JP3398555B2 - Titanium sheet for forming and its manufacturing method - Google Patents
Titanium sheet for forming and its manufacturing methodInfo
- Publication number
- JP3398555B2 JP3398555B2 JP01036897A JP1036897A JP3398555B2 JP 3398555 B2 JP3398555 B2 JP 3398555B2 JP 01036897 A JP01036897 A JP 01036897A JP 1036897 A JP1036897 A JP 1036897A JP 3398555 B2 JP3398555 B2 JP 3398555B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- forming
- thickness
- nitrogen
- nitriding
- 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.)
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Description
【0001】[0001]
【発明の属する技術分野】本発明は、二次加工の際の工
具との焼き付き等による表面疵発生を防止するための耐
疵付き性に優れた成形加工用チタン薄板及びその製造方
法に関するものである。成形加工用チタン薄板の主な用
途は、プレス成形性の必要な板状の熱交換器用の板や、
溶接チタン管等がある。特に、ロール成形し、突き合わ
せ部をTIG溶接する溶接チタン管では、溶接部の健全
性を維持するために、ロール成形の際に潤滑剤を使用で
きないので、素材であるチタン薄板自体に耐疵付き性が
求められている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium thin plate for forming, which is excellent in scratch resistance for preventing the occurrence of surface flaws due to seizure with a tool during secondary working, and a method for producing the same. is there. The main uses of titanium thin plates for forming are plates for heat exchangers that require press formability,
There are welded titanium pipes. In particular, in a welded titanium pipe that is roll-formed and TIG-welded at the abutting part, a lubricant cannot be used during roll-forming in order to maintain the soundness of the welded part, so the titanium thin plate itself, which is the raw material, has scratch resistance. Sex is required.
【0002】[0002]
【従来の技術】チタンの表面を改質するために各種の処
理が行われている。まず、窒化処理については、「チタ
ンの加工技術」((社)チタニウム協会編、日刊工業新
聞社発行、1992年、180頁)に、イオン窒化の例
が記載されている。イオン窒化は、通常のガス窒化と比
較して、効率的に窒化できるものの、処理温度が比較的
高温の850℃以上にて良好な耐摩耗性を有すると記載
されている。その例として、特開平1−10883号公
報には、チタン合金板を鍵の形状に成形した後、約85
0℃にて窒化処理し、耐摩耗性に優れたチタンキーが得
られるとしている。たとえば、アンモニアガス中にて、
16時間処理すると、TiN層の厚さが12μm、拡散
層の厚さが50μm(窒素富化層は62μmと推定され
る)のものが得られている。このように、従来の窒化処
理は、最終製品の形状に仕上がった物に対し、長期間の
耐摩耗性を付与する目的で行われている。しかしなが
ら、成形加工を前提とするチタン薄板に適用すると、例
えば、曲げ加工時に表面が割れるという欠点がある。2. Description of the Related Art Various treatments are performed to modify the surface of titanium. First, regarding the nitriding treatment, an example of ion nitriding is described in "Titanium processing technology" (edited by Titanium Association of Japan, published by Nikkan Kogyo Shimbun, Ltd., 1992, p. 180). Ion nitriding is described as having good wear resistance at a treatment temperature of 850 ° C. or higher, which is relatively high, although ion nitriding can be performed more efficiently than ordinary gas nitriding. As an example, in Japanese Patent Laid-Open No. 10883/1989, after forming a titanium alloy plate into a key shape, about 85
It is said that a titanium key with excellent wear resistance can be obtained by nitriding at 0 ° C. For example, in ammonia gas,
After treatment for 16 hours, a TiN layer having a thickness of 12 μm and a diffusion layer having a thickness of 50 μm (the nitrogen-rich layer is estimated to be 62 μm) are obtained. As described above, the conventional nitriding treatment is performed for the purpose of imparting long-term wear resistance to the finished product in the shape of the final product. However, when it is applied to a titanium thin plate that is premised on a forming process, there is a drawback that the surface is cracked during bending, for example.
【0003】また、特開昭63−111161号公報に
は、チタン合金線材を450〜750℃の温度域で酸化
処理した後、潤滑処理することにより焼き付きのない伸
線方法が提案されている。この酸化処理の方法は、不均
一な青色等の着色が生じるため、チタン薄板に適用した
場合、成形加工後に着色部の除去が必要になるという欠
点がある。Further, Japanese Patent Laid-Open No. 63-111161 proposes a wire drawing method in which a titanium alloy wire is oxidized in a temperature range of 450 to 750 ° C. and then lubricated to prevent seizure. This method of oxidation treatment has a disadvantage that when applied to a titanium thin plate, the colored portion needs to be removed after the molding process, because uneven coloring such as blue color occurs.
【0004】また、特開平3−294471号公報に
は、チタン板の表面に特定膜厚の酸化皮膜を形成した
後、非酸化性雰囲気下で焼鈍して表面硬化層を形成する
ことにより、耐焼き付き性に優れかつ均一な金属光沢を
有するチタン板の製造方法が開示されている。この方法
は、均一な特定膜厚の酸化皮膜を得るために、陽極酸化
法にて形成することになり、製造コストが高いという欠
点がある。Further, in Japanese Patent Laid-Open No. 3-294471, an oxide film having a specific thickness is formed on the surface of a titanium plate and then annealed in a non-oxidizing atmosphere to form a surface hardened layer. A method for producing a titanium plate having excellent seizure properties and having a uniform metallic luster is disclosed. This method has a drawback that the manufacturing cost is high because the oxide film is formed by an anodic oxidation method in order to obtain an oxide film having a uniform specific thickness.
【0005】さらに、特開平1−201452号公報に
は、チタンを特定の圧延油を用いて冷延後、油分を残存
させ非酸化性雰囲気で焼鈍することにより、TiCを主
成分とする表面硬化層を形成し、耐疵付き性が向上する
ことが記載されている。この方法は、洗浄液の洗浄能力
に依存して油分を残存させるために品質が安定しにくい
という欠点がある。Further, in Japanese Patent Laid-Open No. 1-201452, after titanium is cold-rolled with a specific rolling oil, the oil is left and annealed in a non-oxidizing atmosphere to obtain a surface hardening containing TiC as a main component. It is described that a layer is formed and the scratch resistance is improved. This method has a drawback in that the quality is difficult to stabilize because oil remains depending on the cleaning ability of the cleaning liquid.
【0006】[0006]
【発明が解決しようとする課題】このような技術の現状
において、本発明は材質の劣化がなく、不均一な青色等
の着色がなく、安価で品質が安定しやすい特徴を有し、
工具との耐焼き付き性に優れた皮膜を有する成形加工用
チタン薄板、及びその製造方法を課題とする。In the present state of the art, the present invention has the characteristics that there is no deterioration of the material, there is no uneven coloring such as blue, and the quality is cheap and the quality is easy to stabilize.
A titanium thin plate for forming, which has a film excellent in seizure resistance with a tool, and a manufacturing method thereof.
【0007】[0007]
【課題を解決するための手段】上記課題を解決するため
に本発明は、表面に窒素富化層を有し、その厚さが
0.5μm以上、5μm以下であることを特徴とする成
形加工用チタン薄板、好ましくは、その厚さが1.5
μm以上、5μm以下であることを特徴とする成形加工
用チタン薄板を要旨とする。In order to solve the above-mentioned problems, the present invention has a nitrogen-enriched layer on the surface and has a thickness of 0.5 μm or more and 5 μm or less. Titanium sheet, preferably its thickness is 1.5
The gist is a titanium thin plate for forming, which is characterized in that it is not less than μm and not more than 5 μm.
【0008】さらに、チタンを窒化雰囲気中にて加熱温
度が550℃以上、700℃以下の温度にて加熱するこ
とを特徴とする及びの成形加工用チタン薄板の製造
方法、好ましくは、冷延されたままのチタンを窒化雰
囲気中にて加熱温度が600℃以上、700℃以下の温
度にて加熱することを特徴とする及びの成形加工用
チタン薄板の製造方法を要旨とする。Further, the titanium is heated in a nitriding atmosphere at a heating temperature of 550 ° C. or higher and 700 ° C. or lower. A gist of the method for producing a titanium thin plate for forming is characterized in that the as-manufactured titanium is heated in a nitriding atmosphere at a heating temperature of 600 ° C. or higher and 700 ° C. or lower.
【0009】[0009]
【発明の実施の形態】まず、表面に窒素富化層を有し、
その厚さが0.5μm以上、5μm以下であるとしたの
は、厚さが0.5μm未満では、工具との焼き付き性の
改善が十分であるとは言えず、また、厚さが5μm超で
は、薄い金色に着色するために、色むらの問題が発生し
やすいためである。BEST MODE FOR CARRYING OUT THE INVENTION First, a surface having a nitrogen-enriched layer,
The thickness of 0.5 μm or more and 5 μm or less means that if the thickness is less than 0.5 μm, it cannot be said that the seizure property with the tool is sufficiently improved, and that the thickness exceeds 5 μm. Then, since it is colored in a light gold color, a problem of color unevenness is likely to occur.
【0010】一方、一般的に、窒素富化層の厚さが厚い
と材質が劣化する。本発明者は、窒化富化層の厚さが、
板厚の1.5%以下(両面では、3%以下)であれば、
引張特性にほとんど影響がないことを確認し、さらに、
液圧バルジ試験により成形性の劣化のないことも確認し
た。この結果から、成形加工用チタン薄板に使用される
最も薄い板厚0.4mmに対して、6μmの窒素富化層ま
で材質劣化がないが、前述の通り、着色の問題があるた
めに5μm以下としている。On the other hand, generally, when the thickness of the nitrogen-rich layer is large, the material deteriorates. The present inventors have found that the thickness of the nitride-enriched layer is
If the thickness is 1.5% or less (3% or less on both sides),
It was confirmed that there was almost no effect on the tensile properties.
It was also confirmed by a hydraulic bulge test that the moldability did not deteriorate. From this result, there is no material deterioration up to 6 μm of nitrogen-enriched layer with respect to the thinnest plate thickness of 0.4 mm used for forming titanium thin plate, but as described above, there is a coloring problem, so 5 μm or less I am trying.
【0011】さらに、好ましくは、その厚さが、1.5
μm以上、5μm以下であるとしたのは、厚さが1.5
μm以上から、例えば、溶接チタン管のロール成形に対
して、十分な耐焼き付き性を示すからである。Further preferably, the thickness is 1.5
The thickness of 1.5 μm or more and 5 μm or less means that the thickness is 1.5
This is because from μm or more, for example, sufficient seizure resistance is exhibited against roll forming of a welded titanium pipe.
【0012】ここで、表面の窒素富化層の厚さは、比較
的薄いために、ドイツのRSV社製、ANALYMAT
−2504型、グロー放電発光分光分析装置にて、深さ
方向のNとTiの量を主に測定した結果から求めた。分
析装置の測定条件を表1に示す。Since the surface of the nitrogen-rich layer on the surface is relatively thin, it is manufactured by RSV of Germany, ANALYMAT.
It was determined from the results of mainly measuring the amounts of N and Ti in the depth direction with a −2504 type glow discharge emission spectrophotometer. Table 1 shows the measurement conditions of the analyzer.
【0013】[0013]
【表1】 [Table 1]
【0014】発光強度とスパッタリング時間の関係か
ら、組成(NとTiの量)と深さの関係を算出する方法
は、(株)日鐵テクノリサーチにて使用されている方法
を用いた。この方法の概要は、発光強度から組成を求め
るための基準試料は、TiNを用い、スパッタ量から深
さを求めるための密度は、NはTiNから、Tiは金属
チタンから求めている。得られた結果の例を図1に示
す。この図のNの曲線と母材のNのレベルの交点から、
窒素富化層の厚さは、矢印にて示すように、約2.2μ
mと読みとれる。実際には、スパッタリング時に直径4
mm内での深さのバラツキがあるため、この値よりは小さ
いと予想されるが、便宜上、この値を窒素富化層の厚さ
とした。The method used in Nippon Steel Techno Research Co., Ltd. was used to calculate the relationship between composition (amount of N and Ti) and depth from the relationship between emission intensity and sputtering time. The outline of this method is that TiN is used as a reference sample for obtaining the composition from the emission intensity, and the density for obtaining the depth from the amount of sputtering is obtained from N for TiN and Ti for metallic titanium. An example of the obtained results is shown in FIG. From the intersection of the N curve of this figure and the N level of the base metal,
The thickness of the nitrogen-enriched layer is about 2.2μ as shown by the arrow.
It can be read as m. Actually, the diameter is 4 when sputtering.
It is expected that this value will be smaller than this value due to the variation in depth within mm, but for convenience, this value was used as the thickness of the nitrogen-enriched layer.
【0015】本発明の成形加工用チタン薄板の製造方法
は、工業的にチタンコイルの焼鈍に使用されている真空
排気が可能なバッチ式焼鈍炉を前提とした。チタンを窒
化雰囲気中にて加熱温度が550℃以上、700℃以下
の温度にて加熱するのは、まず、窒化雰囲気中での加熱
により、窒素富化層を安価に形成できるからである。さ
らに、550℃未満では、窒化反応が緩慢のため長時間
を要するからであり、一方、700℃超では、窒化反応
が活発となり、窒素富化層は、急激に成長するため、薄
い金色に着色したり、さらには、材質の劣化が問題とな
るからである。ここで、窒化雰囲気とは、例えば、純度
99.999%以上の窒素雰囲気である。アンモニアガ
スは、水素吸収による脆化とそれによる成形性の劣化が
懸念されること、イオン窒化は、コイル状の全表面にほ
ぼ均一に電界を形成することが不可能であることから、
本発明として適当でない。The method for producing a titanium thin plate for forming according to the present invention is premised on a batch type annealing furnace which is industrially used for annealing a titanium coil and which can be evacuated. The reason why titanium is heated in the nitriding atmosphere at a heating temperature of 550 ° C. or higher and 700 ° C. or lower is that the nitrogen-rich layer can be formed at low cost by heating in the nitriding atmosphere. Further, if the temperature is lower than 550 ° C., the nitriding reaction is slow and it takes a long time. This is because the deterioration of the material becomes a problem. Here, the nitriding atmosphere is, for example, a nitrogen atmosphere having a purity of 99.999% or more. Ammonia gas may cause embrittlement due to hydrogen absorption and deterioration of formability due to it, and ion nitriding cannot form an electric field almost uniformly on the entire coil-shaped surface.
Not suitable for the present invention.
【0016】さらに、好ましくは、冷延されたままのチ
タンを窒化雰囲気中にて加熱温度が600℃以上、70
0℃以下の温度にて加熱するのは、窒化とともに焼鈍も
同時に実施できるからである。好ましい加熱温度を60
0℃以上としたのは、加工性に必要な再結晶及び粒成長
を十分に生じさせるためである。なお、冷延されたまま
のチタンを比較的低温で窒化すると、焼鈍後に窒化した
ものと比較して、窒化されやすい現象が認められた。Further, preferably, the as-cold-rolled titanium is heated in a nitriding atmosphere at a heating temperature of 600.degree.
The reason why heating is performed at a temperature of 0 ° C. or lower is that annealing can be performed simultaneously with nitriding. The preferred heating temperature is 60
The reason why the temperature is 0 ° C. or higher is that the recrystallization and grain growth necessary for workability are sufficiently generated. It should be noted that, when the as-cold-rolled titanium was nitrided at a relatively low temperature, it was recognized that the titanium was more likely to be nitrided as compared with the nitrided product after annealing.
【0017】本発明は、窒化雰囲気中での窒化であるの
で、チタンを十分に洗浄し、炉内と導入窒素ガスの不純
ガスを制御すれば、極めて安定した品質で製造できる。Since the present invention uses nitriding in a nitriding atmosphere, if titanium is thoroughly washed and the impure gas of the nitrogen gas introduced in the furnace is controlled, it can be produced with extremely stable quality.
【0018】[0018]
【実施例】表2のNo.1〜4とNo.11〜13に関
しては、板厚0.5mmの純チタン2種の冷延製品コイル
(焼鈍済み)を準備した。また、表2のNo.5、6と
14に関しては、板厚0.5mmの純チタン2種の冷延ま
まのコイル(未焼鈍)を準備した。これらのコイルをバ
ッチ式真空焼鈍炉を用いて、真空引き後、窒化雰囲気中
にて、表2に示す各種加熱温度と加熱時間条件にて窒化
した。次に、これらのコイルをスリットしフープとし、
溶接管を製造し、ロール疵発生の有無により耐焼き付き
性を評価した。また、材質劣化は密着曲げ性により、着
色有無は目視観察により評価した。以上の結果も表2に
示す。Example No. of Table 2 1-4 and No. Regarding 11 to 13, cold rolled product coils (annealed) of two types of pure titanium having a plate thickness of 0.5 mm were prepared. Moreover, No. Regarding Nos. 5, 6 and 14, a cold rolled coil (unannealed) of pure titanium type 2 having a plate thickness of 0.5 mm was prepared. These coils were vacuumed using a batch type vacuum annealing furnace, and then nitrided in a nitriding atmosphere under various heating temperatures and heating time conditions shown in Table 2. Next, slit these coils into hoops,
Welded pipes were manufactured and the seizure resistance was evaluated by the presence or absence of roll flaws. The deterioration of the material was evaluated by the adhesion bendability, and the presence or absence of coloring was evaluated by visual observation. The above results are also shown in Table 2.
【0019】造管の方法は、通常のAr雰囲気中にて焼
鈍し製品としたフープでは、焼き付き疵が発生するレベ
ルにスクイズロールの圧下を大きくかつ一定にする方法
とした。焼き付き疵が解消したものを○、焼き付き疵が
低減したものを△、焼き付き疵が発生したものを×とし
た。密着曲げは、割れの無いものを○、割れの発生した
No.14を×とした。また、オレンジピールの激しい
No.12,13も×とした。着色は、着色の無いもの
を○、極薄金色のものを△、金色に着色したものを×と
した。The method of forming the pipe was a method of making the squeeze roll to have a large and constant reduction to a level where seizure flaws are generated in a hoop which is a product annealed in an ordinary Ar atmosphere. The one in which the burn-in defect was eliminated was evaluated as ◯, the one in which the burn-in defect was reduced was evaluated as Δ, and the one in which the burn-in defect was generated was evaluated as x. For close contact bending, those with no cracks are marked with ○, and cracks with No. 14 was designated as x. Moreover, No. 12 and 13 were also marked with x. As for coloring, those with no coloring were marked with ◯, those with an extremely thin gold color were marked with Δ, and those colored with gold were marked with x.
【0020】例えば、本発明例のNo.1は、チタン製
品コイルを窒素雰囲気中にて550℃にて5時間加熱し
たものであり、その表層には、0.5μmの窒素富化層
がある。造管は、焼き付き疵が低減し、密着曲げは割れ
が無く、着色は無かった。以上の結果、従来製品コイル
よりも優れていると判定し、総合評価を○(良)とし
た。For example, No. 1 of the present invention example. In No. 1, a titanium product coil was heated in a nitrogen atmosphere at 550 ° C. for 5 hours, and the surface layer thereof had a 0.5 μm nitrogen-rich layer. In the pipe making, seizure flaws were reduced, there was no cracking in tight bending, and there was no coloring. As a result of the above, it was determined that the coil was superior to the conventional product coil, and the overall evaluation was evaluated as ◯ (good).
【0021】また、No.5,6と14は、冷延ままの
コイル(未焼鈍)を用いて試験した結果である。No.
5は、600℃の加熱で密着曲げは良好であるが、N
o.14は、550℃の加熱では再結晶及び粒成長が不
十分なために、密着曲げは不良であった。さらに、N
o.5は、焼鈍後に窒化したNo.3と比較して、短時
間で同等の窒素富化層の厚さになっている。No. Nos. 5, 6 and 14 are the results of the test using the as-cold rolled coil (unannealed). No.
No. 5 has good adhesion bending by heating at 600 ° C., but N
o. No. 14 had poor adhesion bending due to insufficient recrystallization and grain growth by heating at 550 ° C. Furthermore, N
o. No. 5 was nitrided after annealing. Compared with No. 3, the nitrogen-enriched layer has the same thickness in a short time.
【0022】以上の結果、表面に0.5μm以上、5.
0μm以下の窒素富化層を有する場合、また、好ましく
は、表面に1.5μm以上、5.0μm以下の窒素富化
層を有する場合、本発明の課題に対して、総合的に優れ
たチタン薄板となりうる。As a result of the above, 0.5 μm or more on the surface,
In the case of having a nitrogen-enriched layer of 0 μm or less, and preferably having a nitrogen-enriched layer of 1.5 μm or more and 5.0 μm or less on the surface, titanium that is comprehensively superior to the problems of the present invention is obtained. It can be a thin plate.
【0023】さらに、このようなチタン薄板は、チタン
を窒化雰囲気中にて加熱温度が550℃以上、700℃
以下の温度にて加熱することにより得られ、好ましく
は、冷延されたままのチタンを窒化雰囲気中にて加熱温
度が600℃以上、700℃以下の温度にて加熱するこ
とにより焼鈍工程と兼ねることができる。Further, such a titanium thin plate has a heating temperature of 550 ° C. or higher and 700 ° C. in a nitriding atmosphere of titanium.
It is obtained by heating at the following temperature, and preferably, as cold-rolled titanium is also heated at a heating temperature of 600 ° C. or higher and 700 ° C. or lower in a nitriding atmosphere, which also serves as an annealing step. be able to.
【0024】[0024]
【表2】 [Table 2]
【0025】[0025]
【発明の効果】本発明によれば、材質劣化、着色の問題
がなく、安定した品質にて、ロール成形等の二次加工の
際に優れた耐焼き付き性を示す成形加工用チタン薄板を
提供できる。EFFECTS OF THE INVENTION According to the present invention, there is provided a titanium thin plate for forming, which is free from problems such as material deterioration and coloring, has stable quality, and exhibits excellent seizure resistance during secondary processing such as roll forming. it can.
【図1】実施例のNo.6の窒素濃度と深さを示す図。FIG. The figure which shows the nitrogen concentration of 6 and depth.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 爲成 純一 山口県光市大字島田3434番地 新日本製 鐵株式会社 光製鐵所内 (56)参考文献 特開 平2−25559(JP,A) (58)調査した分野(Int.Cl.7,DB名) C23C 8/24 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Kosei 3434 Shimada, Hikari City, Yamaguchi Prefecture Shin Nippon Steel Co., Ltd. Hikari Steel Works (56) Reference JP-A-2-25559 (JP, A) ( 58) Fields investigated (Int.Cl. 7 , DB name) C23C 8/24
Claims (2)
0.5μm以上、5μm以下であることを特徴とする成
形加工用チタン薄板。1. A titanium thin plate for forming, which has a nitrogen-enriched layer on its surface and has a thickness of 0.5 μm or more and 5 μm or less.
550℃以上、700℃以下の温度にて加熱することを
特徴とする請求項1記載の成形加工用チタン薄板の製造
方法。2. The method for producing a titanium thin plate for forming according to claim 1, wherein the titanium is heated in a nitriding atmosphere at a heating temperature of 550 ° C. or higher and 700 ° C. or lower.
Priority Applications (1)
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JP01036897A JP3398555B2 (en) | 1997-01-23 | 1997-01-23 | Titanium sheet for forming and its manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP01036897A JP3398555B2 (en) | 1997-01-23 | 1997-01-23 | Titanium sheet for forming and its manufacturing method |
Publications (2)
Publication Number | Publication Date |
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JPH10204609A JPH10204609A (en) | 1998-08-04 |
JP3398555B2 true JP3398555B2 (en) | 2003-04-21 |
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JP01036897A Expired - Fee Related JP3398555B2 (en) | 1997-01-23 | 1997-01-23 | Titanium sheet for forming and its manufacturing method |
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Families Citing this family (5)
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---|---|---|---|---|
JP4920168B2 (en) * | 2003-07-17 | 2012-04-18 | 新日本製鐵株式会社 | Titanium welded tube and manufacturing method thereof |
KR100594998B1 (en) | 2004-05-14 | 2006-06-30 | 주식회사 케이피티 | Method for nitriding of Ti and Ti alloy |
JP4681663B2 (en) * | 2009-07-15 | 2011-05-11 | 株式会社神戸製鋼所 | Titanium plate and method for manufacturing titanium plate |
JP2011251340A (en) * | 2011-06-24 | 2011-12-15 | Nippon Steel Corp | Titanium welded pipe for fretting fatigue resistant member, and method for manufacturing the same |
CN113088846A (en) * | 2021-03-22 | 2021-07-09 | 湖南湘投金天钛金属股份有限公司 | Coloring process of cold-rolled titanium material |
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1997
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JPH10204609A (en) | 1998-08-04 |
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