JPH0443993B2 - - Google Patents
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- Publication number
- JPH0443993B2 JPH0443993B2 JP63050646A JP5064688A JPH0443993B2 JP H0443993 B2 JPH0443993 B2 JP H0443993B2 JP 63050646 A JP63050646 A JP 63050646A JP 5064688 A JP5064688 A JP 5064688A JP H0443993 B2 JPH0443993 B2 JP H0443993B2
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- Prior art keywords
- oxide film
- anodic oxide
- titanium
- film composition
- composition
- Prior art date
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- Other Surface Treatments For Metallic Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、主として装飾品、建材、航空機及
び機械部品などに使用されるチタン及びチタン合
金の陽極酸化皮膜組成物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing an anodic oxide film composition of titanium and titanium alloys, which is mainly used for ornaments, building materials, aircraft, mechanical parts, and the like.
（従来の技術）
従来、チタン及びチタン合金の陽極酸化処理法
として、ホウ酸、ホウ砂、重炭酸ナトリウム、酒
石酸、硫酸及び酢酸などを溶解させた水溶液、又
は前記ホウ酸、ホウ砂、重炭酸ナトリウム、酒石
酸、硫酸及び酢酸などをエチレングリコール溶液
に溶解させた非水溶液を用いて、それぞれ電解浴
を調製し、これら各電解浴中において、チタン及
びチタン合金を電解処理するようにしものが、既
に知られている。(Prior Art) Conventionally, as an anodizing treatment method for titanium and titanium alloys, an aqueous solution in which boric acid, borax, sodium bicarbonate, tartaric acid, sulfuric acid, acetic acid, etc. are dissolved, or the above-mentioned boric acid, borax, bicarbonate, etc. It has already been reported that electrolytic baths are prepared using non-aqueous solutions of sodium, tartaric acid, sulfuric acid, acetic acid, etc. dissolved in ethylene glycol solution, and titanium and titanium alloys are electrolytically treated in these electrolytic baths. Are known.
ところで以上のごとき陽極酸化処理法では、チ
タン及びチタン合金の表面に生成される皮膜の厚
さが、せいぜい数10〜数100オングストローム程
度であつて、所謂干渉膜と言われる非常に薄いも
のしか得られず、従つて手で触つたり雨に濡れた
りすると、前記皮膜が剥離したり、また該皮膜が
変色したりする欠点があつた。 By the way, with the above-mentioned anodic oxidation treatment method, the thickness of the film formed on the surface of titanium and titanium alloys is approximately several tens to several hundred angstroms at most, and only a very thin film called an interference film can be obtained. Therefore, if the film is touched by hand or wet with rain, the film may peel off or change color.
そこで、本発明者等は、以前に特願昭61−
258012号などにおいて、ミクロン単位の皮膜を生
成することができるチタン及びチタン合金の製造
方法を提案した。 Therefore, the inventors of the present invention previously applied for patent application No.
No. 258012 and other papers, we proposed a method for producing titanium and titanium alloys that can produce films on the micron scale.
（発明が解決しようとする課題）
ところで、以上の製造方法では、得られる皮膜
の色が灰色系統に限定される問題があり、その上
該皮膜は耐摩耗性及び潤滑性の点で未だ不充分で
あるなどの問題があつた。(Problems to be Solved by the Invention) However, with the above manufacturing method, there is a problem that the color of the obtained film is limited to a gray color, and furthermore, the film is still insufficient in terms of wear resistance and lubricity. There were problems such as:
本発明は、以上のような問題点に鑑みて、さら
に研究を重ねた結果、各種の色をもつた皮膜を得
ることができ、しかも皮膜の変色や汚れを招くこ
となく、耐摩耗性、硬さ、高耐食性及び潤滑性の
点で優れたチタン及びチタン合金の陽極酸化皮膜
組成物を簡単に得ることができる製造方法を提供
しようとするものである。 In view of the above-mentioned problems, and as a result of further research, the present invention is capable of producing coatings with various colors, without causing discoloration or staining of the coating, and with excellent wear resistance and hardness. The object of the present invention is to provide a manufacturing method that can easily obtain anodized film compositions of titanium and titanium alloys that are excellent in terms of high corrosion resistance and lubricity.
（課題を解決するための手段）
上記目的を達成するため、本発明のチタン及び
チタン合金陽極酸化皮膜組成物の製造方法は、チ
タン及びチタン合金を陽極酸化して陽極酸化皮膜
を形成した後、Al、Ba、Ca、Cu、Cr、Co、Fe、
Mn、Mg、Ni、Sn、Tiなどの金属群から選択さ
れた１種又は１種以上の金属塩が添加された金属
塩水溶液中に浸漬して、加熱処理し、前記極酸化
皮膜の表面に前記金属塩水溶液中の金属イオンを
酸化物（含水和物）として析出させることを特徴
とするものである。(Means for Solving the Problems) In order to achieve the above object, the method for producing a titanium and titanium alloy anodic oxide film composition of the present invention includes: after anodizing titanium and a titanium alloy to form an anodized film, Al, Ba, Ca, Cu, Cr, Co, Fe,
The surface of the polar oxide film is immersed in a metal salt aqueous solution containing one or more metal salts selected from the group of metals such as Mn, Mg, Ni, Sn, and Ti, and heat-treated. This method is characterized in that the metal ions in the aqueous metal salt solution are precipitated as oxides (hydrates).
また、陽極酸化処理が施されたチタン及びチタ
ン合金を浸漬するに際しては、前記金属塩水溶液
に塩基性水溶液に添加してヒドロゾル溶液を調製
し、このヒドロゾル溶液中に浸漬させることが好
ましい。 Further, when immersing titanium and titanium alloys that have been subjected to anodizing treatment, it is preferable to prepare a hydrosol solution by adding the metal salt aqueous solution to a basic aqueous solution, and immerse it in this hydrosol solution.
さらに、陽極酸化処理と浸漬処理とが施された
チタン及びチタン合金を加熱するに際しては、オ
ートクレーブなどを用いた加圧下で行うことが好
ましい。 Furthermore, when heating titanium and titanium alloys that have been subjected to anodizing treatment and dipping treatment, it is preferable to heat the titanium and titanium alloys under pressure using an autoclave or the like.
（作用及び効果）
以上のように、チタン及びチタン合金の陽極酸
化して陽極酸化皮膜を形成した後、Al、Ba、
Ca、Cu、Cr、Co、Fe、Mn、Mg、Ni、Sn、Ti
などの金属群から選択された１種又は１種以上の
金属塩が添加された金属塩水溶液中に浸漬して、
加熱処理することにより、前記金属水溶液中にお
いて金属イオンが加水分解され、酸化物（水和物
も含む）として前記陽極酸化皮膜の表面に析出さ
れ、チタン及びチタン合金の陽極酸化皮膜組成物
が簡単に得られる。(Functions and Effects) As described above, after anodizing titanium and titanium alloy to form an anodized film, Al, Ba,
Ca, Cu, Cr, Co, Fe, Mn, Mg, Ni, Sn, Ti
immersed in a metal salt aqueous solution to which one or more metal salts selected from the metal group such as
By heat treatment, metal ions are hydrolyzed in the metal aqueous solution and precipitated as oxides (including hydrates) on the surface of the anodic oxide film, making it easy to form an anodic oxide film composition for titanium and titanium alloys. can be obtained.
以上のようにして得られた陽極酸化皮膜組成物
は、前記チタン及びチタン合金の浸漬処理時に使
用される前記金属水溶液中の金属イオンが酸化物
（含水和物）として前記陽極酸化皮膜の表面に析
出されるため、前記金属塩水溶液に添加された金
属塩の酸化物（含水和物）特有の特性が付与され
るのであり、従つて、前記陽極酸化皮膜組成物の
摩耗性や硬度及び潤滑性などが高められ、また、
この陽極酸化皮膜組成物は汚れたり変色したりす
ることもなく、しかも前記金属水溶液に添加する
金属塩を選択して、前記陽極酸化皮膜に析出させ
ることにより、前記陽極酸化皮膜組成物を広範囲
にわたつて種々着色することができる。 In the anodic oxide film composition obtained as described above, the metal ions in the metal aqueous solution used during the immersion treatment of titanium and titanium alloys form oxides (hydrates) on the surface of the anodic oxide film. Since the metal salt is precipitated, the metal salt oxide (hydrate) added to the metal salt aqueous solution has characteristics unique to the oxide (hydrate), and therefore the abrasion properties, hardness, and lubricity of the anodic oxide film composition are improved. etc. are enhanced, and
This anodic oxide film composition does not stain or discolor, and by selecting a metal salt to be added to the metal aqueous solution and depositing it on the anodic oxide film, the anodic oxide film composition can be spread over a wide range. It can be colored in various ways.
また、陽極酸化処理が施されたチタン及びチタ
ン合金の浸漬処理時に、前記金属水溶液に塩基性
水溶液例えば水酸化ナトリウムや水酸化アンモニ
ウム及び重炭酸ナトリウムなどを添加することに
より、多核錯イオン〜コロイド粒子状となつた金
属イオンのヒドロゾル溶液が調製されるのである
が、斯かるヒドロゾル溶液中に前記陽極酸化皮膜
を浸漬させることにより、加熱処理時に前記金属
イオンの加水分解反応が促進され、重合度も増す
ため、より多量の金属（含水和物）が析出し、前
述した陽極酸化皮膜組成物が効率良く形成される
のである。 In addition, during the immersion treatment of titanium and titanium alloys that have been subjected to anodizing treatment, by adding a basic aqueous solution such as sodium hydroxide, ammonium hydroxide, sodium bicarbonate, etc. to the metal aqueous solution, polynuclear complex ions to colloidal particles A hydrosol solution of metal ions is prepared, and by immersing the anodic oxide film in the hydrosol solution, the hydrolysis reaction of the metal ions is accelerated during heat treatment, and the degree of polymerization is also reduced. Therefore, a larger amount of metal (hydrate) is precipitated, and the above-mentioned anodic oxide film composition is efficiently formed.
さらに、陽極酸化処理と浸漬処理とが施された
チタン及びチタン合金の加熱処理時に、オートク
レーブなどを用いた加圧下で行うときには、前記
陽極酸化皮膜に析出される前記金属イオンの加水
分解反応が積極的に行われ、その効率が高められ
て、前述した陽極酸化皮膜組成物が効率良く形成
される。 Furthermore, when heat treating titanium and titanium alloys that have been subjected to anodizing treatment and immersion treatment under pressure using an autoclave or the like, the hydrolysis reaction of the metal ions deposited on the anodic oxide film is actively accelerated. The anodic oxidation film composition described above can be formed with high efficiency.
（実施例）
以下、本発明を具体的な実施例を挙げて説明す
る。(Example) Hereinafter, the present invention will be described with reference to specific examples.
実施例 １
先ず、0.2M硫酸と0.3Mリン酸との混合水溶液
中において、純チタンを陽極とし、また純チタン
を陰極として、直流電圧250Vを30分間印加して、
灰白色で膜厚5μmの陽極酸化皮膜を得た。Example 1 First, in a mixed aqueous solution of 0.2M sulfuric acid and 0.3M phosphoric acid, a DC voltage of 250V was applied for 30 minutes using pure titanium as an anode and pure titanium as a cathode.
A gray-white anodic oxide film with a thickness of 5 μm was obtained.
次に、PH2.78の0.04M硫酸鉄アンモニウム（12
水）の水溶液を調製し、この金属塩水溶液中に、
前記で得られた陽極酸化皮膜を浸漬し、オートク
レーブ（圧力５Kg／cm2）を用いて、150℃の温度
で２時間加熱処理した。 Next, 0.04M ferrous ammonium sulfate (12
water), and in this metal salt aqueous solution,
The anodic oxide film obtained above was immersed and heat-treated at a temperature of 150° C. for 2 hours using an autoclave (pressure: 5 kg/cm 2 ).
この結果、均一で黄土色の陽極酸化皮膜組成物
が得られた。この陽極酸化皮膜組成物の走査型電
子顕微鏡による表面写真は、第１図に示した通り
であり、該図から明らかなごとく、前記陽極酸化
皮膜に多数の鉄酸化物（含水和物）が析出されて
いることが理解できる。尚、前記第１図に記載し
た記号は、実際の長さを示している。 As a result, a uniform ocher-colored anodic oxide film composition was obtained. A surface photograph of this anodic oxide film composition taken by a scanning electron microscope is shown in Figure 1, and as is clear from the figure, a large number of iron oxides (hydrates) are precipitated in the anodic oxide film. I can understand what is happening. Note that the symbols shown in FIG. 1 indicate actual lengths.
前記陽極酸化皮膜組成物を、赤外線吸収スペク
トル、熱分析及びＸ線回析で測定した所、前記陽
極酸化皮膜組成物が非晶質の水酸化鉄（含酸化
鉄）であることが判明した。 The anodic oxide film composition was measured by infrared absorption spectrum, thermal analysis, and X-ray diffraction, and it was found that the anodic oxide film composition was amorphous iron hydroxide (iron oxide).
また、前記陽極酸化皮膜組成物を、サカシヤイ
ンウエザーメータを用いて試験した所、1000時間
変色することがなく、また汚れも付着しなかつ
た。 Further, when the anodic oxide film composition was tested using a Sakashya in-weather meter, it did not change color for 1000 hours and did not adhere to dirt.
更に、前記陽極酸化皮膜組成物について、耐摩
耗試験（JIS K7204に準じる摩耗輪による摩耗試
験方法によつて、素地露出に達するまでの回転数
で評価）を行つた所、前記陽極酸化皮膜が1000回
であつたのに対し、前記陽極酸化皮膜組成物が
12000回となり、この陽極酸化皮膜組成物の耐摩
耗性が明らかに向上された。 Furthermore, when the anodic oxide film composition was subjected to an abrasion resistance test (evaluated by the number of rotations until the substrate was exposed by the abrasion test method using an abrasion wheel according to JIS K7204), it was found that the anodic oxide film was 1000% In contrast, the anodic oxide film composition
12,000 times, and the wear resistance of this anodic oxide film composition was clearly improved.
また、前記陽極酸化皮膜組成物について、マイ
クロビツカース硬度計で硬度を測定した所、前記
陽極酸化皮膜がHV320であつたのに対して、前
記陽極酸化皮膜組成物がHV830となり、この陽
極酸化皮膜組成物の硬度も明らかに向上された。 Furthermore, when the hardness of the anodic oxide film composition was measured using a micro-Vickers hardness meter, the anodic oxide film had a hardness of HV320, whereas the anodic oxide film composition had a hardness of HV830. The hardness of the composition was also clearly improved.
実施例 ２
先ず、1.0M硫酸と0.2M過酸化水素水との混合
水溶液中において、純チタンを陽極とし、また純
チタンを陰極として、直流電圧200Vを60分間印
加して、暗灰色で膜厚6.5μmの陽極酸化皮膜を得
た。Example 2 First, in a mixed aqueous solution of 1.0M sulfuric acid and 0.2M hydrogen peroxide, pure titanium was used as an anode and pure titanium was used as a cathode, and a DC voltage of 200V was applied for 60 minutes to change the film thickness in dark gray. A 6.5 μm anodic oxide film was obtained.
次に、PH3.87の0.04M硫酸カリウムクロム（12
水）の水溶液を調製し、この金属塩水溶液中に、
前記で得られた陽極酸化皮膜を浸漬し、圧力４
Kg／cm2の加圧条件下で、溶液温度140〜150℃の温
度に保持し、２時間加熱処理した。 Next, 0.04M potassium chromium sulfate (12
water), and in this metal salt aqueous solution,
The anodic oxide film obtained above was immersed, and the pressure was 4
Under pressurized conditions of Kg/cm 2 , the solution temperature was maintained at 140 to 150° C. and heat treated for 2 hours.
更に、以上で得られた皮膜を電気炉において、
600℃の温度で加熱した。 Furthermore, the film obtained above was placed in an electric furnace.
Heated at a temperature of 600°C.
この結果、均一で暗緑灰色の陽極酸化皮膜組成
物が得られた。この陽極酸化皮膜組成物の走査型
電子顕微鏡による表面写真は、第２図に示した通
りであり、該図から明らかなごとく、前記陽極酸
化皮膜に多数のクムロ酸化物（含水和物）が析出
されていることが理解できる。 As a result, a uniform dark green-gray anodic oxide film composition was obtained. A surface photograph of this anodic oxide film composition taken by a scanning electron microscope is shown in Figure 2, and as is clear from the figure, a large number of cumurooxides (hydrates) are precipitated in the anodic oxide film. I can understand what is happening.
前記陽極酸化皮膜組成物を、赤外線吸収スペク
トル、熱分析及びＸ線回析で測定した所、前記陽
極酸化皮膜組成物が非晶質な酸化クロム（含水酸
化クロム）であることが判明した。 When the anodic oxide film composition was measured by infrared absorption spectrum, thermal analysis, and X-ray diffraction, it was found that the anodic oxide film composition was amorphous chromium oxide (hydrous chromium oxide).
また、前記陽極酸化皮膜組成物を、サンシヤイ
ンウエザーメータを用いて試験した所、1000時間
変色することがなく、また汚れも付着しなかつ
た。 Further, when the anodic oxide film composition was tested using a sunshine weather meter, it did not change color for 1000 hours and did not have any stains attached.
更に、前記陽極酸化皮膜組成物について、前記
実施例１と同様な耐摩耗試験方法を行つた所、前
記陽極酸化皮膜が1200回であつたのに対し、前記
陽極酸化皮膜組成物が15000回となり、この陽極
酸化皮膜組成物の耐摩耗性が明らかに向上され
た。 Furthermore, when the anodic oxide film composition was subjected to the same abrasion resistance test method as in Example 1, the anodic oxide film was tested 1200 times, while the anodic oxide film composition was tested 15000 times. , the abrasion resistance of this anodic oxide coating composition was clearly improved.
また、前記陽極酸化皮膜組成物について、前記
実施例１と同様にして、マイクロビツカース硬度
計で硬度を測定した所、前記陽極酸化皮膜が
HV350であつたのに対し、前記陽極酸化皮膜組
成物がHV960となり、この陽極酸化皮膜組成物
の硬度も明らかに向上された。 Further, the hardness of the anodic oxide film composition was measured using a micro-Vickers hardness meter in the same manner as in Example 1, and it was found that the anodic oxide film was
While the hardness of the anodic oxide film composition was HV350, the hardness of the anodic oxide film composition was HV960, and the hardness of this anodic oxide film composition was also clearly improved.
実施例 ３
先ず、0.5Mリン酸と0.2M過酸化水素水との混
合水溶液中において、純チタンを陽極とし、また
純チタンを陰極として、直流電圧300Vを10分間
印加して、暗灰色で膜厚4.2μmの陽極酸化皮膜を
得た。Example 3 First, in a mixed aqueous solution of 0.5M phosphoric acid and 0.2M hydrogen peroxide, pure titanium was used as an anode and pure titanium was used as a cathode, and a DC voltage of 300V was applied for 10 minutes to form a dark gray film. An anodic oxide film with a thickness of 4.2 μm was obtained.
次に、PH6.05の0.08M硫酸コバルトアンモニ
ム・６水和物の水溶液を調製し、この金属塩水溶
液中に、前記で得られた陽極酸化皮膜を浸漬し、
圧力５Kg／cm2の加圧条件下で、溶液温度150℃の
温度に保持し、２時間加熱処理を行つた。この結
果、暗赤茶色の皮膜が形成された。 Next, an aqueous solution of 0.08M cobalt ammonium sulfate hexahydrate with a pH of 6.05 was prepared, and the anodic oxide film obtained above was immersed in this metal salt aqueous solution.
Under pressurized conditions of 5 kg/cm 2 , the solution temperature was maintained at 150° C. and heat treatment was performed for 2 hours. As a result, a dark reddish-brown film was formed.
更に、以上で得られた皮膜を電気炉において、
800℃の温度で加熱した。 Furthermore, the film obtained above was placed in an electric furnace.
Heated at a temperature of 800°C.
この結果、均一で暗緑色の陽極酸化皮膜組成物
が得られた。この陽極酸化皮膜組成物の走査型電
子顕微鏡による表面写真は、第３図に示した通り
であり、該図から明らかなごとく、前記陽極酸化
皮膜に多数のコバルト酸化物（含水和物）が析出
されていることが理解できる。 As a result, a uniform dark green anodic oxide film composition was obtained. A surface photograph of this anodic oxide film composition taken by a scanning electron microscope is shown in Figure 3, and as is clear from the figure, a large number of cobalt oxides (hydrates) are precipitated in the anodic oxide film. I can understand what is happening.
前記陽極酸化皮膜組成物を、赤外線吸収スペク
トル、熱分析及びＸ線回析で測定した所、前記陽
極酸化皮膜組成物が非晶質なチタン酸コバルトの
固溶体であることが判明した。 When the anodic oxide film composition was measured by infrared absorption spectrum, thermal analysis, and X-ray diffraction, it was found that the anodic oxide film composition was a solid solution of amorphous cobalt titanate.
また、前記陽極酸化皮膜組成物を、サンシヤイ
ンウエザーメータを用いて試験した所、1000時間
変色することがなく、また汚れも付着しなかつ
た。 Further, when the anodic oxide film composition was tested using a sunshine weather meter, it did not change color for 1000 hours and did not have any stains attached.
更に、前記陽極酸化皮膜組成物について、前記
実施例１と同様な耐摩耗試験を行つた所、前記陽
極酸化皮膜が900回であつたのに対し、前記陽極
酸化皮膜組成物が18000回となり、この陽極酸化
皮膜組成物の耐摩耗性が明らかに向上された。 Furthermore, when the anodic oxide film composition was subjected to the same wear resistance test as in Example 1, the anodic oxide film was tested 900 times, whereas the anodic oxide film composition was tested 18,000 times. The abrasion resistance of this anodic oxide film composition was clearly improved.
また、前記陽極酸化皮膜組成物について、前記
実施例１と同様にして、マイクロビツカース硬度
計で硬度を測定した所、前記陽極酸化皮膜が
HV330であつたのに対し、前記陽極酸化皮膜組
成物がHV990となり、この陽極酸化皮膜組成物
の硬度も明らかに向上された。 Further, the hardness of the anodic oxide film composition was measured using a micro-Vickers hardness meter in the same manner as in Example 1, and it was found that the anodic oxide film was
While the hardness of the anodic oxide film composition was HV330, the hardness of the anodic oxide film composition was clearly improved.
実施例 ４
先ず、0.1M硫酸と、0.3Mリン酸、及び0.2M過
酸化水素水との混合水溶液中において、純チタン
を陽極とし、また純チタンを陰極として、直流電
圧300Vを30分間印加して、灰白色で膜厚11μmの
陽極酸化皮膜を得た。Example 4 First, in a mixed aqueous solution of 0.1M sulfuric acid, 0.3M phosphoric acid, and 0.2M hydrogen peroxide, a DC voltage of 300V was applied for 30 minutes using pure titanium as an anode and pure titanium as a cathode. A gray-white anodic oxide film with a thickness of 11 μm was obtained.
次に、炭酸ナトリウムでPH1.4に調製した0.5M
四塩化チタン水溶液を調製し、この金属塩水溶液
中に、前記で得られた陽極酸化皮膜を浸漬し、オ
ートクレーブ（圧力５Kg／cm2）を用いて、溶液温
度100℃温度に保持し、２時間加熱処理した。 Next, 0.5M adjusted to PH1.4 with sodium carbonate
A titanium tetrachloride aqueous solution was prepared, and the anodic oxide film obtained above was immersed in this metal salt aqueous solution, and the solution temperature was maintained at 100° C. using an autoclave (pressure 5 Kg/cm 2 ) for 2 hours. Heat treated.
この結果、均一で灰色がかつた白色の陽極酸化
皮膜組成物が得られた。 As a result, a uniform, grayish white anodic oxide film composition was obtained.
前記陽極酸化皮膜組成物を、赤外線吸収スペク
トル、熱分析及びＸ線回析で測定した所、前記陽
極酸化皮膜組成物が非晶質な水和酸化チタンであ
ることが判明した。 The anodic oxide film composition was measured by infrared absorption spectrum, thermal analysis, and X-ray diffraction, and it was found that the anodic oxide film composition was amorphous hydrated titanium oxide.
また、前記陽極酸化皮膜組成物を、サンシヤイ
ンウエザーメータを用いて試験した所、1000時間
変色することがなく、また汚れも付着しなかつ
た。 Further, when the anodic oxide film composition was tested using a sunshine weather meter, it did not change color for 1000 hours and did not have any stains attached.
更に、前記陽極酸化皮膜組成物について、前記
実施例１と同様な耐摩耗試験方法を行つた所、前
記陽極酸化皮膜が1500回であつたのに対し、前記
陽極酸化皮膜組成物が13000回となり、この陽極
酸化皮膜組成物の耐摩耗性が明らかに向上され
た。 Furthermore, when the anodic oxide film composition was subjected to the same abrasion resistance test method as in Example 1, the anodic oxide film was tested 1500 times, while the anodic oxide film composition was tested 13000 times. , the abrasion resistance of this anodic oxide coating composition was clearly improved.
また、前記陽極酸化皮膜組成物について、前記
実施例１と同様にして、マイクロビツカース硬度
計で硬度を測定した所、前記陽極酸化皮膜が
HV360であつたのに対し、前記陽極酸化皮膜組
成物がHV970となり、この陽極酸化皮膜組成物
の硬度も明らかに向上された。 Further, the hardness of the anodic oxide film composition was measured using a micro-Vickers hardness meter in the same manner as in Example 1, and it was found that the anodic oxide film was
While the hardness of the anodic oxide film composition was HV360, the hardness of the anodic oxide film composition was clearly improved.
実施例 ５
先ず、チタン合金（Ti−4Al−22V系）を使用
し、前記実施例４と同様にして、暗灰色で膜厚
10μmの陽極酸化皮膜を得た。Example 5 First, a titanium alloy (Ti-4Al-22V system) was used, and the film thickness was measured in dark gray in the same manner as in Example 4.
A 10 μm anodic oxide film was obtained.
次に、PH2.78に調製した0.1M硫酸アンモニ
ム・アルミニウム・12水の水溶液を調製し、この
金属塩水溶液中に前記で得られた陽極酸化皮膜を
浸漬し、オートクレーブ（圧力４Kg／cm2）を用い
て，溶液温度150℃の温度に保持し、２時間処理
した。 Next, prepare an aqueous solution of 0.1M ammonium sulfate/aluminum/12 water adjusted to pH 2.78, immerse the anodic oxide film obtained above in this metal salt aqueous solution, and autoclave (pressure 4Kg/cm 2 ). The solution was maintained at a temperature of 150° C. and treated for 2 hours.
更に、前記で得られた皮膜を電気炉を用いて、
800℃の温度で加熱処理した。 Furthermore, the film obtained above was heated in an electric furnace,
Heat treated at a temperature of 800°C.
この結果、均一で灰白色の陽極酸化皮膜組成物
が得られた。 As a result, a uniform, off-white anodic oxide film composition was obtained.
前記陽極酸化皮膜組成物を、赤外線吸収スペク
トル、熱分析及びＸ線回析で測定した所、前記陽
極酸化皮膜組成物が非晶質なアルミナであること
が判明した。 The anodic oxide film composition was measured by infrared absorption spectrum, thermal analysis, and X-ray diffraction, and it was found that the anodic oxide film composition was amorphous alumina.
また、前記陽極酸化皮膜組成物を、サンシヤイ
ンウエザーメータを用いて試験した所、1000時間
変色することがなく、また汚れも付着しなかつ
た。 Further, when the anodic oxide film composition was tested using a sunshine weather meter, it did not change color for 1000 hours and did not have any stains attached.
更に、前記陽極酸化皮膜組成物について、前記
実施例１と同様な耐摩耗試験方法を行つた所、前
記陽極酸化皮膜が1500回であつたのに対し、前記
陽極酸化皮膜組成物が14000回となり、この陽極
酸化皮膜組成物の耐摩耗性が明らかに向上され
た。 Furthermore, when the anodic oxide film composition was subjected to the same abrasion test method as in Example 1, the anodic oxide film was tested 1500 times, while the anodic oxide film composition was tested 14000 times. , the abrasion resistance of this anodic oxide coating composition was clearly improved.
また、前記陽極酸化皮膜組成物について、前記
実施例１と同様にして、マイクロビツカース硬度
計で硬度を測定した所、前記陽極酸化皮膜が
HV370であつたのに対し、前記陽極酸化皮膜組
成物がHV980となり、この陽極酸化皮膜組成物
の硬度も明らかに向上された。 Further, the hardness of the anodic oxide film composition was measured using a micro-Vickers hardness meter in the same manner as in Example 1, and it was found that the anodic oxide film was
While the hardness of the anodic oxide film composition was HV370, the hardness of the anodic oxide film composition was clearly improved.
第１図乃至第３図は、それぞれ本発明で得られ
る陽極酸化皮膜組成物の走査型電子顕微鏡による
表面写真を示すものである。
FIGS. 1 to 3 each show surface photographs taken by a scanning electron microscope of the anodic oxide film composition obtained in the present invention.
Claims (1)
化皮膜を形成した後、Al、Ba、Ca、Cu、Cr、
Co、Fe、Mn、Mg、Ni、Sn、Tiなどの金属群
から選択された１種又は１種以上の金属塩が添加
された金属塩水溶液中に浸漬して、加熱処理し、
前記極酸化皮膜の表面に前記金属塩水溶液中の金
属イオンを酸化物（含水和物）として析出させる
ことを特徴とするチタン及びチタン合金の陽極酸
化皮膜組成物の製造方法。 ２ 金属塩水溶液に塩基性水溶液を添加してヒド
ロゾル溶液を調製し、このヒドロゾル溶液中に浸
漬することを特徴とする請求項１記載のチタン及
びチタン合金の陽極酸化皮膜組成物の製造方法。 ３ 加熱処理をオートクレーブなどを用いて加圧
下で行うことを特徴とする請求項１又は２記載の
チタン及びチタン合金の陽極酸化皮膜組成物の製
造方法。[Claims] 1. After anodizing titanium and titanium alloy to form an anodized film, Al, Ba, Ca, Cu, Cr,
Heat treatment by immersing in a metal salt aqueous solution to which one or more metal salts selected from the metal group such as Co, Fe, Mn, Mg, Ni, Sn, and Ti are added,
A method for producing an anodic oxide film composition for titanium and titanium alloys, characterized in that metal ions in the aqueous metal salt solution are precipitated as oxides (hydrates) on the surface of the anodic oxide film. 2. The method for producing an anodic oxide film composition for titanium and titanium alloys according to claim 1, characterized in that a hydrosol solution is prepared by adding a basic aqueous solution to an aqueous metal salt solution, and the composition is immersed in this hydrosol solution. 3. The method for producing an anodic oxide film composition of titanium and titanium alloy according to claim 1 or 2, wherein the heat treatment is performed under pressure using an autoclave or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5064688A JPH01225793A (en) | 1988-03-04 | 1988-03-04 | Anodic oxide film composition on titanium and titanium alloy and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5064688A JPH01225793A (en) | 1988-03-04 | 1988-03-04 | Anodic oxide film composition on titanium and titanium alloy and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01225793A JPH01225793A (en) | 1989-09-08 |
| JPH0443993B2 true JPH0443993B2 (en) | 1992-07-20 |
Family
ID=12864710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5064688A Granted JPH01225793A (en) | 1988-03-04 | 1988-03-04 | Anodic oxide film composition on titanium and titanium alloy and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01225793A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4883603B2 (en) * | 2005-09-08 | 2012-02-22 | 学校法人近畿大学 | Manufacturing method of bone substitute material |
| US8858775B2 (en) * | 2007-10-03 | 2014-10-14 | Accentus Medical Limited | Method of manufacturing metal with biocidal properties |
| CN103173835B (en) * | 2011-12-22 | 2016-01-06 | 中国科学院大连化学物理研究所 | A kind for the treatment of process of metallic titanium material |
| US11312107B2 (en) * | 2018-09-27 | 2022-04-26 | Apple Inc. | Plugging anodic oxides for increased corrosion resistance |
| CN109537021B (en) * | 2018-11-26 | 2020-07-21 | 天津师范大学 | Preparation method of titanium oxide/tin oxide composite membrane for sodium ion battery cathode |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50121138A (en) * | 1974-03-11 | 1975-09-22 | ||
| JPS5219535A (en) * | 1975-08-06 | 1977-02-14 | Ricoh Co Ltd | Dry type developing powder |
| JPS5318438A (en) * | 1976-08-04 | 1978-02-20 | Mitsui Keikinzoku Kako | Process for forming electrolytic pigmentation coatings on aluminum and aluminum alloy |
| JPS634095A (en) * | 1986-06-23 | 1988-01-09 | Seiko Instr & Electronics Ltd | Colored external parts of titanium or titanium alloy |
| JPS6350497A (en) * | 1986-08-18 | 1988-03-03 | Crown Denken:Kk | Method for coloring titanium material |
-
1988
- 1988-03-04 JP JP5064688A patent/JPH01225793A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01225793A (en) | 1989-09-08 |
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