JP3246298B2 - Method for producing pure titanium or titanium alloy material with beautiful surface - Google Patents
Method for producing pure titanium or titanium alloy material with beautiful surfaceInfo
- Publication number
- JP3246298B2 JP3246298B2 JP30016495A JP30016495A JP3246298B2 JP 3246298 B2 JP3246298 B2 JP 3246298B2 JP 30016495 A JP30016495 A JP 30016495A JP 30016495 A JP30016495 A JP 30016495A JP 3246298 B2 JP3246298 B2 JP 3246298B2
- Authority
- JP
- Japan
- Prior art keywords
- pickling
- titanium
- titanium alloy
- pure titanium
- pure
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、表面の美麗な純チ
タンまたはチタン合金材（以下、チタン材料と総称する
ことがある）を製造する方法に関するものであり、特
に、表面の審美性が強く要求される分野に利用されるこ
との多い純チタンまたはチタン合金展伸材を製造するに
あたり有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing pure titanium or a titanium alloy material having a beautiful surface (hereinafter, may be collectively referred to as a titanium material). It is useful in producing pure titanium or titanium alloy wrought materials often used in the required fields.
【０００２】[0002]
【従来の技術】圧延工程等における加熱や塑性加工後の
焼鈍によって、チタン材料の表面には酸化物等の汚染層
が形成されるが、この表面汚染層を除去する方法とし
て、研磨等の機械的除去方法の他、酸により洗浄除去す
る方法（酸洗）が行われている。該酸洗は、１０％程度
の硝酸と５％程度のフッ酸を含有する水溶液（硝フッ酸
液）に上記チタン材料を浸漬し、その後水洗するという
方法である。これらの方法によってチタン材料の汚染層
が除去され、二次加工時における成形性及び機械的性質
や耐食性等の品質を保っている。2. Description of the Related Art A contaminated layer such as an oxide is formed on the surface of a titanium material by heating in a rolling process or annealing after plastic working. As a method for removing the surface contaminated layer, a machine such as polishing is used. In addition to the selective removal method, a method of washing and removing with an acid (acid washing) is performed. The pickling is a method in which the above titanium material is immersed in an aqueous solution containing about 10% nitric acid and about 5% hydrofluoric acid (a nitric hydrofluoric acid solution), and then washed with water. By these methods, the contaminant layer of the titanium material is removed, and the quality such as moldability and mechanical properties and corrosion resistance during secondary processing is maintained.
【０００３】[0003]
【発明が解決しようとする課題】従来のチタン材料は、
化学，電力といった分野で利用されており、従って上記
従来の除去方法を施した程度のチタン材料であっても、
支障なく用いることができた。しかし、上記従来の方法
では、チタン材料表面に、部分的な光沢の違いや着色に
よる斑がしばしば生じる為、近年、表面の美麗さが一層
強く要求される建材や看板等に用いられ始めるに至って
問題視される様になってきた。The conventional titanium materials are:
It is used in fields such as chemistry and electric power.
It could be used without any problems. However, in the above-mentioned conventional method, spots due to partial gloss difference and coloring often occur on the surface of the titanium material, and in recent years, the titanium material has begun to be used for building materials, signboards and the like that require a more beautiful surface. It has come to be seen as a problem.
【０００４】そこで、上記酸洗を綺麗な表面が得られる
まで２度，３度と繰り返し行うという方法が考えられた
が、この場合は生産性が非常に低下し、またコストが高
くなるといった問題がある。Therefore, a method has been conceived in which the above-mentioned pickling is repeated two or three times until a clean surface is obtained. However, in this case, the productivity is extremely reduced and the cost is increased. There is.
【０００５】本発明は以上の様な問題に鑑みてなされた
もので、生産性の低下やコストの高騰を招くことなく、
表面の斑を防止した美麗なチタン材料を得る方法を提供
することを目的とする。[0005] The present invention has been made in view of the above problems, without causing a decrease in productivity and a rise in cost.
It is an object of the present invention to provide a method for obtaining a beautiful titanium material in which surface unevenness is prevented.
【０００６】[0006]
【課題を解決するための手段】本発明に係るチタン材料
の製造方法は、純チタンまたはチタン合金に対して、前
記酸洗液が１５mm／秒以上の流速で接する様にして酸洗
することを要旨とする（以下、方法と称することがあ
る）。そして更に、前記酸洗が純チタンまたはチタン合
金の５μｍ以上の深さに及ぶものである。According to the present invention, there is provided a method for producing a titanium material, wherein the pickling liquid is contacted with pure titanium or a titanium alloy at a flow rate of 15 mm / sec or more. A summary (hereinafter, may be referred to as a method). Further, the pickling extends to a depth of 5 μm or more of pure titanium or a titanium alloy.
【０００７】また本発明に係る製造方法は、純チタンま
たはチタン合金を酸洗液を用いて酸洗した後水洗する方
法において、前記酸洗の後、前記純チタンまたはチタン
合金が乾燥する以前に、前記水洗を行うことを要旨とす
る（以下、方法と称することがある）。そして更に、
純チタンまたはチタン合金に酸洗液を１５mm／秒以上の
流速で接するようにして上記酸洗を行うものとする（方
法＋方法）。Further, in the method according to the present invention, the pure titanium or the titanium alloy is pickled using an pickling liquid and then washed with water, and after the pickling, before the pure titanium or the titanium alloy is dried. The gist is that the washing is performed (hereinafter, sometimes referred to as a method). And furthermore
The above-mentioned pickling is performed by bringing a pickling solution into contact with pure titanium or a titanium alloy at a flow rate of 15 mm / sec or more (method + method).
【０００８】或いは、同じく純チタンまたはチタン合金
を酸洗液を用いて酸洗した後水洗する方法において、前
記酸洗の後、３重量％以上の過酸化水素水溶液により前
記純チタンまたはチタン合金を処理し、その後水洗する
ことを要旨とする（以下、方法と称することがあ
る）。[0008] Alternatively, in a method in which pure titanium or a titanium alloy is also washed with an acid using a pickling solution and then washed with water, the pure titanium or titanium alloy is washed with a 3% by weight or more aqueous hydrogen peroxide solution after the pickling. The gist is to treat and then wash with water (hereinafter sometimes referred to as a method).
【０００９】更に、１５mm／秒以上の流速を持つ酸洗液
により純チタンまたはチタン合金の酸洗を行った後、３
重量％以上の過酸化水素水溶液により前記純チタンまた
はチタン合金を処理し、その後水洗することが好ましい
（方法＋方法）。加えて、この酸洗の量が、前記純
チタンまたはチタン合金の５μｍ以上の深さに及ぶもの
であることがより好ましい。また上述の、純チタンまた
はチタン合金に酸洗液を１５mm／秒以上の流速で接する
ようにして酸洗した後、前記純チタンまたはチタン合金
が乾燥する以前に水洗を行う方法（方法＋方法）に
おいて、上記酸洗の量が、前記純チタンまたはチタン合
金の５μｍ以上の深さに及ぶものであることがより好ま
しい。Further, pure titanium or a titanium alloy is pickled with a pickling liquid having a flow rate of 15 mm / sec or more.
It is preferable to treat the pure titanium or titanium alloy with an aqueous solution of hydrogen peroxide of at least% by weight and then wash with water (method + method). In addition, it is more preferable that the amount of the pickling should extend to a depth of 5 μm or more of the pure titanium or titanium alloy. Further, a method (method + method) in which after the pickling liquid is brought into contact with the pure titanium or the titanium alloy at a flow rate of 15 mm / sec or more and pickled, the water is washed before the pure titanium or the titanium alloy is dried (method + method). In the above, it is more preferable that the amount of the pickling is one that reaches a depth of 5 μm or more of the pure titanium or titanium alloy.
【００１０】[0010]
【発明の実施の形態】純チタンまたはチタン合金材の表
面斑の発生原因を解明すべく鋭意研究したところ、表面
の斑は光沢の違いによるものと着色によるものとに大分
することができ、このうち光沢の違いによる斑について
は、酸洗液に純チタンまたはチタン合金（以下、被酸洗
材と総称することがある）を浸漬した際に、被酸洗材の
部位によって酸洗速度に差を生じ、この為光沢に差を生
じて斑となることが分かった。酸洗液に被酸洗材を徐々
に浸漬した場合には、先に浸漬された部分と後に浸漬さ
れた部分とに、酸洗速度の差を生じることは当然である
が、たとえ被酸洗材を酸洗液に均等に浸漬する様にして
も、上記斑を起こす酸洗速度の差が生じるものであっ
た。BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have conducted intensive studies to elucidate the causes of surface irregularities of pure titanium or titanium alloy materials. As a result, surface irregularities can be roughly classified into those due to differences in gloss and those due to coloring. Regarding the unevenness due to the difference in luster, when pure titanium or a titanium alloy (hereinafter, sometimes collectively referred to as “acid pickling material”) is immersed in the pickling liquid, the pickling speed differs depending on the portion of the pickling material. It was found that there was a difference in gloss, which resulted in spots. If the pickled material is gradually immersed in the pickling solution, it is natural that there will be a difference in the pickling rate between the previously immersed portion and the later immersed portion. Even if the material is evenly immersed in the pickling solution, a difference in the pickling speed causing the above-mentioned spots occurs.
【００１１】上記酸洗速度の差の原因としては、酸洗反
応時に発生する気泡によって反応が妨げられることが考
えられ、また浸漬初期における浴中の酸洗液の微妙な濃
度斑が、酸洗反応が進むにつれて濃淡の大きな濃度斑と
なり、被酸洗材の部位によって不均一な反応速度となる
こと等が考えられる。The reason for the difference in the pickling speed is considered to be that the reaction is hindered by bubbles generated during the pickling reaction, and that the delicate unevenness of the concentration of the pickling solution in the bath in the early stage of immersion is caused by the pickling. It is conceivable that, as the reaction proceeds, a large density unevenness occurs, resulting in an uneven reaction rate depending on the portion of the material to be pickled.
【００１２】本発明の方法においては、被酸洗材を酸
洗液に浸漬して酸洗する際に、被酸洗材の表面に対して
酸洗液を流動させる様にしたから、該被酸洗材から発生
した気泡が液流れによって剥離し、また上述の様な酸洗
液の濃度斑が撹拌によって軽減する等の影響もあり、こ
れらによって被酸洗材の表面における酸洗反応が全体的
に均一化されて進行することになり、光沢の違いによる
表面の斑が肉眼で感知され得ない程に低減される。In the method of the present invention, when the pickling material is immersed in the pickling solution and pickled, the pickling solution is caused to flow on the surface of the pickling material. Bubbles generated from the pickling material are peeled off by the liquid flow, and the concentration unevenness of the pickling solution as described above is reduced by stirring. In this case, the surface becomes uneven and the unevenness due to the difference in gloss is reduced so that it cannot be perceived by the naked eye.
【００１３】上記酸洗液の流動については、流速が被酸
洗材に対して１５mm／秒以上であれば、反応を均一にす
る効果を発揮する。尚、３０mm／秒以上ではその効果が
飽和する。With regard to the flow of the pickling solution, if the flow rate is 15 mm / sec or more with respect to the pickling material, the effect of making the reaction uniform is exhibited. At 30 mm / sec or more, the effect is saturated.
【００１４】酸洗時間が短く比較的遅い流速で酸洗を行
った場合は、大きな気泡が所々で除かれる程度であり、
また酸洗液の濃度斑の解消が不十分であること等から、
酸洗反応を表面全体に均一にするという効果の発現が不
十分となる。また、反応初期段階では濃度斑がなくても
酸洗反応が不均一に起こる（非定常に酸洗反応が起こ
る）と考えられるから、酸洗時間が短か過ぎる場合は、
たとえ比較的速い流速であっても、非定常に酸洗反応が
進行している段階で酸洗を中止することになる為、被酸
洗材の部位による進行速度に差を生じ、不均一な表面と
なる。そこで、酸洗反応が均一になったか否かについ
て、被酸洗材の酸洗量を指標として現すと、前記被酸洗
材の表面から平均５μｍ以上の深さに及ぶまで酸洗した
場合は、酸洗反応速度が均一となっており、好ましい。When the pickling time is short and the pickling is performed at a relatively low flow rate, large bubbles are removed in some places.
Also, because the concentration unevenness of the pickling solution is insufficiently eliminated,
The effect of making the pickling reaction uniform over the entire surface is insufficient. In addition, in the early stage of the reaction, it is considered that the pickling reaction occurs unevenly even if there is no concentration unevenness (the pickling reaction occurs unsteadily). If the pickling time is too short,
Even if the flow rate is relatively high, the pickling will be stopped at the stage where the pickling reaction is progressing unsteadily. Surface. Therefore, regarding whether or not the pickling reaction has become uniform, when the pickling amount of the pickled material is expressed as an index, when pickling is performed to an average depth of 5 μm or more from the surface of the pickled material, In addition, the pickling reaction rate is uniform, which is preferable.
【００１５】次に、着色による純チタンまたはチタン合
金材料の表面の斑について述べる。酸洗プロセスは、通
常前述の様に、まず酸洗液により酸洗処理をした後水洗
を行うが、該酸洗の後、水洗の前に、被酸洗材の表面が
乾燥してしまうと、水洗後に上記乾燥した部分が発色
し、着色斑が生じるということが分かった。この着色斑
は、その後水洗を十分に行っても除去することができな
い。尚、被酸洗材表面は、酸洗の際の反応熱によって温
度が上昇して乾燥し易くなっているから、着色斑も発生
し易くなっている。Next, the unevenness of the surface of the pure titanium or titanium alloy material due to coloring will be described. As described above, the pickling process is usually performed by first pickling with a pickling solution and then washing with water. However, after the pickling, if the surface of the material to be pickled is dried before washing with water. It was found that after washing with water, the dried portion developed color, causing color spots. The colored spots cannot be removed even after sufficient washing with water. In addition, since the temperature of the pickling material surface is increased by the reaction heat at the time of pickling and is easily dried, coloring spots are also easily generated.
【００１６】しかし、本発明の方法では、酸洗の後、
被酸洗材の表面が乾燥する前に水洗する様にしたから、
上記着色斑を回避することができる。また、上記方法
の様に、酸洗の後、３重量％以上の過酸化水素水溶液に
よって被酸洗材を処理し、次に水洗することでも、上記
着色斑を回避できることが分かった。However, in the method of the present invention, after pickling,
Since the surface of the pickled material was washed with water before drying,
The above-mentioned coloring spots can be avoided. It was also found that the coloring spots can be avoided by treating the material to be pickled with an aqueous solution of 3% by weight or more of hydrogen peroxide after pickling and then washing with water as in the above method.
【００１７】被酸洗材の表面は酸洗時の反応熱により５
０℃程度まで上昇する場合があり、この様な場合には上
記方法の説明で述べた様に、速やかに乾燥が進んでし
まうので、乾燥前に手際良く水洗することは困難なこと
がある。しかし、上記方法の場合は、酸洗後の乾燥如
何にかかわることなく着色斑を回避することができる。
また、上記方法の場合は、上記過酸化水素水溶液での
処理の後、乾燥するか否かにもかかわることがなく着色
斑を防止できる。The surface of the material to be pickled is heated by the reaction heat during pickling.
The temperature may rise to about 0 ° C., and in such a case, as described in the description of the above-described method, the drying proceeds rapidly, so that it may be difficult to cleanly wash with water before drying. However, in the case of the above method, coloring spots can be avoided without regard to drying after pickling.
In addition, in the case of the above method, after the treatment with the aqueous hydrogen peroxide solution, coloring spots can be prevented irrespective of whether or not drying is performed.
【００１８】上記過酸化水素水溶液による処理の方法と
しては、該水溶液の噴霧や、該水溶液に被酸洗材を浸漬
する方法等が挙げられる。また過酸化水素水溶液の濃度
としては、噴霧の場合には散布量によって異なるが、概
ね前記の様に３重量％以上が良く、５重量％以上とすれ
ば効果を十分に発揮させつつ噴霧量を少なくすることが
できるので好ましい。Examples of the method of treatment with the aqueous hydrogen peroxide solution include a method of spraying the aqueous solution and a method of immersing the material to be pickled in the aqueous solution. The concentration of the aqueous hydrogen peroxide solution varies depending on the spraying amount in the case of spraying, but is preferably 3% by weight or more, as described above, and if it is 5% by weight or more, the effect is sufficiently exhibited while the effect is sufficiently exhibited. It is preferable because it can be reduced.
【００１９】更に、上記方法と上記方法、或いは上
記方法と上記方法を組み合わせれば、光沢の差によ
る斑および着色による斑の双方を防止でき、全く斑のな
いチタン材料を得ることができてより好ましい。Further, by combining the above method and the above method, or combining the above method and the above method, it is possible to prevent both unevenness due to difference in gloss and unevenness due to coloring, and to obtain a titanium material having no unevenness. preferable.
【００２０】[0020]
＜実験１＞（上記方法について） 大きさ30mm（幅）×100mm （長さ）×1mm （厚さ）のJI
S H 4600の１種に相当する純チタン板を、700 ℃で１分
間大気中にて酸化を施して表面を汚染し、これを試料と
した。<Experiment 1> (About the above method) JI of size 30mm (width) x 100mm (length) x 1mm (thickness)
A pure titanium plate corresponding to one kind of SH 4600 was oxidized in the air at 700 ° C. for 1 minute to contaminate the surface, and this was used as a sample.
【００２１】酸洗液として１０％硝酸−５％フッ酸水溶
液をビーカーに入れて４０℃に保ち、ここに上記試料の
一部分を50mm程浸漬し、下記表１に示す時間、下記表１
の流速（試料表面に対する流速）となる様に、マグネテ
ィックスターラーによって撹拌，もしくは静置すること
によって酸洗を行った。その後速やかに水洗を行い、乾
燥した。酸洗液への試料の浸漬部分について厚み減量を
測定して酸洗量とし、また試料表面の光沢の差による斑
の発生状況を観察した。これらの結果を表１に併記す
る。A 10% nitric acid-5% hydrofluoric acid aqueous solution was placed as a pickling solution in a beaker and kept at 40 ° C., and a portion of the above sample was immersed for about 50 mm in the beaker.
Pickling was carried out by stirring or standing with a magnetic stirrer so that the flow rate became a flow rate (flow rate with respect to the sample surface). Then, it was quickly washed with water and dried. The thickness reduction was measured for the portion of the sample immersed in the pickling solution to determine the amount of pickling, and the occurrence of spots due to the difference in gloss on the sample surface was observed. These results are also shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１から分かる様に、試料（被酸洗材）に
対して酸洗液が流動していない（流速０mm／秒）比較例
１，３や、流速１０mm／秒という様に流動が緩やかな比
較例２では、試料表面に斑が観察されたが、酸洗液が試
料に対して流速１５mm／秒以上で流動している実施例１
〜５，参考例１の場合はほとんど斑が観察されなかっ
た。また流速０mm／秒の場合（比較例３）は表面斑が観
察されるが、短時間の酸洗であっても、参考例１の様に
流速を与えることで表面斑が軽減する。As can be seen from Table 1, the pickling liquid does not flow with respect to the sample (material to be pickled) (flow rate 0 mm / sec). In Comparative Example 2, although unevenness was observed on the surface of the sample, the pickling solution was flowing at a flow rate of 15 mm / sec or more with respect to the sample.
In the cases of ５，5 and Reference Example 1, almost no spots were observed. In the case of a flow rate of 0 mm / sec (Comparative Example 3), surface spots are observed, but even with a short-time pickling, the surface spots are reduced by giving a flow rate as in Reference Example 1.
【００２４】＜実験２＞（上記方法について） 前記実験１の試料と同様の、汚染層を有する純チタンの
試料を用いた。１０％硝酸−５％フッ酸水溶液（酸洗
液）をビーカーに入れて４０℃に保ち、ここに上記試料
の一部分を50mm程浸漬し、酸洗液の流速が試料表面に対
して３０mm／秒となる様にマグネティックスターラーに
よって４０秒間撹拌して酸洗した。実施例７については
酸洗後乾燥する前に水洗を行い、比較例４についてはド
ライヤーの熱風を吹きかけて乾燥した後、水洗を行っ
た。これらの表面について着色斑の有無を観察した。そ
の結果を下記表２に示す。<Experiment 2> (Regarding the Method) A pure titanium sample having a contaminated layer, similar to the sample of Experiment 1, was used. A 10% nitric acid-5% hydrofluoric acid aqueous solution (pickling solution) was placed in a beaker and maintained at 40 ° C., and a portion of the sample was immersed in the same by about 50 mm. The mixture was stirred with a magnetic stirrer for 40 seconds and pickled. In Example 7, washing with water was performed before pickling and drying. In Comparative Example 4, drying was performed by blowing hot air from a dryer, and then washing with water was performed. These surfaces were observed for the presence of coloring spots. The results are shown in Table 2 below.
【００２５】[0025]
【表２】 [Table 2]
【００２６】表２から分かる様に、乾燥を経て水洗した
比較例４では着色による表面斑が観察されたが、乾燥し
ないうちに水洗した実施例７は斑が発生しなかった。As can be seen from Table 2, in Comparative Example 4 which was washed with water after drying, surface spots due to coloring were observed, but in Example 7 which was washed with water before drying, no spots were generated.
【００２７】＜実験３＞（上記方法について） 前記実験１，２の試料と同様の、汚染層を有する純チタ
ンの試料を用い、実施例８〜１３，比較例５〜８として
下記の如く処理を施した。尚、下記において「乾燥」の
字句がないものは、乾燥前に次の処理を行ったことを現
す。 実施例８〜１０ ：酸洗→乾燥→H2O2水溶液処理→乾燥→水洗 実施例１１，比較例５：酸洗→乾燥→H2O2水溶液処理→水洗 実施例１２，比較例６：酸洗→H2O2水溶液処理→乾燥→水洗 実施例１３ ：酸洗→H2O2水溶液処理→水洗 比較例７ ：酸洗→乾燥→水洗→H2O2水溶液処理→水洗 比較例８ ：酸洗→乾燥→水洗<Experiment 3> (Regarding the above method) Using the same pure titanium sample having a contaminated layer as the samples of Experiments 1 and 2, processing was performed as Examples 8 to 13 and Comparative Examples 5 to 8 as follows. Was given. In the following, those without the term “dry” indicate that the following processing was performed before drying. Examples 8 to 10: Pickling → drying → H 2 O 2 aqueous solution treatment → drying → water washing Example 11, Comparative Example 5: Pickling → drying → H 2 O 2 aqueous solution treatment → water washing Example 12, Comparative Example 6: Pickling → H 2 O 2 aqueous solution treatment → drying → water washing Example 13: Pickling → H 2 O 2 aqueous solution treatment → water washing Comparative Example 7: Pickling → drying → water washing → H 2 O 2 aqueous solution treatment → water washing Comparative Example 8 : Pickling → drying → washing with water
【００２８】上記酸洗処理工程としては、上記実験２と
同様に、１０％硝酸−５％フッ酸水溶液（酸洗液）をビ
ーカーに入れて４０℃に保ち、ここに上記試料の一部分
を50mm程浸漬し、酸洗液の流速が試料表面に対して３０
mm／秒となる様にマグネティックスターラーによって４
０秒間撹拌した。上記H2O2水溶液処理工程としては、下
記表３に示す濃度の過酸化水素水溶液を用い、噴霧器に
より試料表面に噴霧した。上記乾燥工程は上記実験２と
同様に、ドライヤーの熱風を吹きかけることにより行っ
た。これらについて試料表面の着色斑の有無を観察し
た。その結果、および各処理条件をまとめて表３に示
す。In the pickling treatment step, a 10% nitric acid-5% hydrofluoric acid aqueous solution (pickling solution) was placed in a beaker and kept at 40 ° C., and a part of the sample was placed at 50 mm in the same manner as in Experiment 2. And the flow rate of the pickling solution is 30
mm / sec with magnetic stirrer to 4
Stirred for 0 seconds. In the H 2 O 2 aqueous solution treatment step, a hydrogen peroxide aqueous solution having a concentration shown in Table 3 below was used and sprayed on the sample surface by a sprayer. The drying step was performed by blowing hot air from a dryer, as in Experiment 2. For these, the presence or absence of colored spots on the sample surface was observed. Table 3 shows the results and the respective processing conditions.
【００２９】[0029]
【表３】 [Table 3]
【００３０】以上の結果から分かる様に、過酸化水素水
溶液で処理したものは、酸洗後の乾燥の有無にかかわら
ず、また最終的な水洗の前の乾燥（H2O2水溶液処理後の
乾燥）の有無にかかわらず、斑は生じなかった。また、
H2O2水溶液の濃度としては、２％と薄い場合（比較例
５，６）では効果がなく、３％以上が良いことが分か
る。As can be seen from the above results, those treated with an aqueous solution of hydrogen peroxide were dried regardless of whether or not they were dried after pickling, and were dried before final washing with water (after the treatment with an aqueous H 2 O 2 solution). With or without dryness), no spots were formed. Also,
When the concentration of the H 2 O 2 aqueous solution is as low as 2% (Comparative Examples 5 and 6), there is no effect, and it is understood that 3% or more is good.
【００３１】一方、比較例７から分かる様に、酸洗後に
乾燥し、一旦水洗を行ったものは、その後たとえ過酸化
水素水溶液によって処理を施しても着色斑が観察され
た。従って、水洗前に過酸化水素水溶液による処理を行
う必要があることが分かる。On the other hand, as can be seen from Comparative Example 7, coloring spots were observed on those dried after pickling and once washed with water, even after being treated with an aqueous hydrogen peroxide solution. Therefore, it is understood that it is necessary to perform the treatment with the aqueous hydrogen peroxide solution before washing with water.
【００３２】[0032]
【発明の効果】以上の様に本発明によれば、表面に斑が
なく美麗な純チタンまたはチタン合金材を製造すること
ができ、しかも生産性の低下なく、またコストを安く行
うことができる。As described above, according to the present invention, a beautiful pure titanium or titanium alloy material having no unevenness on the surface can be manufactured, and further, the productivity can be reduced and the cost can be reduced. .
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C23G 1/12 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) C23G 1/12
Claims (6)
いて酸洗する方法において、 前記純チタンまたはチタン合金に対して、前記酸洗液が
１５mm／秒以上の流速で接するようにし、 前記酸洗が純チタンまたはチタン合金の５μｍ以上の深
さに及ぶものであることを特徴とする表面の美麗な純チ
タンまたはチタン合金材の製造方法。1. A pure titanium or titanium alloy using an pickling liquid
In the method of pickling, the pickling liquid is applied to the pure titanium or titanium alloy.
To contact at least a flow rate of 15 mm / sec, beautiful pure titanium or manufacturing method of a titanium alloy material surface, wherein said pickling is intended to cover 5μm or more of the depth of the pure titanium or titanium alloy.
いて酸洗し、その後水洗する表面の美麗な純チタンまた
はチタン合金材の製造方法において、 前記酸洗の後、３重量％以上の過酸化水素水溶液により
前記純チタンまたはチタン合金材を処理し、その後水洗
することを特徴とする表面の美麗な純チタンまたはチタ
ン合金材の製造方法。2. A method for producing pure titanium or a titanium alloy material having a beautiful surface with pure titanium or a titanium alloy pickled using an acid washing liquid and then water-washed, wherein after the acid washing, 3% by weight or more A method for producing pure titanium or a titanium alloy material having a beautiful surface, comprising treating the pure titanium or titanium alloy material with an aqueous solution of hydrogen peroxide and then washing with water.
いて酸洗する方法において、 前記純チタンまたはチタン合金に対して、前記酸洗液が
１５mm／秒以上の流速で接するようにし、 この 酸洗の後、乾燥する以前に、前記水洗を行うことを
特徴とする表面の美麗な純チタンまたはチタン合金材の
製造方法。3. A pickling solution for pure titanium or a titanium alloy.
In the method of pickling, the pickling liquid is applied to the pure titanium or titanium alloy.
To contact at least a flow rate of 15 mm / sec, after this pickling, prior to drying, to carry out the washing
A method for producing pure titanium or titanium alloy material with a beautiful surface.
行う請求項１に記載の表面の美麗な純チタンまたはチタ
ン合金材の製造方法。After wherein said pickling, prior to drying, beautiful pure titanium or manufacturing method of a titanium alloy material surface according to claim 1 for washing.
いて酸洗する方法において、 前記純チタンまたはチタン合金に対して、前記酸洗液が
１５mm／秒以上の流速で接するようにし、 この 酸洗の後、３重量％以上の過酸化水素水溶液により
前記純チタンまたはチタン合金を処理し、その後水洗す
ることを特徴とする表面の美麗な純チタンまたはチタン
合金材の製造方法。5. A pure titanium or titanium alloy using an pickling liquid.
In the method of pickling, the pickling liquid is applied to the pure titanium or titanium alloy.
To contact at a flow rate of more than 15 mm / sec, after this pickling, 3 to process the pure titanium or titanium alloy by weight percent aqueous solution of hydrogen peroxide, beautiful net subsequent washing surfaces, which comprises Manufacturing method of titanium or titanium alloy material.
素水溶液により前記純チタンまたはチタン合金を処理
し、その後水洗する請求項１に記載の表面の美麗な純チ
タンまたはチタン合金材の製造方法。6. The pure titanium or titanium alloy material according to claim 1 , wherein the pure titanium or titanium alloy is treated with an aqueous solution of 3% by weight or more of hydrogen peroxide after the pickling, and then washed with water. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30016495A JP3246298B2 (en) | 1995-11-17 | 1995-11-17 | Method for producing pure titanium or titanium alloy material with beautiful surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30016495A JP3246298B2 (en) | 1995-11-17 | 1995-11-17 | Method for producing pure titanium or titanium alloy material with beautiful surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09143769A JPH09143769A (en) | 1997-06-03 |
| JP3246298B2 true JP3246298B2 (en) | 2002-01-15 |
Family
ID=17881524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30016495A Expired - Fee Related JP3246298B2 (en) | 1995-11-17 | 1995-11-17 | Method for producing pure titanium or titanium alloy material with beautiful surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3246298B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267831B1 (en) | 1998-05-06 | 2001-07-31 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method of making a titanium or titanium alloy strip having a decorative surface appearance |
| CN111364046B (en) * | 2020-03-16 | 2023-10-31 | 宁夏中色金航钛业有限公司 | Brightening pickling method for rare metal and alloy processing material thereof and pickling solution |
-
1995
- 1995-11-17 JP JP30016495A patent/JP3246298B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09143769A (en) | 1997-06-03 |
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