JPH07103458B2 - Method of modifying titanium plate - Google Patents
Method of modifying titanium plateInfo
- Publication number
- JPH07103458B2 JPH07103458B2 JP61110267A JP11026786A JPH07103458B2 JP H07103458 B2 JPH07103458 B2 JP H07103458B2 JP 61110267 A JP61110267 A JP 61110267A JP 11026786 A JP11026786 A JP 11026786A JP H07103458 B2 JPH07103458 B2 JP H07103458B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- titanium plate
- corrosion resistance
- skin pass
- plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 51
- 239000010936 titanium Substances 0.000 title claims description 51
- 229910052719 titanium Inorganic materials 0.000 title claims description 49
- 238000000034 method Methods 0.000 title description 6
- 238000005260 corrosion Methods 0.000 claims description 28
- 230000007797 corrosion Effects 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 238000002715 modification method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 238000005554 pickling Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001362 Ta alloys Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- -1 titanium hydride Chemical compound 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
本発明はチタン板の改質方法に関する。 The present invention relates to a method for modifying a titanium plate.
チタンはもともと耐食性に優れた材料であると同時に、
圧延、熱処理、溶接等を行っても耐食性が変化しないと
いう特徴を持っている。そのため、各種化学プラント及
び、産業機械等に耐食材料として用いられている。 化学プラント及び産業機械に用いられているチタン板は
大型鉄鋼ミルを用い、圧延により製造される。すなわ
ち、一般的に次の工程を経てチタン板は製造される。ス
ラブ→粗圧延→仕上圧延→巻取り→焼鈍→脱スケール→
冷間圧延→脱脂→最終焼鈍。 ここでコイル圧延されるチタン板は、工業用純チタン、
Ti−0.2％Pd合金、Ti−５％Ta合金、Ti−0.8％Ni−0.3
％Mo合金、Ti−3.5％Al−２％Ｖ合金等である。これら
チタコイルの製造時に考慮している事はチタンの圧延方
法及び圧延後のチタンコイルの機械的強度の変化等に関
する事が主である。 チタンは耐食性に優れている材料であるが、特殊な環境
下では腐食される事がある。チタンが腐食を受けると、
チタンの本来の熱力学的に活性な性質により、非常に大
きな腐食速度になる。またチタンが水素を吸収するとチ
タン水素化物が生成し、チタンを脆性的な性質を変えて
しまうと言う問題点がある。 これらの問題点を解決する為に、 （１）チタンにPd,V,Mo,Ta等の合金元素を添加する、 （２）最終焼鈍されたチタン板の表面に、Pd,PdO等の貴
金属又はその酸化物をコーティングする、 （３）最終焼鈍されたチタン板の表面を酸化してTiO2の
保護皮膜を形成する、等の対策が検討されており、一部
は実用化されている。Titanium is originally a material with excellent corrosion resistance,
It has the characteristic that the corrosion resistance does not change even if rolling, heat treatment, welding, etc. are performed. Therefore, it is used as a corrosion resistant material in various chemical plants and industrial machines. Titanium plates used in chemical plants and industrial machines are manufactured by rolling using a large steel mill. That is, generally, a titanium plate is manufactured through the following steps. Slab → rough rolling → finish rolling → winding → annealing → descaling →
Cold rolling → degreasing → final annealing. The titanium plate that is coil rolled here is industrial pure titanium,
Ti-0.2% Pd alloy, Ti-5% Ta alloy, Ti-0.8% Ni-0.3
% Mo alloy, Ti-3.5% Al-2% V alloy and the like. The main consideration in the production of these titanium coils is the method of rolling titanium and the change in mechanical strength of the titanium coil after rolling. Titanium is a material with excellent corrosion resistance, but it may be corroded in a special environment. When titanium is corroded,
The inherent thermodynamically active nature of titanium results in very high corrosion rates. Further, there is a problem that when titanium absorbs hydrogen, titanium hydride is generated, which changes the brittle property of titanium. In order to solve these problems, (1) alloy elements such as Pd, V, Mo, Ta, etc. are added to titanium, (2) noble metals such as Pd, PdO, etc. on the surface of the finally annealed titanium plate or Measures such as coating the oxide, (3) oxidizing the surface of the finally annealed titanium plate to form a protective film of TiO 2 are being studied, and some have been put to practical use.
しかし、上記（１）〜（３）の技術は、高価な金属等を
使用するためコストが高くなってしまうという問題点が
ある。However, the above techniques (1) to (3) have a problem that the cost becomes high because an expensive metal or the like is used.
本発明は、最終焼鈍されたチタン板の酸洗を行った後、
0.5〜15％の板厚減少量でスキンパスを加えることによ
り、耐食性及び耐水素吸収性を改善することを特徴とす
るチタン板の改良方法である。 ここでチタン板の材質としては、たとえば、工業用純チ
タン、Ti−0.2Pd合金、Ti−５％Ta合金、Ti−0.8Ni−0.
3Mo合金等のコイル状圧延が可能なチタン及びチタン合
金である。 本発明では、最終焼鈍されたチタン板の酸洗を行なう。
これは、焼鈍処理で生じた薄い酸化皮膜を除去する為の
プロセスである。酸はたとえばHF,HF−HNO3混酸、H2S
O4、HCll等を使用できる。なお生産性の面からは、HF−
HNO3混酸が望ましい。 酸洗後、チタン板の板厚減少量で0.5％〜15％のスキン
パスを行う。 尚、酸洗を行った後にスキンパスをする事によりチタン
板の耐食性が向上する理由として考えられる事は、チタ
ン板の表面には大気中で薄い酸化皮膜が生成するが、こ
の皮膜の組成、構造及び結晶学的方位により耐食性、耐
水素吸収性が異なることによる。すなわち、チタンの酸
化皮膜は立方晶でありＣ軸が圧延面に垂直に方位した場
合に最も耐食性、耐水素吸収性が良くなる。従って真空
焼鈍や大気中暴露では酸化皮膜のＣ軸は垂直の方位では
無く、スキンパスを施すとＣ軸が垂直に方位する為と考
えられる。 次に本発明の構成要件であるスキンパスの影響について
実施例をもとに説明する。The present invention, after carrying out pickling of the final annealed titanium plate,
This is a method for improving a titanium plate, characterized by improving the corrosion resistance and the hydrogen absorption resistance by adding a skin pass with a reduction amount of 0.5 to 15%. Here, as the material of the titanium plate, for example, industrial pure titanium, Ti-0.2Pd alloy, Ti-5% Ta alloy, Ti-0.8Ni-0.
Titanium and titanium alloys such as 3Mo alloy that can be rolled into a coil. In the present invention, the final annealed titanium plate is pickled.
This is a process for removing the thin oxide film generated by the annealing treatment. The acid is, for example, HF, HF-HNO 3 mixed acid, H 2 S
O 4 , HCll, etc. can be used. From the aspect of productivity, HF-
HNO 3 mixed acid is preferred. After pickling, 0.5% to 15% skin pass is applied to reduce the thickness of the titanium plate. The reason why the corrosion resistance of the titanium plate is improved by performing a skin pass after pickling is that a thin oxide film is formed on the surface of the titanium plate in the air. And the corrosion resistance and hydrogen absorption resistance differ depending on the crystallographic orientation. That is, the oxide film of titanium is a cubic crystal, and the corrosion resistance and hydrogen absorption resistance are best when the C axis is oriented perpendicular to the rolling surface. Therefore, it is considered that the C axis of the oxide film does not have a vertical orientation in vacuum annealing or exposure to the atmosphere, but the C axis has a vertical orientation when skin pass is applied. Next, the influence of the skin pass, which is a constituent feature of the present invention, will be described based on examples.
【実施例】（実施例１） （スキンパス等の影響） 試験片は板厚1mmの工業用純チタン（JIS2種）を2mm×4m
mの大きさに機械加工した後、真空焼鈍（NA）、大気焼
鈍後酸洗（AP）、AP＋スキンパス（AP→SKP）を施こし
たものを用いた。スキンパス率は0.2〜20％とした。 耐食性の評価は平均腐食速度により行った。平均腐食速
度（mm/h）は試験片の重量減少量をもとに比重と面積か
ら計算により腐食減厚量（mm）を求め、その値を実験時
間（ｈ）で割って求めた。 実験は試験片を沸騰している１％HCl＋0.01％Fe3+溶液
に48時間浸漬で行っ。、実験結果を第１図に示す。 第１図より、チタン板にAP→SKPを施したものは、VAあ
るいはAPを施したものより耐食性があるが、スキンパス
率0.2％未満では耐食性は良くないことが分かる。 スキンパス率が0.5％を超えると耐食性の向上が顕著と
なるが15％を越すと、その効果が飽和することが分か
る。 このことから、AP後のスキンパス率の範囲を0.5〜15％
とした。 （実施例２） （腐食性） 実施例１と同様の試験片で各種酸溶液中での耐食性の評
価を行った。 耐食性の評価は平均腐食速度（mm/h）により行った。 尚、スキンパス率は５％とした。 実験結果を表１に示す。表１よりVAを施したチタン板と
APを施したチタン板とには耐食性に大きな差はみられな
いが、AP→SKPを施したチタン板はVAを施したチタン板
や、APを施したチタン板に比較し、格段に平均腐食速度
が小さいことが分かる。このことから、最終製品である
チタン板に対するスキンパスは、該チタン板の耐食性向
上に効果があることが分かる。 （実施例３） （チタン材の影響） 各種チタン材をVA、AP、AP→SKPの各々の処理を行い実
施例１と同様の試験片を作成し、実施例１と同様の耐食
性の試験を行った。 実験結果を表２に示す。表２より、実験を行ったチタン
材ではAP→SKP材の耐食性が良いことが分かる。このこ
とからスキンパスによる耐食性の向上は各種チタン材に
対して有効であることが分かる。 （実施例４） （耐水素吸収性） チタン材に対する水素の吸収は定電流電解により行っ
た。すなわち実施例１に示した試験片を陰極とし、Ptめ
っきTiを陽極として、室温の0.05MH2SO4中で純チタンに
1mA/cm2の電流を流した。 定電流電解の時間は24時間、96時間とした。チタン中の
水素含有料を表３に示す。表３から、チタン板の水素量
はAP→SKPを施したチタン板が最も少なく、スキンパス
によりチタン板の耐水素吸収性が向上することが分か
る。 [Example] (Example 1) (Influence of skin pass, etc.) The test piece was made of industrial pure titanium (JIS type 2) with a plate thickness of 1 mm, 2 mm x 4 m.
After machining into a size of m, vacuum annealing (NA), atmospheric annealing followed by pickling (AP), and AP + skin pass (AP → SKP) were used. The skin pass rate was 0.2 to 20%. The corrosion resistance was evaluated by the average corrosion rate. The average corrosion rate (mm / h) was calculated by calculating the corrosion thickness reduction (mm) from the specific gravity and the area based on the weight reduction of the test piece, and dividing the value by the experimental time (h). The experiment was carried out by soaking the test piece in a boiling 1% HCl + 0.01% Fe 3+ solution for 48 hours. The experimental results are shown in FIG. It can be seen from FIG. 1 that the titanium plate subjected to AP → SKP has more corrosion resistance than the one subjected to VA or AP, but the corrosion resistance is not good when the skin pass ratio is less than 0.2%. It can be seen that when the skin pass ratio exceeds 0.5%, the corrosion resistance is remarkably improved, but when it exceeds 15%, the effect is saturated. From this, the range of skin pass rate after AP is 0.5 to 15%
And (Example 2) (Corrosion) The same test piece as in Example 1 was evaluated for corrosion resistance in various acid solutions. The corrosion resistance was evaluated by the average corrosion rate (mm / h). The skin pass rate was 5%. The experimental results are shown in Table 1. From Table 1, the titanium plate with VA
Although there is no significant difference in corrosion resistance with the titanium plate with AP, the titanium plate with AP → SKP is much more corrosive than the titanium plate with VA or AP. You can see that the speed is small. From this, it is understood that the skin pass for the final product, the titanium plate, is effective in improving the corrosion resistance of the titanium plate. (Example 3) (Effect of Titanium Material) Various titanium materials were subjected to VA, AP, and AP → SKP treatments to prepare a test piece similar to that of Example 1, and a corrosion resistance test similar to that of Example 1 was performed. went. The experimental results are shown in Table 2. From Table 2, it can be seen that the tested titanium material has good corrosion resistance from AP to SKP material. From this, it is understood that the improvement of corrosion resistance by skin pass is effective for various titanium materials. (Example 4) (Hydrogen absorption resistance) Absorption of hydrogen to the titanium material was performed by constant current electrolysis. That is, using the test piece shown in Example 1 as a cathode and Pt-plated Ti as an anode, pure titanium was formed in 0.05MH 2 SO 4 at room temperature.
A current of 1 mA / cm 2 was applied. The time of constant current electrolysis was 24 hours and 96 hours. Table 3 shows the hydrogen-containing materials in titanium. From Table 3, it can be seen that the amount of hydrogen in the titanium plate is the smallest in the titanium plate subjected to AP → SKP, and the hydrogen absorption resistance of the titanium plate is improved by the skin pass.
本発明によれば、チタン板を酸洗の後、0.5〜15％の板
厚減少量でスキンパスを行うことにより、チタン板の耐
食性と耐水素吸収性を向上させることができる。According to the present invention, corrosion resistance and hydrogen absorption resistance of a titanium plate can be improved by pickling the titanium plate and then performing a skin pass with a thickness reduction amount of 0.5 to 15%.
第１図はスキンパス率と平均腐食速度との関係を示すグ
ラフである。FIG. 1 is a graph showing the relationship between the skin pass rate and the average corrosion rate.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−108252（ＪＰ，Ａ) 特開 昭58−42761（ＪＰ，Ａ) ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-57-108252 (JP, A) JP-A-58-42761 (JP, A)
Claims (1)
後、0.5〜15％の板厚減少量でスキンパスを加えること
により、耐食性及び耐水素吸収性を改善することを特徴
とするチタン板の改質方法。1. A titanium characterized in that after the final annealed titanium plate is pickled, a skin pass is added in a thickness reduction amount of 0.5 to 15% to improve corrosion resistance and hydrogen absorption resistance. Plate modification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61110267A JPH07103458B2 (en) | 1986-05-13 | 1986-05-13 | Method of modifying titanium plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61110267A JPH07103458B2 (en) | 1986-05-13 | 1986-05-13 | Method of modifying titanium plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62267458A JPS62267458A (en) | 1987-11-20 |
| JPH07103458B2 true JPH07103458B2 (en) | 1995-11-08 |
Family
ID=14531353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61110267A Expired - Lifetime JPH07103458B2 (en) | 1986-05-13 | 1986-05-13 | Method of modifying titanium plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07103458B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3406898B2 (en) | 2000-07-28 | 2003-05-19 | 新日本製鐵株式会社 | Titanium material that does not easily cause discoloration and method for producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5941508B2 (en) * | 1980-12-24 | 1984-10-08 | 株式会社神戸製鋼所 | Manufacturing method of titanium hot rolled sheet |
| JPS5842761A (en) * | 1981-09-08 | 1983-03-12 | Kobe Steel Ltd | Manufacture of titanium plate |
-
1986
- 1986-05-13 JP JP61110267A patent/JPH07103458B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62267458A (en) | 1987-11-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |