JPH04323392A - Method for pickling titanium material - Google Patents

Method for pickling titanium material

Info

Publication number
JPH04323392A
JPH04323392A JP8886191A JP8886191A JPH04323392A JP H04323392 A JPH04323392 A JP H04323392A JP 8886191 A JP8886191 A JP 8886191A JP 8886191 A JP8886191 A JP 8886191A JP H04323392 A JPH04323392 A JP H04323392A
Authority
JP
Japan
Prior art keywords
pickling
mol
ion
ions
titanium material
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
Application number
JP8886191A
Other languages
Japanese (ja)
Inventor
Kenji Morita
健治 森田
Hideaki Fukai
英明 深井
Toshio Sakiyama
崎山 利夫
Hiroyoshi Suenaga
末永 博義
Kuninori Minagawa
邦典 皆川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP8886191A priority Critical patent/JPH04323392A/en
Publication of JPH04323392A publication Critical patent/JPH04323392A/en
Pending legal-status Critical Current

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  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

PURPOSE:To uniformly remove a tough scale layer formed on the surface of a Ti material by pickling it with a simple equipment while satisfactorily maintaining the shape and surface roughness of the Ti material. CONSTITUTION:A Ti material is pickled by immersion in an aq. soln. contg. 0.2-2.0mol/l fluorine ions (F<->), 1.0-7.0mol/l chlorine ions (Cl<->) and 0.05-8.0mol/l ammonium ions (NH4<+>) at >=50 deg.C or by spraying with the soln. to remove scale formed on the surface of the Ti material.

Description

【発明の詳細な説明】[Detailed description of the invention]

【0001】0001

【産業上の利用分野】この発明は、チタン材表面をむら
なく脱スケールすることができるチタン材の酸洗処理方
法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for pickling titanium materials, which can evenly descale the surface of titanium materials.

【0002】0002

【従来技術及び発明が解決しようとする課題】チタン製
品の製造工程中、熱処理、熱間加工によりその表面に酸
化スケールが生じるが、この酸化スケールは美観上また
は機械加工上問題となるため、これを除去して使用する
ことが一般的である。この表面酸化スケールを除去する
方法は各種あるが、例えばMaterials  & 
 Methods,Vol.38(1953),No.
10,p.107の記載によれば、薄いスケールは硫酸
浸漬後、硝弗酸浸漬することが、また厚いスケールはソ
ルト処理後、硝弗酸浸漬、更に濃弗酸浸漬をすることに
より除去することがよいといわれている。
[Prior Art and Problems to be Solved by the Invention] During the manufacturing process of titanium products, oxide scale is generated on the surface due to heat treatment and hot working. It is common to remove the . There are various methods to remove this surface oxide scale, such as Materials &
Methods, Vol. 38 (1953), No.
10, p. According to the description in No. 107, thin scales can be removed by immersion in sulfuric acid, followed by nitric-fluoric acid immersion, and thick scales can be removed by immersion in nitric-fluoric acid and then concentrated hydrofluoric acid after salt treatment. It is said.

【0003】しかし、チタン材の表面層に形成される厚
く強固なスケール、特に650℃以上で熱処理した場合
に表面に形成されるスケールの除去は通常の酸洗液(例
えば硝酸−弗酸の混合液、弗酸−塩素−過酸化水素の水
溶液)による酸洗では不可能とされている。そのため、
このチタン材の表面の強固なスケールを除去する方法と
しては、 (1)溶融アルカリ塩浴を用いる方法。 (2)ショットブラスト等によるスケール破壊後、通常
の酸洗を用いる方法。 (3)特開昭55−145183に開示されているよう
な、超音波を作用させながら酸洗を行う方法。 などが、通常行われている。しかし、上記の方法は、以
下の点で欠点をもっている。
However, it is difficult to remove thick and strong scales that form on the surface layer of titanium materials, especially scales that form on the surface when heat treated at temperatures above 650°C. It is said that pickling with a hydrofluoric acid-chlorine-hydrogen peroxide solution is impossible. Therefore,
Methods for removing this hard scale on the surface of titanium materials include: (1) A method using a molten alkali salt bath. (2) A method using ordinary pickling after scale destruction by shot blasting or the like. (3) A method of pickling while applying ultrasonic waves, as disclosed in JP-A-55-145183. etc. are usually done. However, the above method has the following drawbacks.

【0004】(1)の方法では、溶融アルカリ塩浴は4
50〜600℃という高温を用い、さらに混酸水溶液に
浸漬するため工程が煩雑となり、さらに酸濃度を適当に
調整しないと脱スケールできなかったり、母材まで溶解
されて表面が粗れたりして良好な表面肌とはならない。
In method (1), the molten alkali salt bath is
The process is complicated because high temperatures of 50 to 600°C are used and immersion in a mixed acid aqueous solution is required, and descaling may not be possible unless the acid concentration is adjusted appropriately, or the base material may be dissolved and the surface may become rough. It does not become a superficial skin.

【0005】(2)の方法では、湿式処理と乾式処理を
組み合わせた方法であるから処理が煩雑でありしかも処
理効率が低いという難点がある。さらに、ショットブラ
ストにより表面が粗くなり、しかもその粗くなった表面
が混酸水溶液処理後も残るため、良好な表面が得られな
い。また、薄物に適応する場合、製品に変形を及ぼす場
合がある。 (3)の方法の場合には、大がかりな装置を必要とする
[0005] Method (2) is a method that combines wet processing and dry processing, and therefore has the disadvantage that the processing is complicated and the processing efficiency is low. Furthermore, the shot blasting makes the surface rough, and the roughened surface remains even after the mixed acid aqueous solution treatment, making it impossible to obtain a good surface. Furthermore, when applied to thin materials, the product may be deformed. Method (3) requires large-scale equipment.

【0006】この発明はかかる事情に鑑みてなされたも
のであって、チタン材の形状および表面粗さを良好に維
持しつつ、簡便な設備でむらなくチタン材の表層に形成
される強固なスケール層スケールを除去することができ
るチタン材の酸洗処理方法を提供することを目的とする
[0006] The present invention was made in view of the above circumstances, and it is possible to form a strong scale evenly on the surface layer of a titanium material using simple equipment while maintaining the shape and surface roughness of the titanium material well. An object of the present invention is to provide a method for pickling a titanium material that can remove layer scale.

【0007】[0007]

【課題を解決するための手段】本発明者等は、ショット
ブラスト、超音波等の機械的操作を伴うことなくチタン
材の表層に形成される強固なスケール層(650℃以上
で形成されたスケール層)を除去する方法について詳細
に検討した結果、酸性中のF− イオン、Cl−、及び
NH4 + イオンを含む混合水溶液に浸漬、あるいは
この水溶液をスプレーすることにより容易に除去出来る
ことを新たに見出したものである。
[Means for Solving the Problems] The present inventors have discovered that a strong scale layer formed on the surface layer of titanium material (scale formed at 650°C or higher) can be formed on the surface layer of titanium material without mechanical operations such as shot blasting or ultrasonic waves. As a result of a detailed study on the method for removing the F- ion, Cl- ion, and NH4 + ion, we found that it can be easily removed by immersion in a mixed aqueous solution containing F- ions, Cl- ions, and NH4 + ions in an acidic environment, or by spraying this aqueous solution. This is what I found.

【0008】すなわち、本発明は、弗素イオン(F− 
イオン):0.2〜2.0モル/リットル、塩素イオン
(Cl− イオン):1.0〜7.0モル/リットル、
アンモニウムイオン(NH4 + イオン):0.05
〜8.0モル/リットルを含有する水溶液に浸漬するか
または該液をスプレーしてチタン材表面に形成されたス
ケールを除去することを特徴とするチタン材の酸洗処理
方法を提供する。
That is, the present invention provides fluorine ions (F-
ion): 0.2 to 2.0 mol/liter, chloride ion (Cl- ion): 1.0 to 7.0 mol/liter,
Ammonium ion (NH4 + ion): 0.05
Provided is a method for pickling a titanium material, characterized in that scale formed on the surface of the titanium material is removed by immersing the material in an aqueous solution containing ~8.0 mol/liter or by spraying the solution.

【0009】この洗浄液の脱スケール能力は極めて大き
く、従来のような前処理を必要としない。特に、温度が
50℃以上の時、安定した脱スケール能力を有するので
、制御は容易である。なお、ここでチタン材とは、チタ
ンを50at%以上含有する材料をいい、純チタン、各
種チタン合金、チタン基各種金属間化合物をいう。本発
明に係る酸洗処理方法において使用される混酸、添加剤
及びその含有割合について、図面を参照しつつ説明する
。 (1)酸性中の弗素イオン(弗酸)について。
[0009] The descaling ability of this cleaning liquid is extremely large and does not require pretreatment as in the prior art. In particular, when the temperature is 50° C. or higher, it has stable descaling ability and is easy to control. Note that the titanium material herein refers to a material containing 50 at % or more of titanium, and refers to pure titanium, various titanium alloys, and various titanium-based intermetallic compounds. The mixed acid, additives, and their content ratios used in the pickling treatment method according to the present invention will be explained with reference to the drawings. (1) Regarding fluorine ions (hydrofluoric acid) in acidic conditions.

【0010】酸性中の弗素イオンは酸洗速度を維持する
のに必要なイオンであり、図1に示すように、最低で0
.2モル/l以上である必要があり、含有量が多ければ
多いほど酸洗速度は上昇するが、50℃以上で弗酸含有
量が2.0モル/l以上ある場合は酸洗速度は安定せず
制御困難となる上に、酸洗むらが起こり均一な板厚分布
が得られない。 (2)酸性中の塩素イオン(塩酸)について。 弗酸単独溶液では、チタン材の酸洗が進むと次第に酸洗
速度が低下してくる。これは次式に示すように、Ti+
4HF→TiF4 +2H2 の反応が起こり、チタン1モルについて弗素4モルが消
費されることが原因である。そのため、弗素イオンと共
に塩素イオンを含有させることによって、      
2Ti+4HF+3HCl→TiF4 +TiCl3 
+7/2H2
Fluorine ions in acidic conditions are necessary to maintain the pickling speed, and as shown in FIG.
.. It must be at least 2 mol/l, and the higher the content, the higher the pickling speed will be, but if the hydrofluoric acid content is 2.0 mol/l or more at 50°C or higher, the pickling speed will be stable. Not only is this difficult to control, but also uneven pickling occurs, making it impossible to obtain a uniform plate thickness distribution. (2) Regarding chlorine ions (hydrochloric acid) in acidic conditions. In a hydrofluoric acid solution alone, the pickling speed gradually decreases as the titanium material is pickled. This is expressed as shown in the following equation, Ti+
This is caused by the reaction of 4HF→TiF4 +2H2, in which 4 moles of fluorine are consumed per 1 mole of titanium. Therefore, by containing chlorine ions together with fluorine ions,
2Ti+4HF+3HCl→TiF4 +TiCl3
+7/2H2

【0011】の反応が生じ、塩素イオン含有によりチタ
ン1モルの溶解について弗素イオンの消費が4モルから
2モルと減少し酸洗能力が持続するようになる。この効
果を得るためには、図2に示すように塩素イオンが最低
でも1.0モル/l必要となる。また、塩素イオンを7
.0モル/l以上としても効果は上がらない。 (3)アンモニウムイオンについて。
The following reaction occurs, and due to the inclusion of chlorine ions, the consumption of fluorine ions decreases from 4 mol to 2 mol per 1 mol of titanium, and the pickling ability is maintained. In order to obtain this effect, as shown in FIG. 2, at least 1.0 mol/l of chlorine ions is required. In addition, 7 chloride ions
.. Even if it exceeds 0 mol/l, the effect will not increase. (3) Regarding ammonium ions.

【0012】アンモニウムイオンは酸化スケールをむら
なく除去するために必要なイオンであり、図3に示すよ
うに、強酸性中において、アンモニウムイオンが0.0
5モル/l以下の場合は板厚分布(酸洗むら)が大きい
が、0.05モル/l以上となると板厚分布が小さくな
り、0.2モル/l以上で板厚差を押える効果は飽和し
、その効果は8.0モル/lまで持続する。8.0モル
/l以上では、アンモニウムイオンは50℃以上の水に
容易に溶解しない。 (4)温度について。
Ammonium ions are necessary to remove oxide scale evenly, and as shown in FIG. 3, ammonium ions are 0.0
If it is less than 5 mol/l, the thickness distribution (uneven pickling) will be large, but if it is more than 0.05 mol/l, the thickness distribution will become smaller, and if it is more than 0.2 mol/l, the effect of suppressing the difference in thickness is saturated and its effect persists up to 8.0 mol/l. At 8.0 mol/l or more, ammonium ions are not easily dissolved in water at 50° C. or higher. (4) Regarding temperature.

【0013】図4に示すように、温度50℃以下では脱
スケール効果は小さく、全面酸洗することが困難である
。従って、液温は50℃以上とすることが好ましい。 100℃近くであっても、酸洗速度には大差はない。
As shown in FIG. 4, the descaling effect is small at temperatures below 50° C., making it difficult to pickle the entire surface. Therefore, the liquid temperature is preferably 50°C or higher. Even if the temperature is close to 100°C, there is not much difference in the pickling speed.

【0014】[0014]

【実施例】サンプルとして、50×50×1mmの板状
の純チタン、Ti−6Al−4V,Ti−15V−3C
r−3Sn,TiAlの各チタン材を作製し、各700
℃×3時間の大気熱処理を施し表面にスケール層を形成
した。溶液として、1リットル中の弗酸、塩酸、塩化ア
ンモニウム、弗化ナトリウムの濃度を種々変化させたも
のを使用した。それぞれの濃度範囲は、 弗酸                0.0〜3.5
%塩酸                0.0〜7.
4%塩化アンモニウム    0.0〜4.0wt%弗
化ナトリウム      0.0〜3.0wt%とした
。酸洗液温度は、25℃から100℃まで変化させた。
[Example] As a sample, a plate-shaped pure titanium of 50 x 50 x 1 mm, Ti-6Al-4V, Ti-15V-3C
Each titanium material of r-3Sn and TiAl was produced, and each
A scale layer was formed on the surface by performing atmospheric heat treatment for 3 hours at ℃. Solutions were used in which the concentrations of hydrofluoric acid, hydrochloric acid, ammonium chloride, and sodium fluoride in 1 liter were varied. The concentration range of each is: Hydrofluoric acid 0.0-3.5
% Hydrochloric acid 0.0-7.
4% ammonium chloride 0.0 to 4.0 wt% Sodium fluoride 0.0 to 3.0 wt%. The pickling solution temperature was varied from 25°C to 100°C.

【0015】また、酸洗速度の評価は各サンプルを10
分間酸洗した上で減少した質量を天秤で測定した。酸洗
むらは各サンプルを10分間酸洗した上で板厚の最大値
と最小値の差(板厚差)を板厚計で測定して評価した。 処理枚数の評価として何枚のサンプルが10分間の酸洗
で全面脱スケールできるかを評価方法とした。
[0015] In addition, the pickling speed was evaluated by
After pickling for a minute, the mass loss was measured on a balance. Pickling unevenness was evaluated by pickling each sample for 10 minutes and measuring the difference between the maximum and minimum plate thickness (plate thickness difference) using a plate thickness meter. The number of samples to be processed was evaluated by determining how many samples could be completely descaled by pickling for 10 minutes.

【0016】表1は、各イオン濃度に於ける各サンプル
の10分後の質量の減少量(図1に対応)と、板厚の最
大値と最小値の差(板厚差)(図3に対応)を示したも
のである。なお、表1中、実施例はこの発明の範囲内の
液組成を有するもの、比較例はその範囲から外れる液組
成を有するものを示す。この表1に示すように、本発明
の範囲内の実施例の場合には、スケ−ルを有効に除去で
きており、また厚さむらも少ないことが確認された。
Table 1 shows the amount of mass decrease after 10 minutes for each sample at each ion concentration (corresponding to Figure 1) and the difference between the maximum and minimum plate thickness (plate thickness difference) (Figure 3). ). In Table 1, Examples indicate those having liquid compositions within the range of the present invention, and Comparative Examples indicate those having liquid compositions outside the range. As shown in Table 1, in the case of the examples within the scope of the present invention, it was confirmed that scale could be effectively removed and there was little unevenness in thickness.

【0017】表2は、弗酸0.235%、弗化ナトリウ
ム0.5wt%、塩化アンモニウム0.3wt%(弗素
イオン濃度0.237モル/l、アンモニウムイオン0
.056モル/lに相当する)としたときの、80℃で
の塩素イオンのモル濃度と全面酸洗脱スケール処理が可
能な枚数を示したものである(図2に対応)。この表2
に示すように、塩素イオンモル濃度が1.0〜7.0モ
ル/リットルであれば、酸洗能力の持続力が良好である
ことが確認された。
Table 2 shows hydrofluoric acid 0.235%, sodium fluoride 0.5wt%, ammonium chloride 0.3wt% (fluorine ion concentration 0.237 mol/l, ammonium ion 0).
.. This figure shows the molar concentration of chlorine ions at 80° C. and the number of sheets that can be subjected to full-surface pickling and descaling treatment (corresponding to FIG. 2). This table 2
As shown in Figure 2, it was confirmed that when the molar concentration of chloride ions was 1.0 to 7.0 mol/liter, the sustaining ability of pickling was good.

【0018】表3は、塩酸5.55%、弗酸0.235
%、弗化ナトリウム0.5wt%、塩化アンモニウム0
.3wt%(弗素イオン濃度0.237モル/l、塩素
イオン1.58モル/l、アンモニウムイオン0.05
6モル/lに相当する)の時の、温度と10分間の質量
の減少量を示したものである。(図4に対応)この表3
に示すように、液温が50℃以上の場合に、良好なスケ
−ル除去能力を発揮することができることが確認された
Table 3 shows hydrochloric acid 5.55%, hydrofluoric acid 0.235%
%, sodium fluoride 0.5wt%, ammonium chloride 0
.. 3wt% (fluorine ion concentration 0.237 mol/l, chlorine ion 1.58 mol/l, ammonium ion 0.05
The graph shows the temperature and the amount of mass decrease over 10 minutes at a temperature of 6 mol/l). (Corresponding to Figure 4) This table 3
As shown in Figure 2, it was confirmed that good scale removal ability could be exhibited when the liquid temperature was 50°C or higher.

【0019】[0019]

【発明の効果】この発明によれば、チタン材の形状およ
び表面粗さを良好に維持しつつ、簡便な設備でむらなく
チタン材の表層に形成される強固なスケール層スケール
を除去することができるチタン材の酸洗処理方法を提供
することができる。
[Effects of the Invention] According to the present invention, it is possible to uniformly remove the hard scale layer formed on the surface layer of a titanium material using simple equipment while maintaining the shape and surface roughness of the titanium material well. It is possible to provide a method for pickling a titanium material.

【0020】[0020]

【表1】[Table 1]

【0021】[0021]

【表2】[Table 2]

【0022】[0022]

【表3】[Table 3]

【図面の簡単な説明】[Brief explanation of drawings]

【図1】80℃の塩酸弗酸系水溶液中の弗素濃度とスケ
−ル除去量の関係を示すグラフ。
FIG. 1 is a graph showing the relationship between the fluorine concentration and the amount of scale removed in a hydrochloric acid/fluoric acid aqueous solution at 80°C.

【図2】水溶液中の塩素イオン濃度と処理枚数との関係
を示すグラフ。
FIG. 2 is a graph showing the relationship between the chlorine ion concentration in an aqueous solution and the number of sheets processed.

【図3】水溶液中のアンモニウムイオン濃度と板厚差と
の関係を示すグラフ。
FIG. 3 is a graph showing the relationship between ammonium ion concentration in an aqueous solution and plate thickness difference.

【図4】水溶液の温度とスケ−ル除去量との関係を示す
グラフ。
FIG. 4 is a graph showing the relationship between the temperature of the aqueous solution and the amount of scale removed.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】  弗素イオン(F− イオン):0.2
〜2.0モル/リットル、塩素イオン(Cl− イオン
):1.0〜7.0モル/リットル、アンモニウムイオ
ン(NH4 + イオン):0.05〜8.0モル/リ
ットルを含有する水溶液に浸漬するかまたは該液をスプ
レーしてチタン材表面に形成されたスケールを除去する
ことを特徴とするチタン材の酸洗処理方法。
[Claim 1] Fluorine ion (F- ion): 0.2
~2.0 mol/liter, chloride ion (Cl- ion): 1.0-7.0 mol/liter, ammonium ion (NH4 + ion): 0.05-8.0 mol/liter in an aqueous solution containing A method for pickling a titanium material, which comprises removing scale formed on the surface of the titanium material by immersion or spraying the liquid.
【請求項2】  前記水溶液の液温が50℃以上である
ことを特徴とする請求項1に記載のチタン材の酸洗処理
方法。
2. The method for pickling a titanium material according to claim 1, wherein the temperature of the aqueous solution is 50° C. or higher.
JP8886191A 1991-04-19 1991-04-19 Method for pickling titanium material Pending JPH04323392A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8886191A JPH04323392A (en) 1991-04-19 1991-04-19 Method for pickling titanium material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8886191A JPH04323392A (en) 1991-04-19 1991-04-19 Method for pickling titanium material

Publications (1)

Publication Number Publication Date
JPH04323392A true JPH04323392A (en) 1992-11-12

Family

ID=13954783

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8886191A Pending JPH04323392A (en) 1991-04-19 1991-04-19 Method for pickling titanium material

Country Status (1)

Country Link
JP (1) JPH04323392A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004031333A1 (en) * 2002-09-30 2004-04-15 Nippon Steel Corporation Cleaning agent and cleaning method for ridding titanium and titanium alloy building materials of discoloration
JP2012224894A (en) * 2011-04-18 2012-11-15 Sumitomo Metal Ind Ltd Method of removing scale on titanium plate

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JPS5540670A (en) * 1978-07-26 1980-03-22 Glaxo Group Ltd Novel pyrimidone derivative*its manufacture and its medical composition

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JPS5540670A (en) * 1978-07-26 1980-03-22 Glaxo Group Ltd Novel pyrimidone derivative*its manufacture and its medical composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004031333A1 (en) * 2002-09-30 2004-04-15 Nippon Steel Corporation Cleaning agent and cleaning method for ridding titanium and titanium alloy building materials of discoloration
US7547671B2 (en) 2002-09-30 2009-06-16 Nippon Steel Corporation Discoloration removal cleaning agent for titanium and titanium alloy building materials, and discoloration removal cleaning method
JP2012224894A (en) * 2011-04-18 2012-11-15 Sumitomo Metal Ind Ltd Method of removing scale on titanium plate

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