JPH09143769A - Production of pure titanium or titanium alloy material having beautiful surface - Google Patents
Production of pure titanium or titanium alloy material having beautiful surfaceInfo
- Publication number
- JPH09143769A JPH09143769A JP30016495A JP30016495A JPH09143769A JP H09143769 A JPH09143769 A JP H09143769A JP 30016495 A JP30016495 A JP 30016495A JP 30016495 A JP30016495 A JP 30016495A JP H09143769 A JPH09143769 A JP H09143769A
- Authority
- JP
- Japan
- Prior art keywords
- pickling
- titanium
- titanium alloy
- pure titanium
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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)
Abstract
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。尚、本明細書において、酸洗前のも
のを純チタンまたはチタン合金と称し、酸洗後のものを
純チタンまたはチタン合金材（若しくはチタン材料）と
称している。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing pure titanium or titanium alloy material having a beautiful surface (hereinafter, also referred to as titanium material in general). It is useful for producing a pure titanium or titanium alloy wrought material that is often used in a required field. In the present specification, those before pickling are referred to as pure titanium or titanium alloy, and those after pickling are referred to as pure titanium or titanium alloy material (or titanium material).
【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 of removing this contaminated layer, a machine such as polishing is used. In addition to the selective removal method, a method of removing by washing with an acid (pickling) is performed. The pickling is a method of immersing the titanium material in an aqueous solution (nitric hydrofluoric acid solution) containing about 10% nitric acid and about 5% hydrofluoric acid, and then washing with water. By these methods, the contamination layer of the titanium material is removed, and the quality such as formability and mechanical properties during secondary processing and corrosion resistance are 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 material is
It is used in fields such as chemistry and power, and therefore even titanium materials that have been subjected to the above conventional removal methods,
It could be used without any problems. However, in the above-mentioned conventional method, since a difference in gloss and a spot due to coloring often occur on the titanium material surface, in recent years, it has begun to be used for building materials, signboards, etc. where surface beauty is strongly required. It's becoming 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 considered in which the above-mentioned pickling is repeated twice or three times until a clean surface is obtained, but in this case, the productivity is extremely lowered 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。The present invention has been made in view of the above problems, and does not cause 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 which prevents surface spots.
【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）。更に、前記酸洗が純チタンまたはチタン合金の５
μｍ以上の深さに及ぶものであることが望ましい。In the method for producing a titanium material according to the present invention, pure titanium or a titanium alloy is pickled by contacting the pickling solution at a flow rate of 15 mm / sec or more. It will be the gist (hereinafter sometimes referred to as a method). Further, the pickling is performed with pure titanium or titanium alloy 5
It is desirable that the depth is at least μm.
【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）。The production method according to the present invention is a method of pickling pure titanium or a titanium alloy with a pickling solution and then washing with water, after the pickling and before the pure titanium or titanium alloy is dried. The main point is to perform the washing with water (hereinafter, sometimes referred to as a 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）。Alternatively, in the same manner as above, in a method of pickling pure titanium or a titanium alloy with a pickling solution and then washing with water, the pure titanium or titanium alloy is washed with an aqueous solution of hydrogen peroxide of 3% by weight or more after the pickling. The point is to treat and then wash with water (hereinafter sometimes referred to as a method).
【０００９】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、
水洗を行うことが好ましい（方法＋方法）。或い
は、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、これらの酸洗の量が、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。Furthermore, after the pure titanium or titanium alloy is pickled with a pickling solution in contact with the pure titanium or titanium alloy at a flow rate of 15 mm / sec or more, before the pure titanium or titanium alloy is dried,
Washing with water is preferable (method + method). Alternatively, pure titanium or a titanium alloy is pickled with a pickling solution having a flow rate of 15 mm / sec or more, and then the pure titanium or titanium alloy is treated with a hydrogen peroxide aqueous solution of 3% by weight or more, and then washed with water. It is preferable (method + method). In addition, it is more preferable that the amount of these picklings 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 As a result of intensive research to elucidate the cause of surface unevenness of pure titanium or a titanium alloy material, the unevenness of the surface can be largely classified into the difference in gloss and the difference in color. Regarding the unevenness due to the difference in gloss, when pure titanium or titanium alloy (hereinafter sometimes collectively referred to as pickled material) is immersed in the pickling solution, the pickling speed varies depending on the part of the pickled material. It was found that this caused a difference in gloss and resulted in unevenness. When the pickling material is gradually dipped in the pickling solution, a difference in pickling speed naturally occurs between the previously dipped portion and the subsequently dipped portion. Even if the material was evenly dipped in the pickling solution, there was a difference in pickling speed that caused the above-mentioned unevenness.
【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。It is considered that the cause of the difference in the pickling speed is that air bubbles generated during the pickling reaction hinder the reaction, and that the delicate concentration unevenness of the pickling solution in the bath at the initial stage of the immersion is due to the pickling. It is conceivable that as the reaction progresses, the density unevenness becomes large and the reaction rate becomes non-uniform depending on the site 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 made to flow over the surface of the pickling material. Bubbles generated from the pickling material are separated by the liquid flow, and the concentration unevenness of the pickling solution as described above is also reduced by stirring, etc., so that the pickling reaction on the surface of the pickled material as a whole is affected. The surface unevenness due to the difference in gloss is reduced to the extent 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。Regarding the flow of the pickling solution, if the flow rate is 15 mm / sec or more with respect to the material to be pickled, the effect of making the reaction uniform is exhibited. The effect is saturated at 30 mm / sec or more.
【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 carried out at a relatively slow flow rate, large bubbles are removed in some places,
In addition, because the concentration unevenness of the pickling solution is insufficiently resolved,
The effect of making the pickling reaction uniform over the entire surface becomes insufficient. In the initial stage of the reaction, the pickling reaction is considered to occur nonuniformly (even if the pickling reaction occurs unsteadily) even if there is no unevenness in concentration, so if the pickling time is too short,
Even if the flow rate is relatively high, pickling will be stopped at a stage where the pickling reaction is progressing unsteadily, so there will be differences in the rate of progress depending on the site of the material to be pickled, resulting in uneven It becomes the surface. Therefore, regarding whether or not the pickling reaction has become uniform, the pickling amount of the material to be pickled is used as an index, and when pickling is performed from the surface of the material to be picked up to a depth of 5 μm or more on average, 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 pure titanium or titanium alloy material due to coloring will be described. In the pickling process, as described above, usually, a pickling treatment is first performed with a pickling solution, followed by washing with water. If the surface of the material to be pickled is dried after the pickling and before the washing with water. After washing with water, it was found that the above-mentioned dried portion was colored to cause colored spots. The colored spots cannot be removed even after sufficient washing with water. The surface of the material to be pickled is likely to cause colored spots because the temperature of the surface of the material to be pickled rises easily due to the reaction heat during pickling.
【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 material to be pickled is washed with water before it dries,
It is possible to avoid the colored spots. It was also found that the above-mentioned colored spots can be avoided by treating the material to be pickled with an aqueous solution of hydrogen peroxide of 3% by weight or more and then washing with water after pickling 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 becomes 5 due to the reaction heat during pickling.
The temperature may rise to about 0 ° C., and in such a case, as described in the explanation of the above method, the drying proceeds rapidly, so that it may be difficult to wash with water well before the drying. However, in the case of the above-mentioned method, it is possible to avoid the coloring unevenness regardless of whether the pickling is followed by the drying.
Further, in the case of the above method, it is possible to prevent the coloring unevenness regardless of whether or not it is dried after the treatment with the hydrogen peroxide aqueous solution.
【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 spraying the aqueous solution and immersing the material to be pickled in the aqueous solution. The concentration of the aqueous hydrogen peroxide solution varies depending on the spray amount in the case of spraying, but it is generally 3% by weight or more as described above, and if it is 5% by weight or more, the spraying amount can be sufficiently exerted 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。Furthermore, 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 30 mm (width) x 100 mm (length) x 1 mm (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。As a pickling solution, a 10% nitric acid-5% hydrofluoric acid aqueous solution was placed in a beaker and kept at 40 ° C., a part of the above sample was immersed in the beaker for about 50 mm, and the time shown in the following table 1 and the following table 1
The pickling was carried out by stirring with a magnetic stirrer or by leaving it still so that the flow rate was (the flow rate with respect to the sample surface). Then, it was quickly washed with water and dried. The thickness reduction of the portion where the sample was dipped in the pickling solution was measured to determine the pickling amount, 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
〜６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、実施例５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 solution did not flow to the sample (material to be pickled) (flow rate 0 mm / sec), and the flow rate was 10 mm / sec. In mild Comparative Example 2, spots were observed on the surface of the sample, but the pickling solution was flowing over the sample at a flow rate of 15 mm / sec or more Example 1
In the case of ~ 6, almost no spots were observed. When the flow velocity is 0 mm / sec (Comparative Example 3), surface spots are observed,
Even if pickling for a short time, surface unevenness is reduced by applying a flow rate as in Example 5.
【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 above method) The same sample of pure titanium having a contaminated layer as the sample of Experiment 1 was used. 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 above sample was immersed therein for about 50 mm, and the flow rate of the pickling solution was 30 mm / sec with respect to the sample surface. It was stirred for 40 seconds with a magnetic stirrer and pickled. In Example 7, washing with water was performed after pickling and before drying, and in Comparative Example 4, hot air was blown from the dryer to dry and then washing with water. The presence or absence of colored spots was observed on these surfaces. 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 dried and washed with water, surface unevenness due to coloring was observed, but in Example 7 which was washed with water before drying, no unevenness occurred.
【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 samples of pure titanium having a contaminated layer as the samples of Experiments 1 and 2, the following treatments were carried out as Examples 8 to 13 and Comparative Examples 5 to 8. Was applied. In addition, in the following, when there is no word of "drying", it means that the following treatment 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 step, as in Experiment 2, 10% nitric acid-5% hydrofluoric acid aqueous solution (pickling solution) was placed in a beaker and kept at 40 ° C., where a part of the sample was 50 mm. Soak, and the flow rate of the pickling solution is 30 with respect to the sample surface.
4 by magnetic stirrer to be mm / sec
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 the sample surface was sprayed with 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. The results and the processing conditions are summarized in Table 3.
【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 before or after the final washing with water (after the treatment with the H 2 O 2 aqueous solution), regardless of whether or not they were dried after the pickling. No spots were formed with or without dryness. Also,
It can be seen that the concentration of the H 2 O 2 aqueous solution is as small as 2% (Comparative Examples 5 and 6) with no effect, and 3% or more is preferable.
【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, in the case where the product was pickled, dried, and once washed with water, color spots were observed even after the treatment with an aqueous hydrogen peroxide solution. Therefore, it is understood that it is necessary to perform the treatment with the hydrogen peroxide aqueous 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, it is possible to produce a pure titanium or titanium alloy material which has a beautiful surface and has no spots, and further, the productivity is not lowered and the cost can be reduced. .
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 method of pickling pure titanium or a titanium alloy with a pickling solution, wherein the pickling solution is in contact with the pure titanium or titanium alloy at a flow rate of 15 mm / sec or more. A method for producing pure titanium or titanium alloy material having a beautiful surface.
５μｍ以上の深さに及ぶものである請求項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。2. The method for producing pure titanium or titanium alloy material having a beautiful surface according to claim 1, wherein the pickling is performed to a depth of 5 μm or more of 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、表
面が乾燥する以前に、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 method for producing a pure titanium or titanium alloy material having a beautiful surface, in which pure titanium or a titanium alloy is pickled with a pickling solution, and then washed with water. After the pickling, before the surface is dried. A method for producing pure titanium or titanium alloy material having a beautiful surface, which comprises performing the above-mentioned water washing.
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。4. A method for producing a pure titanium or titanium alloy material having a beautiful surface, which comprises pickling pure titanium or a titanium alloy with a pickling solution and then washing with water.
A method for producing a pure titanium or titanium alloy material having a beautiful surface, which comprises treating the pure titanium or titanium alloy material with a hydrogen peroxide aqueous solution of at least wt% and then washing with water.
行う請求項１または２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。5. The method for producing pure titanium or titanium alloy material having a beautiful surface according to claim 1 or 2, wherein after the pickling, before the drying, washing with water is performed.
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または２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 having a beautiful surface according to claim 1, wherein after the pickling, the pure titanium or titanium alloy is treated with a hydrogen peroxide aqueous solution of 3% by weight or more, and then washed with water. Method for manufacturing alloy material.
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 true JPH09143769A (en) | 1997-06-03 |
| JP3246298B2 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) |
Cited By (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 |
| CN111364046A (en) * | 2020-03-16 | 2020-07-03 | 宁夏中色金航钛业有限公司 | Bright pickling method and pickling solution for rare metal and alloy processing material thereof |
-
1995
- 1995-11-17 JP JP30016495A patent/JP3246298B2/en not_active Expired - Fee Related
Cited By (3)
| 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 |
| CN111364046A (en) * | 2020-03-16 | 2020-07-03 | 宁夏中色金航钛业有限公司 | Bright pickling method and pickling solution for rare metal and alloy processing material thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3246298B2 (en) | 2002-01-15 |
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