
このようなチタンまたはチタン酸化物と反応させる金属
溶液としては、バリウム、ストロンチウム、カルシウム
等の金属の｛ヒ合物、塩等からなる水溶液を使用するこ
とができる．
水熱反応には、たとえば通常のオートクレープを用いる
ことができる。オートクレープからなる反応装置として
は第１図のものを例示することができる。The method of this invention forms a composite metal/titanium oxide thin film directly on the surface of titanium or titanium oxide by simply subjecting titanium or titanium oxide to a hydrothermal reaction in a metal solution. Various types of titanium or titanium oxide can be used, such as a titanium metal plate, a titanium metal thin film formed by sputtering or the like on an insulating substrate, an oriented titanium thin film, a titanium oxide plate, a titanium oxide thin film, etc. Single crystal products or porous products can be used. As the metal solution to be reacted with such titanium or titanium oxide, an aqueous solution consisting of arsenide, salt, etc. of metals such as barium, strontium, and calcium can be used. For example, an ordinary autoclave can be used for the hydrothermal reaction. As an example of a reaction apparatus consisting of an autoclave, the one shown in FIG. 1 can be exemplified.
同図のオートクレープ（１）は、外容器（２）の外周に
ヒーター（３）を設けている．内容器（４）はテフ口ン
等で製造されており、金属チタン板またはチタン酸化物
板（５）を設置し、金属溶：ａ（６）を入れられるよう
にしている．また、外容器（２）の上部には若体（７）
を設け、外容器（２）の内部を密閉できるようにしてい
る。また、この内部の温度はコントローラーで調整でき
るようにしてもいる．水熟反応における温度、圧力、金
属溶液の濃度など反応条件は、出発原料とするチタンま
たはチタン酸化物の形態、金属溶液の種類などに応じて
適宜定めることができる．たとえば、金属溶液として水
酸化バリウム水溶液を使用する場合、処理温度は一般に
１００゜Ｃ以上とするのが好ましく、特に２００゜Ｃ程
度で良好な薄膜を形成することができる．
（作 用）
このような水熱反応により、従来の物理蒸着法、化学蒸
着法または有機金属塗布法に比べて比較的低温で結晶の
成長を促進させることができ、出発材料とする金属チタ
ンまたはチタン酸化物の表面に均一で結晶性に優れた薄
膜を直接的に形成することが可能となる．
（実施例）
以下、実施例を示してこの発明を具体的に説明する．
実施例１
第１図に示したオートクレープの内容器の中に純度９９
．９％の金属チタン板を設置し、０．５Ｎの｝３ａ （
ＯＨ） ２ ・８１１２０を入れた．これを温度２００
℃、飽和蒸気圧２．０Ｍ Ｐ ａで１時間水熱反応させ
た．
その結果、金属チタン板上にチタン酸バリウム（ＢａＴ
ｉＯｘ）薄膜を得た．
この薄膜をＸ線回折分析したところ、第２図の回折パタ
ーンを得た．これにより金属チタン板上にチタン酸バリ
ウムの単一相の結晶の薄膜が生成していることが確認さ
れた。The autoclave (1) shown in the figure is equipped with a heater (3) around the outer periphery of the outer container (2). The inner container (4) is made of Teflon or the like, and has a metal titanium plate or titanium oxide plate (5) installed therein so that the metal molten a(6) can be placed therein. In addition, the upper part of the outer container (2) contains a young body (7).
is provided so that the inside of the outer container (2) can be sealed. The internal temperature can also be adjusted using a controller. Reaction conditions such as temperature, pressure, and concentration of metal solution in the water ripening reaction can be determined as appropriate depending on the form of titanium or titanium oxide used as a starting material, the type of metal solution, etc. For example, when a barium hydroxide aqueous solution is used as the metal solution, the treatment temperature is generally preferably 100°C or higher, and a good thin film can be formed particularly at about 200°C. (Function) Such a hydrothermal reaction can promote crystal growth at a relatively low temperature compared to conventional physical vapor deposition, chemical vapor deposition, or organometallic coating methods. It becomes possible to directly form a uniform thin film with excellent crystallinity on the surface of titanium oxide. (Examples) The present invention will be specifically explained below with reference to Examples. Example 1 In the inner container of the autoclave shown in FIG.
．． A 9% titanium metal plate was installed, and a 0.5N}3a (
OH) 2 ・81120 was added. This temperature is 200
A hydrothermal reaction was carried out for 1 hour at ℃ and saturated vapor pressure of 2.0 MPa. As a result, barium titanate (BaT) was deposited on the metal titanium plate.
iOx) thin film was obtained. When this thin film was analyzed by X-ray diffraction, the diffraction pattern shown in Figure 2 was obtained. This confirmed that a thin film of single-phase crystals of barium titanate was formed on the metal titanium plate.
実施例２
水熱反応時間を１０分として実施例１と同様に反応させ
、金属チタン板上にチタン酸バリウム薄膜を得た．
この薄膜をＸ線回折分析したところ、この場合も単一相
の結晶の薄膜が生成していることが確認された。Example 2 A reaction was carried out in the same manner as in Example 1 with a hydrothermal reaction time of 10 minutes to obtain a barium titanate thin film on a metal titanium plate. When this thin film was analyzed by X-ray diffraction, it was confirmed that a single-phase crystal thin film was also formed in this case.
実施例３
水熱反応時間を３０分として実施例１と同様に反応させ
、金属チタン板上にチタン酸バリウム薄膜を得た．
この薄膜をＸ線回折分析したところ、この場合も単一相
の結晶の薄膜が生成していることが確認できた．
実施例４
酸化チタン板（Ｔｉｅ２＞を実施例１と同様に水熟反応
させ、その酸化チタン板上にチタン酸バリウム薄１漠を
得た．
この薄膜をＸ線回折分析したところ、第３図の回折パタ
ーンを得た．これにより単一相の結晶の薄膜が生或して
いることが確認された．実施例５
スパッタリングにより形成した絶縁基板上のチタン薄膜
を実施例１と同様に水熟反応させ、そのチタン薄膜上に
チタン酸バリウム薄膜を得た。Example 3 A reaction was carried out in the same manner as in Example 1 with a hydrothermal reaction time of 30 minutes to obtain a barium titanate thin film on a metal titanium plate. When this thin film was analyzed by X-ray diffraction, it was confirmed that a single-phase crystal thin film was formed in this case as well. Example 4 A titanium oxide plate (Tie2> was subjected to a water-ripening reaction in the same manner as in Example 1, and a barium titanate thin film was obtained on the titanium oxide plate. When this thin film was analyzed by X-ray diffraction, Fig. 3 A diffraction pattern was obtained.This confirmed that a single-phase crystal thin film was formed.Example 5 A titanium thin film formed by sputtering on an insulating substrate was water-cured in the same manner as in Example 1. The reaction was carried out to obtain a barium titanate thin film on the titanium thin film.
この薄膜をＸ線回折分析したところ、第４図の回折パタ
ーンを得た．これにより単一相の結晶の薄膜が生成して
いることが確認された．実施例６
水酸化ストロンチウム溶液を用いて実施例ｌ〜５と同様
の水熟処理をすることにより、チタン酸ストロンチウム
の薄膜を得た．
（発明の効果）
この発明により、簡便な水熟反応により比較的低温の反
応条件下で均一で結晶性に優れたチタン酸バリウム等の
複合酸化物の薄膜を金属チタンまたはチタン酸化物の表
面に直接得ることが可能となる．異形形状表面への薄膜
形成も容易となる．When this thin film was analyzed by X-ray diffraction, the diffraction pattern shown in Figure 4 was obtained. This confirmed the formation of a thin film of single-phase crystals. Example 6 A thin film of strontium titanate was obtained by carrying out the same water aging treatment as in Examples 1 to 5 using a strontium hydroxide solution. (Effects of the Invention) According to the present invention, a thin film of a complex oxide such as barium titanate, which is uniform and has excellent crystallinity, is formed on the surface of metallic titanium or titanium oxide under relatively low temperature reaction conditions by a simple water ripening reaction. It is possible to obtain it directly. It is also easy to form thin films on irregularly shaped surfaces.
第１図は、この発明で使用することのできるオートクレ
ープの断面図である．
第２図は、金属チタン板上に形成したチタン酸バリウム
薄膜のＸＩ１回折パターンである．第３図は、酸化チタ
ン板上に形成したチタン酸バリウム薄膜のＸ線回折パタ
ーンである．第４図は、スパッタリングにより形成した
チタン薄膜上のチタン酸バリウム薄膜のＸ線回折パター
ンである．FIG. 1 is a sectional view of an autoclave that can be used in this invention. Figure 2 shows the XI1 diffraction pattern of a barium titanate thin film formed on a metal titanium plate. Figure 3 shows the X-ray diffraction pattern of a barium titanate thin film formed on a titanium oxide plate. Figure 4 is an X-ray diffraction pattern of a barium titanate thin film on a titanium thin film formed by sputtering.
Claims (3)
応させ、その表面に複合チタン酸化物薄膜を形成するこ
とを特徴とする複合チタン酸化物薄膜の製造方法。(1) A method for producing a composite titanium oxide thin film, which comprises subjecting titanium or titanium oxide to a hydrothermal reaction in a metal solution to form a composite titanium oxide thin film on the surface thereof.
水酸化カルシウムの水溶液もしくは、バリウム、ストロ
ンチウム、またはカルシウムを含むアルカリ性水溶液中
で水熱反応させる請求項（１）記載の複合チタン酸化物
薄膜の製造方法。(2) The method for producing a composite titanium oxide thin film according to claim (1), wherein the hydrothermal reaction is carried out in an aqueous solution of barium hydroxide, strontium hydroxide, or calcium hydroxide, or an alkaline aqueous solution containing barium, strontium, or calcium. .
してなる複合チタン酸化物薄膜。(3) A composite titanium oxide thin film formed by the method according to claim (1) or (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30363989A JPH03162584A (en) | 1989-11-22 | 1989-11-22 | Thin film of titanium-containing multiple oxide and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30363989A JPH03162584A (en) | 1989-11-22 | 1989-11-22 | Thin film of titanium-containing multiple oxide and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03162584A true JPH03162584A (en) | 1991-07-12 |
Family
ID=17923418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30363989A Pending JPH03162584A (en) | 1989-11-22 | 1989-11-22 | Thin film of titanium-containing multiple oxide and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03162584A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010150087A (en) * | 2008-12-25 | 2010-07-08 | Sakai Chem Ind Co Ltd | Titanium dioxide pigment and production method thereof |
| JP2011006292A (en) * | 2009-06-26 | 2011-01-13 | Sakai Chem Ind Co Ltd | Titanium dioxide particles and method for producing the same |
| CN110129785A (en) * | 2019-06-12 | 2019-08-16 | 重庆理工大学 | A kind of surface treatment method of TiNb alloy |
-
1989
- 1989-11-22 JP JP30363989A patent/JPH03162584A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010150087A (en) * | 2008-12-25 | 2010-07-08 | Sakai Chem Ind Co Ltd | Titanium dioxide pigment and production method thereof |
| JP2011006292A (en) * | 2009-06-26 | 2011-01-13 | Sakai Chem Ind Co Ltd | Titanium dioxide particles and method for producing the same |
| CN110129785A (en) * | 2019-06-12 | 2019-08-16 | 重庆理工大学 | A kind of surface treatment method of TiNb alloy |
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