JP2004025201A - Manufacturing method of cold drawn steel pipe - Google Patents
Manufacturing method of cold drawn steel pipe Download PDFInfo
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- JP2004025201A JP2004025201A JP2002181869A JP2002181869A JP2004025201A JP 2004025201 A JP2004025201 A JP 2004025201A JP 2002181869 A JP2002181869 A JP 2002181869A JP 2002181869 A JP2002181869 A JP 2002181869A JP 2004025201 A JP2004025201 A JP 2004025201A
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Abstract
【課題】潤滑油を用いて冷間引抜き加工した後、雰囲気炉内で低温焼鈍を行っても、焼鈍残渣が生じない、表面性状に優れた冷間引抜き鋼管の製造方法を提供する。
【解決手段】下記の▲1▼〜▲4▼の工程からなる冷間引抜き鋼管の製造方法。
▲1▼素管をホウ酸のアルカリ金属塩または/およびリン酸のアルカリ金属塩を含有する水溶液に浸漬して、前記素管の内外面にそれら金属塩の皮膜を形成する。▲2▼その皮膜の上にS含有量が3質量%以下で、粘度が4×10−4〜10−3m2/s(400〜1000cSt)の潤滑油を塗布する。▲3▼冷間引抜き加工する。▲4▼炉内に1時間当たり炉容積に対して0.5倍以上のCO含有ガスを供給しながら650℃以下で熱処理する。
【選択図】なしAn object of the present invention is to provide a method for producing a cold drawn steel pipe excellent in surface properties, in which even if low temperature annealing is performed in an atmosphere furnace after cold drawing using a lubricating oil, no annealing residue is generated.
A method for manufacturing a cold drawn steel pipe, comprising the following steps (1) to (4).
(1) The tube is immersed in an aqueous solution containing an alkali metal salt of boric acid and / or an alkali metal salt of phosphoric acid to form a film of the metal salt on the inner and outer surfaces of the tube. {Circle over (2)} A lubricating oil having an S content of 3% by mass or less and a viscosity of 4 × 10 −4 to 10 −3 m 2 / s (400 to 1000 cSt) is applied on the film. (3) Cold drawing. {Circle around (4)} A heat treatment is performed at 650 ° C. or less while supplying a CO-containing gas at least 0.5 times the furnace volume per hour into the furnace.
[Selection diagram] None
Description
【0001】
【産業上の利用分野】
本発明は、冷間仕上げ機械構造用鋼管として自動車その他の産業分野で使用されている冷間引抜き鋼管の製造方法に関する。
【0002】
【従来の技術】
自動車用をはじめとして種々の産業分野で使用されている冷間仕上げ機械構造用鋼管は、コストダウン等の観点から、管の内外面の研削を行わずに使用される場合が増加している。
【0003】
鋼管の冷間引抜き加工の前処理としては、酸洗処理等により脱スケールした後、素管の表面にリン酸塩皮膜等の化成皮膜を形成させる化成処理が一般的に行われてきた。しかし、化成処理に比較して工程が簡略で、作業工数やランニングコストを削減することができるという利点を有し、また、化成処理では材料表面での化学反応(リン酸鉄の生成)を伴うため表面の平滑性が損なわれるという問題もあることから、潤滑油を素管の表面に塗布する油潤滑処理が多用されるようになってきた。
【0004】
一方、機械構造用鋼管においては高強度化が要求されることが多く、冷間加工により生じた加工歪を多く残して高強度を確保するため、比較的低い温度で応力除去のための熱処理が行われることも多い(以下、この熱処理を「低温焼鈍」ともいう)。また、熱処理(焼鈍)時における鋼管表面のスケールの発生を少なくしてスケール厚さを薄くするために、雰囲気炉を用いる雰囲気焼鈍が行われる場合も多い。
【0005】
ところが、油潤滑処理を行った上で、雰囲気炉を用いて低温焼鈍するという条件が重なると、潤滑油が焼鈍時に熱分解しにくいため十分に揮発除去されず、管の表面に、粉末状に付着する「スス」や、油の焼け残った状態の「こびり付き」などの焼鈍残渣として残存する。
【0006】
このような鋼管が出荷され、ユーザーで洗浄、切削等の加工処理が施されると、前記の焼鈍残渣の残存に起因して、洗浄水や切削油の汚れ、設備周りの汚れが生じるなど、加工環境の良好性が損なわれる。そのため、管の表面に残存する焼鈍残渣は、鋼管の製品としての品位を低下させ、また、それに伴う種々のトラブルの要因ともなる。
【0007】
これに対し、特開昭62−236896号公報では、断面減少率が30%以上に冷間引抜き加工するに際し、硫黄系極圧添加剤10〜60重量%を混合した潤滑油を用いる潤滑方法が提案されている。しかし、この方法で冷間引抜き加工した後の鋼管を650℃以下の低温で焼鈍処理すると、硫黄系極圧添加剤が潤滑油の熱分解を妨げ、焼鈍残渣が残る。
【0008】
また、特開平10−286616号公報では、抽伸(冷間引抜き加工)時に中空マンドレルを介して管内面に潤滑油を塗布する装置であって、前記中空マンドレル内の残油をタンクに戻す配管経路にリリーフ弁が設けられた管内面塗油装置が提案されている。この装置を用いれば、所定の内面塗油後、抽伸待ち中に中空マンドレルの先端部から洩れた潤滑油が口絞り部から他端に向かって流れ込み、その後の熱処理の過程で炭化して内面汚れを発生させるという問題が解消されるとしている。しかし、潤滑油そのものを改善しているわけではないため、冷間引抜き加工後の650℃以下の低温焼鈍で焼鈍残渣が残る場合がある。
【0009】
【発明が解決しようとする課題】
冷間仕上げ機械構造用鋼管を表面の研削をせずに使用する際に、前記鋼管に求められる性能として、以下の(1)〜(3)が挙げられる。
【0010】
(1)製品としての品格を高めるため鋼管表面のスケール厚さを薄くすること、具体的には、冷間引抜き加工を行い、焼鈍処理を施した後に、鋼管表面のスケール厚さが0.5〜10μm程度であること。
(2)冷間引抜き加工により生じた加工歪を、焼鈍処理の際にもとの状態には戻さずに多く残し、高い強度を確保すること。
(3)鋼管表面に焼鈍残渣の付着、残存による汚れがなく、表面性状に優れていること、具体的な目安としては、焼鈍残渣の付着量が3g/m2以下であること。
【0011】
前述したように、前記の(1)は、雰囲気炉を用いて雰囲気焼鈍することにより、また、前記の(2)は、低温焼鈍することにより達成される。
【0012】
しかし、(3)については、次のような問題がある。すなわち、化成処理に比較して表面の平滑性に優れるとともに工程が簡略で、ランニングコストが安いことから、鋼管の冷間引抜き加工の前処理として油潤滑処理が採用されるが、その場合、油潤滑に用いられている油を焼鈍処理で完全に熱分解するには650℃より高い温度に加熱する必要がある。しかし、潤滑油を塗布した鋼管を雰囲気炉でそれより低い温度で焼鈍処理を行い、焼鈍残渣を3g/m2以下とするには、冷間引抜き加工後、焼鈍処理の前に潤滑油を除去するか、焼鈍処理後に焼鈍残渣を取り除くことが必要になる。
【0013】
また、油潤滑処理においては、管と工具の界面で油切れが生じたときにも潤滑性を確保できるように、潤滑油に硫黄(含硫黄化合物)を含有する硫黄系極圧添加剤を加えるのが一般的であるが、この硫黄系極圧添加剤が焼鈍残渣の生成を助長する。
【0014】
本発明は、このような従来の技術における問題点を解決するためになされたもので、その目的は、雰囲気炉内で低温焼鈍を行う(すなわち、スケール厚さが薄く、高強度を有する鋼管を得る)という前提の下に、潤滑油を用いて冷間引抜き加工を行っても、管の表面に「スス」や「こびり付き」(「汚れ」ともいう)等の焼鈍残渣が生じることがない、表面性状に優れた冷間引抜き鋼管の製造方法を提供することにある。
【0015】
【課題を解決するための手段】
本発明者らは、上記の課題を解決するために検討を重ねた。その結果、油潤滑処理において、潤滑性を高めるために潤滑油に加える硫黄系極圧添加剤は、それ自身が焼鈍残渣として残りやすい上に、ベースの潤滑油の熱分解を妨げることが判明した。したがって、硫黄系極圧添加剤は極力少なくすることが必要である。
【0016】
また、極圧添加剤中の硫黄含有量を低く抑えることにより油膜切れが生じ、焼き付きが発生しやすくなるが、これを防ぐためには、冷間引抜き加工に先立って、素管の表面に潤滑油の保持性に優れたホウ酸のアルカリ金属塩の皮膜を形成しておくことが効果的である。ホウ酸のアルカリ金属塩の代わりにリン酸のアルカリ金属塩の皮膜を形成させても同様の効果が得られる。
【0017】
さらに、雰囲気焼鈍時に、CO含有ガスを供給して揮発したガスの置換を促進することが効果的である。
【0018】
本発明は上記の知見に基づいてなされたもので、その要旨は、以下に記す冷間引抜き鋼管の製造方法にある。
【0019】
下記の▲1▼〜▲4▼の工程からなる冷間引抜き鋼管の製造方法。
▲1▼素管をホウ酸のアルカリ金属塩を含有する水溶液に浸漬して、前記素管の内外面にホウ酸のアルカリ金属塩の皮膜を形成する。
▲2▼その皮膜の上にS含有量が3質量%以下で、粘度が4×10−4〜10−3m2/s(400〜1000cSt)の潤滑油を塗布する。
▲3▼潤滑油を塗布した素管を冷間引抜き加工する。
▲4▼前記加工後の素管を、炉内に1時間当たり炉容積に対して0.5倍以上のCO含有ガスを供給しながら650℃以下で熱処理する。
【0020】
前記▲1▼の工程において、ホウ酸のアルカリ金属塩を含有する水溶液の代わりにリン酸のアルカリ金属塩を含有する水溶液を用い、素管の内外面にリン酸のアルカリ金属塩の皮膜を形成させても同様の効果が得られる。
【0021】
また、同じく▲1▼の工程において、ホウ酸のアルカリ金属塩を含有する水溶液の代わりにホウ酸のアルカリ金属塩およびリン酸のアルカリ金属塩を含有する水溶液を用い、素管の内外面にホウ酸のアルカリ金属塩およびリン酸のアルカリ金属塩の皮膜を形成させてもよい。
【0022】
ここでいう「冷間引抜き鋼管」とは、炭素鋼、クロム鋼やクロムモリブデン鋼等の合金鋼、ステンレス鋼の素管に冷間引抜き加工を施して得られる鋼管で、自動車その他の産業分野で使用される鋼管をいう。
【0023】
なお、前記の工程▲4▼における「CO含有ガス」とは、例えば、体積%で、CO:0.1〜3.0%、CO2:10.0〜14.0%、H2:0.1〜1.5%、残部N2からなるガスをいう。
【0024】
【発明の実施の形態】
以下に、本発明の冷間引抜き鋼管の製造方法について詳細に説明する。
【0025】
本発明の冷間引抜き鋼管の製造方法は、上記の▲1▼〜▲4▼の工程からなるものである。
【0026】
▲1▼の工程では、素管をホウ酸のアルカリ金属塩を含有する水溶液に浸漬して、前記素管の内外面にホウ酸のアルカリ金属塩の皮膜を形成する。
【0027】
ホウ酸のアルカリ金属塩の皮膜は、素管との密着性が良好であり、次の▲2▼の工程でこの皮膜上に塗布される潤滑油の保持性に優れている。したがって、素管の表面にホウ酸のアルカリ金属塩の皮膜を形成させ、その上に潤滑油を塗布することにより、冷間引抜き加工の際の素管と引抜き用工具との間の摩擦力を低減させ、素管と引抜き用工具との焼き付きを防止することができる。
【0028】
ホウ酸のアルカリ金属塩の皮膜厚は、0.4〜20μmとするのが好ましい。皮膜厚が20μmを超えると剥離し易くなる。また、潤滑油が管の表面に残留し、熱処理の際、焼鈍残渣として残存する場合もある。一方、皮膜厚が0.4μm未満では、素管と引抜き用工具の直接的な接触が生、かつ、潤滑油の保持力が低下するため、潤滑性が低下することがある。
【0029】
ホウ酸のアルカリ金属塩としては、ホウ酸リチウム、ホウ酸カリウム、ホウ酸ナトリウム等が挙げられる。その中でも、ホウ酸カリウムが好ましい。
【0030】
素管の内外面にホウ酸のアルカリ金属塩の皮膜を形成させるには、先ず、素管を、前記のホウ酸のアルカリ金属塩を含有する水溶液に浸漬する。皮膜の厚さは、浸漬時間や水溶液の温度などで調節し、処理後の皮膜厚が好ましくは0.4〜20μmとなるようにする。なお、水溶液中のホウ酸のアルカリ金属塩の濃度は、皮膜の厚さ、浸漬時間等を勘案して決定すればよいが、例えば、2〜10質量%の範囲とするのが適切である。また、水溶液の温度は、70〜100℃の範囲とするのがよい。
【0031】
次いで、浸漬後の素管を乾燥させる。なお、乾燥は、150℃程度の乾燥室に装入する通常の方法により行えばよい。これによって、素管の内外面にホウ酸のアルカリ金属塩の皮膜が形成される。
【0032】
▲2▼の工程は、上記▲1▼の工程で形成された皮膜の上に、S含有量が3質量%以下で、粘度が4×10−4〜10−3m2/s(400〜1000cSt)の潤滑油を塗布する工程である。
【0033】
潤滑油のS含有量を3質量%以下とするのは、例えば潤滑油に硫黄系極圧添加剤を加えること等により、3質量%を超えてSを含有させた場合、焼鈍残渣量が増大するとともに、潤滑油の熱分解が妨げられるからである。したがって、潤滑油のS含有量は、焼鈍残渣の生成を抑えるという観点からは極力少なくすることが望ましく、Sが含まれていなくてもよい。しかし、Sがわずかでも含まれると、焼き付きが生じにくくなる効果があるので、実用上、S含有量は1.5〜3質量%とするのが望ましい。
【0034】
潤滑油の粘度(動粘度)を4×10−4〜10−3m2/s(400〜1000cSt)とするのは、粘度が4×10−4m2/sより低いと、冷間引抜き加工の際の素管と引抜き用工具間への潤滑油の引込み量が不足し、素管と引抜き用工具とが直接接触して素管に疵が発生することがあり、10−3m2/sより高いと、潤滑油の素管への付着量が増えて経済的に不利だからである。
【0035】
潤滑油を▲1▼の工程で形成された皮膜上に塗布するには、従来用いられている方法を使用すればよい。例えば、素管の外周囲に配置したノズルから潤滑油を素管の外面に供給する方法、また、素管の内部に挿入する中空マンドレルバーに設けた孔から潤滑油を素管の内面に供給する方法が適用できる。
【0036】
▲3▼の工程は、潤滑油を塗布した素管を冷間引抜き加工する工程である。この冷間引抜き加工は一般的な手法で行えばよい。
【0037】
▲4▼の工程は、前記冷間引抜き加工後の素管を、炉内に1時間当たり炉容積に対して0.5倍以上のCO含有ガスを供給しながら、650℃以下で熱処理する工程である。
【0038】
COを含有するガス雰囲気中で熱処理するのは、雰囲気中の酸素を排除し、鋼管の表面に酸化スケールが生成するのを抑えるためである。ただし、雰囲気中に酸素が含まれていないので潤滑油中の炭素が酸化されず、処理温度が650℃以下と低いので、ススや汚れ(こびり付き)などの焼鈍残渣として残留する。そこで、CO含有ガスを供給し、いわば絶えず換気を続けながらススや汚れの残留を防止する。
【0039】
熱処理に用いる炉は、バッチ式の密閉炉でもよいし、ローラーハース型の炉で、被処理材の装入部および装出部が解放されている連続炉でもよい。製造を連続的に行い、かつ換気を十分に行えるので、連続炉を用いることが好ましい。
【0040】
炉へのCO含有ガスの供給量は、1時間当たり炉容積に対して0.5倍以上の量とする。炉容積の0.5倍より少なければ熱分解した潤滑油がススとなって鋼管の表面に再付着し易くなるからである。また、前記ガスの供給量が多くなりすぎると効果に対しコストがかかりすぎ、経済的に不利になるため、供給量は炉容積の4倍以下とするのが好ましい。なお、例えば、「1時間当たり炉容積に対して4倍のガスの供給」とは、炉内に少量ずつガスを供給する一方、炉から同量のガスを排出し、1時間で炉容積の4倍の量のガスを供給することを意味する。
【0041】
熱処理の温度は650℃以下とする。前述したように、650℃以下という比較的低い温度で熱処理を行い、冷間引抜き加工により生じた加工歪を多く残して高強度を確保するためである。
【0042】
以上述べた本発明の冷間引抜き鋼管の製造方法において、▲1▼の工程で、ホウ酸のアルカリ金属塩を含有する水溶液の代わりにリン酸のアルカリ金属塩を含有する水溶液を用い、素管の内外面にリン酸のアルカリ金属塩の皮膜を形成させても同様の効果が得られる。すなわち、この皮膜も素管との密着性が良好で、潤滑油の保持性に優れ、冷間引抜き加工の際の素管と引抜き用工具との焼き付きを抑制することができる。
【0043】
なお、この場合、ホウ酸のアルカリ金属塩とリン酸のアルカリ金属塩ではその作用効果が若干相違し、前者は素管と皮膜の密着性を高め、さらに皮膜の上に塗布される潤滑油の保持性を高めて素管と引抜き用工具との焼き付きを防止する効果を有するのに対し、後者は皮膜の上に塗布される潤滑油の保持性を高めるとともに、それ自身も素管と引抜き用工具との直接接触を防ぎ、焼き付きを防止する効果を有する。
【0044】
リン酸のアルカリ金属塩を含有する水溶液を用いた場合の好ましい皮膜厚は、ホウ酸のアルカリ金属塩の場合と同様、0.4〜20μmである。
【0045】
リン酸のアルカリ金属塩としては、第二リン酸ナトリウム、第三リン酸ナトリウム、ピロリン酸ナトリウム等が挙げられる。その中でも、第二リン酸ナトリウムが好ましい。
【0046】
素管の内外面におけるリン酸のアルカリ金属塩の皮膜の形成も、ホウ酸のアルカリ金属塩の場合と同様、浸漬法により行えばよい。水溶液中のリン酸のアルカリ金属塩の濃度は、例えば、0.1〜0.5質量%の範囲とするのが適切であり、水溶液の温度は、60〜100℃の範囲とするのがよい。浸漬後の素管の乾燥についても、ホウ酸のアルカリ金属塩の場合と同様に行えばよい。
【0047】
また、同じく▲1▼の工程において、ホウ酸のアルカリ金属塩を含有する水溶液の代わりにホウ酸のアルカリ金属塩およびリン酸のアルカリ金属塩を含有する水溶液を用い、素管の内外面にホウ酸のアルカリ金属塩およびリン酸のアルカリ金属塩の皮膜を形成させても同様の効果が得られる。なお、この場合の作用効果は、ホウ酸のアルカリ金属塩を用いた場合とリン酸のアルカリ金属塩を用いた場合の中間的な作用効果を示すこととなる。
【0048】
ホウ酸のアルカリ金属塩およびリン酸のアルカリ金属塩を含有する水溶液を用いた場合の好ましい皮膜厚、皮膜の形成、その後の乾燥についても、ホウ酸のアルカリ金属塩の場合と同様に行えばよい。なお、前記水溶液中の両アルカリ金属塩の濃度は、それらの合計の濃度が例えば、0.1〜3.0質量%の範囲となるようにするのが適切である。
【0049】
上述した本発明の冷間引抜き鋼管の製造方法によれば、スケール厚さが薄く、高強度を有し、管の表面にススや汚れのない、表面性状に優れた冷間仕上げ機械構造溶鋼管を得ることができる。
【0050】
【実施例】
〔実施例1〕
JIS G 3445(機械構造用炭素鋼鋼管)に規定されるSTKM13Aを対象として、外径70.0mm×肉厚4.0mmの素管を外径60.0mm×肉厚3.4mmに冷間引抜き加工し、雰囲気炉内で、COを2.1体積%含有するガスを、1時間当たり炉容積の2倍に相当する量供給しながら、560℃または700℃で20分の焼鈍処理を行って冷間引抜き鋼管を得た。このときの焼鈍処理時における焼き付きの有無、および焼鈍残渣量を調査するとともに、得られた鋼管の引張強さを測定した。なお、冷間引抜き加工の前処理として、油潤滑処理を行った。
【0051】
表1に調査結果を示す。同表の「焼き付き」の欄の、例えば「4/5」は、同一条件で得られた5本の冷間引抜き鋼管のうちの4本に焼き付きが生じたことを表す。「0/5」、「1/5」または「2/5」であれば、良好とした。「焼鈍残渣」の欄において、○印は焼鈍残渣量が3g/m2以下、△印は同じく3g/m2を超え5g/m2以下、×印は同じく5g/m2超え、であることを意味し、○印であれば、良好と評価した。また、「引張強さ」は、510MPa以上であれば良好と評価した。「総合評価」の欄の◎印は極めて良好、○印は良好で、△印および×印は、程度の違いはあるがいずれも不良であることを意味する。◎印または○印であれば、良好と評価した。なお、表1には、使用した潤滑油のS含有量および粘度、潤滑油を塗布する前の皮膜の形成(表1には、「下地処理」と記した)に用いたアルカリ金属塩の種類、ならびに熱処理温度も併せて示した。
【0052】
【表1】
【0053】
表1の結果から明らかなように、潤滑油のS含有量が本発明で規定する範囲内であって、ホウ酸またはリン酸のアルカリ金属塩の皮膜が形成されている場合(本発明例1〜3)は、良好な結果が得られた。
【0054】
これに対し、潤滑油のS含有量が本発明で規定する範囲から外れる場合、アルカリ金属塩の皮膜が形成されていても、焼き付きは認められないものの焼鈍残渣量が多く(比較例1〜3)、アルカリ金属塩の皮膜が形成されていなければ、さらに焼き付きが生じる場合もあった(比較例6および7)。なお、熱処理温度が本発明で規定する温度より高い比較例2では引張強さが低かった。
【0055】
また、潤滑油のS含有量が本発明で規定する範囲内であっても、アルカリ金属塩の皮膜がなければ、焼鈍残渣量は少なかったが、焼き付きが生じた(比較例4および5)。なお、熱処理温度が規定よりも高い比較例5では引張強さが低かった。
〔実施例2〕
質量%で、C:0.19%、Si:0.20%、Mn:0.71%、Cr:0.06%(残部はFeと不純物)を含有する炭素鋼の鋼管を対象として、実施例1の場合と同様に、外径70.0mm×肉厚4.0mmの素管を外径60.0mm×肉厚3.4mmに冷間引抜き加工し、実施例1の場合と同じ条件により雰囲気炉内で焼鈍処理を行い、冷間引抜き鋼管を得た。このときの焼鈍処理時における焼き付きの有無、および焼鈍残渣量を調査するとともに、得られた鋼管の引張強さを測定した。なお、冷間引抜き加工の前処理として、油潤滑処理を行った。
【0056】
表2に調査結果を示す。同表の「焼き付き」および「焼鈍残渣」の欄における結果の表示方法は、実施例1の場合と同じである。「引張強さ」は、510MPa以上であれば良好と評価した。また、「総合評価」の欄の記号の意味も実施例1の場合と同じで、◎印または○印であれば、良好と評価した。なお、表2には、使用した潤滑油のS含有量および粘度、潤滑油を塗布する前の皮膜の形成(表2には、「下地処理」と記した)に用いたアルカリ金属塩の種類、ならびに熱処理温度も併せて示した。
【0057】
【表2】
【0058】
表2の結果から明らかなように、潤滑油のS含有量および粘度、ならびに熱処理温度が本発明で規定する範囲内であって、ホウ酸または/およびリン酸のアルカリ金属塩の皮膜が形成されている場合(本発明例4〜12)は、良好な結果が得られた。
【0059】
これに対し、潤滑油のS含有量が本発明で規定する範囲から外れる場合、アルカリ金属塩の皮膜が形成されていても、焼鈍残渣量が多く(比較例8、10、13、14および18)、熱処理温度が本発明で規定する温度より高ければ、焼鈍残渣量は少なかったが引張強さが低かった(比較例9および15)。
【0060】
また、潤滑油のS含有量が本発明で規定する範囲内であって、アルカリ金属塩の皮膜が形成されていても、熱処理温度が本発明で規定する温度より高ければ引張強さが低く(比較例11)、粘度が本発明で規定する範囲より低い場合は、焼き付きが生じた(比較例12、16および17)。
【0061】
【発明の効果】
本発明の冷間引抜き鋼管の製造方法によれば、スケール厚さが薄く、高強度を有し、管の表面にススや汚れのない、表面性状に優れた冷間仕上げ機械構造溶鋼管を得ることができる。[0001]
[Industrial applications]
The present invention relates to a method for producing a cold drawn steel pipe used in automobiles and other industrial fields as a steel pipe for cold finishing machine structural use.
[0002]
[Prior art]
BACKGROUND ART Steel tubes for cold finishing machine structures used in various industrial fields including automobiles are increasingly used without grinding the inner and outer surfaces of the tubes from the viewpoint of cost reduction and the like.
[0003]
As a pre-treatment for cold drawing of a steel pipe, a chemical conversion treatment of forming a chemical conversion film such as a phosphate film on the surface of a raw tube has been generally performed after descaling by pickling or the like. However, compared with the chemical conversion treatment, the process is simpler and has the advantage that the number of working steps and running costs can be reduced. In addition, the chemical conversion treatment involves a chemical reaction (production of iron phosphate) on the material surface. For this reason, there is also a problem that the surface smoothness is impaired, so that an oil lubrication treatment for applying a lubricating oil to the surface of a raw tube has come to be frequently used.
[0004]
On the other hand, steel pipes for machine structural use are often required to have high strength, and heat treatment for removing stress at relatively low temperature is required in order to secure high strength while leaving a large amount of work strain generated by cold working. It is often performed (hereinafter, this heat treatment is also referred to as “low-temperature annealing”). Atmosphere annealing using an atmosphere furnace is often performed in order to reduce the scale thickness on the surface of the steel pipe during heat treatment (annealing) and to reduce the scale thickness.
[0005]
However, if the conditions of low-temperature annealing using an atmosphere furnace after performing the oil lubrication treatment overlap, the lubricating oil is not sufficiently decomposed during the annealing, so it is not sufficiently volatilized and removed. It remains as an annealing residue such as "soot" adhering or "sticking" in a state where the oil remains unburned.
[0006]
When such a steel pipe is shipped and subjected to processing such as cleaning and cutting by the user, due to the residual of the above-mentioned annealing residue, cleaning water and dirt of cutting oil, dirt around the facilities are generated, The goodness of the processing environment is impaired. For this reason, the annealing residue remaining on the surface of the pipe lowers the quality of the steel pipe as a product, and also causes various troubles.
[0007]
On the other hand, Japanese Patent Application Laid-Open No. 62-236896 discloses a lubricating method using a lubricating oil mixed with 10 to 60% by weight of a sulfur-based extreme pressure additive when performing cold drawing to a cross-sectional reduction rate of 30% or more. Proposed. However, when the steel pipe after cold drawing by this method is annealed at a low temperature of 650 ° C. or lower, the sulfur-based extreme pressure additive hinders the thermal decomposition of the lubricating oil, leaving an annealing residue.
[0008]
JP-A-10-286616 discloses a device for applying lubricating oil to the inner surface of a pipe via a hollow mandrel at the time of drawing (cold drawing), and a piping path for returning residual oil in the hollow mandrel to a tank. There is proposed a pipe inner surface oiling device provided with a relief valve. If this device is used, after the predetermined inner surface is coated, the lubricating oil leaking from the tip of the hollow mandrel flows from the mouth drawing portion toward the other end during drawing while waiting for drawing, and is carbonized during the subsequent heat treatment process to cause inner surface contamination. It is said that the problem of generating is solved. However, since the lubricating oil itself has not been improved, annealing residues may remain in low-temperature annealing at 650 ° C. or lower after cold drawing.
[0009]
[Problems to be solved by the invention]
When a steel tube for cold finishing machine structural use is used without grinding the surface, the following (1) to (3) are mentioned as the performance required for the steel tube.
[0010]
(1) To reduce the scale thickness of the steel pipe surface in order to enhance the quality as a product, specifically, after performing cold drawing and annealing, the scale thickness of the steel pipe surface is reduced to 0.5. About 10 to about 10 μm.
(2) A large amount of processing strain caused by cold drawing is not returned to the original state at the time of annealing, but is left large, and high strength is secured.
(3) The surface of the steel pipe is free of stains due to adhesion and remaining of the annealing residue, and has excellent surface properties. As a specific guide, the amount of the adhesion of the annealing residue is 3 g / m 2 or less.
[0011]
As described above, the above (1) is achieved by performing an atmosphere annealing using an atmosphere furnace, and the above (2) is achieved by performing a low temperature annealing.
[0012]
However, (3) has the following problem. In other words, oil lubrication is used as a pre-treatment for cold drawing of steel pipes because of its excellent surface smoothness, simplified process, and low running cost compared to chemical conversion. In order to completely decompose the oil used for lubrication by the annealing treatment, it is necessary to heat the oil to a temperature higher than 650 ° C. However, in order to perform annealing at a temperature lower than that of the steel pipe coated with lubricating oil in an atmosphere furnace to reduce the annealing residue to 3 g / m 2 or less, the lubricating oil is removed after cold drawing and before annealing. Alternatively, it is necessary to remove the annealing residue after the annealing treatment.
[0013]
In the oil lubrication treatment, a sulfur-based extreme pressure additive containing sulfur (sulfur-containing compound) is added to the lubricating oil so that lubrication can be ensured even when oil runs out at the interface between the pipe and the tool. Generally, this sulfur-based extreme pressure additive promotes the formation of an annealing residue.
[0014]
The present invention has been made to solve such problems in the conventional technology, and an object of the present invention is to perform low-temperature annealing in an atmosphere furnace (that is, a steel pipe having a small scale thickness and high strength). Under the premise that even if cold drawing is performed using lubricating oil, annealing residue such as "soot" or "sticking" (also referred to as "dirt") does not occur on the pipe surface. An object of the present invention is to provide a method for manufacturing a cold drawn steel pipe having excellent surface properties.
[0015]
[Means for Solving the Problems]
The present inventors have studied to solve the above problems. As a result, in the oil lubrication process, it was found that the sulfur-based extreme pressure additive added to the lubricating oil in order to enhance the lubricity easily left itself as an annealing residue and hindered the thermal decomposition of the base lubricating oil. . Therefore, it is necessary to minimize the sulfur-based extreme pressure additive.
[0016]
In addition, by suppressing the sulfur content in the extreme pressure additive to a low level, oil film breakage occurs and seizure tends to occur, but in order to prevent this, lubricating oil must be applied to the surface of the raw pipe prior to cold drawing. It is effective to form a film of an alkali metal salt of boric acid which is excellent in the retentivity. The same effect can be obtained by forming a film of an alkali metal salt of phosphoric acid instead of the alkali metal salt of boric acid.
[0017]
Further, it is effective to supply a CO-containing gas to promote the replacement of the volatilized gas during the atmosphere annealing.
[0018]
The present invention has been made based on the above findings, and the gist of the present invention is a method for manufacturing a cold drawn steel pipe described below.
[0019]
A method for producing a cold drawn steel pipe comprising the following steps (1) to (4).
(1) The tube is immersed in an aqueous solution containing an alkali metal salt of boric acid to form a film of an alkali metal salt of boric acid on the inner and outer surfaces of the tube.
{Circle over (2)} A lubricating oil having an S content of 3% by mass or less and a viscosity of 4 × 10 −4 to 10 −3 m 2 / s (400 to 1000 cSt) is applied on the film.
{Circle around (3)} Cold drawing the tube coated with lubricating oil.
{Circle over (4)} The heat-treated raw tube is heat-treated at 650 ° C. or lower while supplying a CO-containing gas in the furnace at a rate of 0.5 times or more the furnace volume per hour.
[0020]
In the step (1), an aqueous solution containing an alkali metal salt of phosphoric acid is used instead of the aqueous solution containing an alkali metal salt of boric acid, and a film of an alkali metal salt of phosphoric acid is formed on the inner and outer surfaces of the raw tube. The same effect can be obtained by doing so.
[0021]
Also, in the step (1), an aqueous solution containing an alkali metal salt of boric acid and an alkali metal salt of phosphoric acid is used instead of the aqueous solution containing the alkali metal salt of boric acid. A film of an alkali metal salt of an acid and an alkali metal salt of phosphoric acid may be formed.
[0022]
The term `` cold drawn steel pipe '' as used herein refers to a steel pipe obtained by cold drawing a carbon steel, alloy steel such as chrome steel or chromium molybdenum steel, or stainless steel, and is used in automobiles and other industrial fields. Refers to the steel pipe used.
[0023]
The “CO-containing gas” in the step (4) is, for example, 0.1 to 3.0% by volume of CO, 10.0 to 14.0% of CO 2 , and H 2 : 0 by volume%. .1~1.5% refers to gas the balance being N 2.
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the method for producing a cold drawn steel pipe of the present invention will be described in detail.
[0025]
The method for producing a cold drawn steel pipe of the present invention comprises the above steps (1) to (4).
[0026]
In step (1), the tube is immersed in an aqueous solution containing an alkali metal salt of boric acid to form a film of an alkali metal salt of boric acid on the inner and outer surfaces of the tube.
[0027]
The film of an alkali metal salt of boric acid has good adhesion to the base tube, and has excellent retention of lubricating oil applied on the film in the next step (2). Therefore, by forming a film of an alkali metal salt of boric acid on the surface of the raw tube and applying lubricating oil thereon, the frictional force between the raw tube and the drawing tool during cold drawing is reduced. The seizure between the raw tube and the drawing tool can be prevented.
[0028]
The film thickness of the boric acid alkali metal salt is preferably from 0.4 to 20 μm. When the film thickness exceeds 20 μm, it is easy to peel off. In some cases, the lubricating oil remains on the surface of the tube and remains as an annealing residue during heat treatment. On the other hand, when the coating thickness is less than 0.4 μm, direct contact between the raw tube and the drawing tool occurs, and the holding power of the lubricating oil is reduced, so that the lubricity may be reduced.
[0029]
Examples of the alkali metal salts of boric acid include lithium borate, potassium borate, and sodium borate. Among them, potassium borate is preferred.
[0030]
In order to form a film of an alkali metal borate on the inner and outer surfaces of the tube, the tube is first immersed in an aqueous solution containing the alkali metal borate. The thickness of the film is adjusted by the immersion time, the temperature of the aqueous solution, and the like, so that the film thickness after the treatment is preferably 0.4 to 20 μm. The concentration of the alkali metal salt of boric acid in the aqueous solution may be determined in consideration of the thickness of the film, the immersion time, and the like, but is suitably, for example, in the range of 2 to 10% by mass. The temperature of the aqueous solution is preferably in the range of 70 to 100 ° C.
[0031]
Next, the tube after immersion is dried. The drying may be performed by a usual method of charging the drying room at about 150 ° C. Thereby, a film of an alkali metal salt of boric acid is formed on the inner and outer surfaces of the raw tube.
[0032]
In the step (2), the S content is 3% by mass or less and the viscosity is 4 × 10 −4 to 10 −3 m 2 / s (400 to 400 μm) on the film formed in the step (1). This is a step of applying a lubricating oil of 1000 cSt).
[0033]
The reason why the S content of the lubricating oil is set to 3% by mass or less is that when the S content exceeds 3% by mass, for example, by adding a sulfur-based extreme pressure additive to the lubricating oil, the amount of the annealing residue increases. In addition, thermal decomposition of the lubricating oil is hindered. Therefore, the S content of the lubricating oil is desirably as small as possible from the viewpoint of suppressing the generation of annealing residues, and S may not be contained. However, if S is contained even a little, there is an effect that seizure hardly occurs. Therefore, in practical use, the S content is desirably 1.5 to 3% by mass.
[0034]
The reason why the viscosity (kinematic viscosity) of the lubricating oil is set to 4 × 10 −4 to 10 −3 m 2 / s (400 to 1000 cSt) is that when the viscosity is lower than 4 × 10 −4 m 2 / s, cold drawing is performed. Insufficient amount of lubricating oil is drawn between the raw tube and the drawing tool at the time of processing, and the raw tube and the drawing tool may come into direct contact with each other to cause a flaw in the raw tube, which may be 10 −3 m 2. This is because if it is higher than / s, the amount of lubricating oil adhering to the raw pipe increases, which is economically disadvantageous.
[0035]
In order to apply the lubricating oil onto the film formed in the step (1), a conventionally used method may be used. For example, a method of supplying lubricating oil to the outer surface of the raw tube from a nozzle arranged around the outer periphery of the raw tube, or supplying lubricating oil to the inner surface of the raw tube through a hole provided in a hollow mandrel bar inserted into the raw tube Method can be applied.
[0036]
The step (3) is a step of cold drawing the raw tube coated with the lubricating oil. This cold drawing may be performed by a general method.
[0037]
Step (4) is a step of heat-treating the raw tube after the cold drawing at 650 ° C. or lower while supplying a CO-containing gas in the furnace at a rate of 0.5 times or more the furnace volume per hour. It is.
[0038]
The heat treatment in the gas atmosphere containing CO is for eliminating oxygen in the atmosphere and for suppressing the formation of oxide scale on the surface of the steel pipe. However, since oxygen is not contained in the atmosphere, carbon in the lubricating oil is not oxidized, and since the processing temperature is as low as 650 ° C. or less, it remains as an annealing residue such as soot and dirt (sticking). Therefore, a CO-containing gas is supplied to prevent soot and dirt from remaining while ventilation is constantly being performed.
[0039]
The furnace used for the heat treatment may be a batch-type closed furnace or a roller hearth-type furnace, and may be a continuous furnace in which the loading and unloading sections for the material to be treated are opened. It is preferable to use a continuous furnace because the production is performed continuously and the ventilation can be sufficiently performed.
[0040]
The supply amount of the CO-containing gas to the furnace is 0.5 times or more the furnace volume per hour. If the furnace volume is less than 0.5 times, the thermally decomposed lubricating oil becomes soot and easily adheres to the surface of the steel pipe. In addition, if the supply amount of the gas is too large, the cost is too high for the effect and it is economically disadvantageous. Therefore, the supply amount is preferably four times or less the furnace volume. For example, "supply of gas four times the furnace volume per hour" means that gas is supplied into the furnace little by little, while the same amount of gas is discharged from the furnace, and the furnace volume is reduced in one hour. This means supplying four times the amount of gas.
[0041]
The temperature of the heat treatment is 650 ° C. or less. As described above, heat treatment is performed at a relatively low temperature of 650 ° C. or less, and high strength is secured while leaving a large amount of processing strain generated by cold drawing.
[0042]
In the method for producing a cold drawn steel pipe of the present invention described above, in step (1), an aqueous solution containing an alkali metal salt of phosphoric acid is used instead of the aqueous solution containing an alkali metal salt of boric acid. The same effect can be obtained by forming a film of an alkali metal salt of phosphoric acid on the inner and outer surfaces of the film. In other words, this film also has good adhesion to the raw tube, excellent retention of lubricating oil, and can suppress seizure between the raw tube and the drawing tool during cold drawing.
[0043]
In this case, the effects of the alkali metal salt of boric acid and the alkali metal salt of phosphoric acid are slightly different, and the former enhances the adhesion between the base tube and the film and further improves the lubricating oil applied on the film. While it has the effect of increasing the retention and preventing seizure between the raw tube and the drawing tool, the latter enhances the retention of the lubricating oil applied on the coating, and itself is used for the raw tube and the drawing tool. It has the effect of preventing direct contact with the tool and preventing seizure.
[0044]
The preferred film thickness when using an aqueous solution containing an alkali metal salt of phosphoric acid is 0.4 to 20 μm, as in the case of the alkali metal salt of boric acid.
[0045]
Examples of the alkali metal salts of phosphoric acid include dibasic sodium phosphate, tribasic sodium phosphate, sodium pyrophosphate and the like. Among them, dibasic sodium phosphate is preferred.
[0046]
The formation of the film of the alkali metal salt of phosphoric acid on the inner and outer surfaces of the raw tube may be performed by the immersion method as in the case of the alkali metal salt of boric acid. The concentration of the alkali metal salt of phosphoric acid in the aqueous solution is suitably, for example, in the range of 0.1 to 0.5% by mass, and the temperature of the aqueous solution is preferably in the range of 60 to 100 ° C. . The drying of the tube after immersion may be performed in the same manner as in the case of the alkali metal salt of boric acid.
[0047]
Also, in the step (1), an aqueous solution containing an alkali metal salt of boric acid and an alkali metal salt of phosphoric acid is used instead of the aqueous solution containing the alkali metal salt of boric acid. The same effect can be obtained by forming a film of an alkali metal salt of an acid and an alkali metal salt of phosphoric acid. The operation and effect in this case are intermediate between the case where the alkali metal salt of boric acid is used and the case where the alkali metal salt of phosphoric acid is used.
[0048]
The preferred film thickness, film formation, and subsequent drying when using an aqueous solution containing an alkali metal salt of boric acid and an alkali metal salt of phosphoric acid may be performed in the same manner as in the case of the alkali metal salt of boric acid. . The concentration of both alkali metal salts in the aqueous solution is suitably adjusted so that the total concentration thereof is in the range of, for example, 0.1 to 3.0% by mass.
[0049]
According to the method for producing a cold drawn steel pipe of the present invention described above, the scale thickness is small, the strength is high, there is no soot or dirt on the pipe surface, and the cold-finished machine structural molten steel pipe having excellent surface properties. Can be obtained.
[0050]
【Example】
[Example 1]
For a STKM13A specified in JIS G 3445 (carbon steel pipe for machine structural use), cold-draw a base tube with an outer diameter of 70.0 mm x wall thickness of 4.0 mm to an outer diameter of 60.0 mm x wall thickness of 3.4 mm. After processing, an annealing treatment was performed at 560 ° C. or 700 ° C. for 20 minutes in an atmosphere furnace while supplying a gas containing 2.1% by volume of CO in an amount corresponding to twice the furnace volume per hour. A cold drawn steel pipe was obtained. At this time, the presence or absence of seizure during the annealing treatment and the amount of annealing residue were investigated, and the tensile strength of the obtained steel pipe was measured. Note that an oil lubrication treatment was performed as a pretreatment for the cold drawing.
[0051]
Table 1 shows the survey results. For example, “4/5” in the column of “Seizure” in the table indicates that seizure occurred in four of the five cold drawn steel pipes obtained under the same conditions. If it was "0/5", "1/5" or "2/5", it was judged as good. In the column of “annealing residue”, ○ indicates that the amount of the annealing residue is 3 g / m 2 or less, Δ indicates that the amount is also more than 3 g / m 2 and 5 g / m 2 or less, and X indicates that the amount is 5 g / m 2 or more. Means that the mark was good. The “tensile strength” was evaluated as good if it was 510 MPa or more. In the column of “Comprehensive Evaluation”, the mark 極 め て is extremely good, the mark ○ is good, and the mark △ and the mark x indicate that there is a difference in the degree, but both are bad. ◎ or 印 was evaluated as good. Table 1 shows the S content and viscosity of the lubricating oil used, and the type of alkali metal salt used for forming the film before applying the lubricating oil (in Table 1, described as “undercoat treatment”). , And the heat treatment temperature are also shown.
[0052]
[Table 1]
[0053]
As is clear from the results in Table 1, the case where the S content of the lubricating oil is within the range specified in the present invention and a film of an alkali metal salt of boric acid or phosphoric acid is formed (Example 1 of the present invention) In 3), good results were obtained.
[0054]
On the other hand, when the S content of the lubricating oil is out of the range specified in the present invention, even though a film of an alkali metal salt is formed, seizure is not recognized but the amount of annealing residue is large (Comparative Examples 1 to 3). ), If the film of the alkali metal salt was not formed, seizure might occur further (Comparative Examples 6 and 7). In Comparative Example 2, in which the heat treatment temperature was higher than the temperature specified in the present invention, the tensile strength was low.
[0055]
In addition, even when the S content of the lubricating oil was within the range specified in the present invention, the amount of annealing residue was small, but seizure occurred (Comparative Examples 4 and 5) without the alkali metal salt film. In Comparative Example 5, in which the heat treatment temperature was higher than the specified value, the tensile strength was low.
[Example 2]
Conducted on carbon steel pipes containing 0.19% of C, 0.20% of Si, 0.71% of Mn, and 0.06% of Cr (the balance being Fe and impurities) by mass%. Similarly to the case of Example 1, a raw tube having an outer diameter of 70.0 mm × thickness of 4.0 mm was cold drawn to an outer diameter of 60.0 mm × thickness of 3.4 mm, under the same conditions as in Example 1. Annealing treatment was performed in an atmosphere furnace to obtain a cold drawn steel pipe. At this time, the presence or absence of seizure during the annealing treatment and the amount of annealing residue were investigated, and the tensile strength of the obtained steel pipe was measured. Note that an oil lubrication treatment was performed as a pretreatment for the cold drawing.
[0056]
Table 2 shows the survey results. The display method of the results in the columns of “burn-in” and “annealing residue” in the same table is the same as that in the first embodiment. "Tensile strength" was evaluated as good if it was 510 MPa or more. The meanings of the symbols in the column of “Comprehensive evaluation” are the same as those in Example 1, and a mark of “◎” or “○” is evaluated as good. Table 2 shows the S content and viscosity of the used lubricating oil, and the type of alkali metal salt used for forming the film before applying the lubricating oil (in Table 2, described as “undercoat treatment”). , And the heat treatment temperature are also shown.
[0057]
[Table 2]
[0058]
As is clear from the results in Table 2, the S content and viscosity of the lubricating oil and the heat treatment temperature were within the ranges specified in the present invention, and a film of an alkali metal salt of boric acid or / and phosphoric acid was formed. (Examples 4 to 12 of the present invention), good results were obtained.
[0059]
On the other hand, when the S content of the lubricating oil is out of the range specified in the present invention, the amount of the annealing residue is large (Comparative Examples 8, 10, 13, 14, and 18) even if the alkali metal salt film is formed. ), When the heat treatment temperature was higher than the temperature specified in the present invention, the amount of annealing residue was small but the tensile strength was low (Comparative Examples 9 and 15).
[0060]
Further, even if the S content of the lubricating oil is within the range specified in the present invention and the alkali metal salt film is formed, if the heat treatment temperature is higher than the temperature specified in the present invention, the tensile strength is low ( In Comparative Example 11), when the viscosity was lower than the range specified in the present invention, seizure occurred (Comparative Examples 12, 16 and 17).
[0061]
【The invention's effect】
According to the method for producing a cold drawn steel pipe of the present invention, a cold-finished machine structural steel pipe having a thin scale, high strength, no soot or dirt on the surface of the pipe, and excellent in surface properties is obtained. be able to.
Claims (3)
▲1▼素管をホウ酸のアルカリ金属塩を含有する水溶液に浸漬して、前記素管の内外面にホウ酸のアルカリ金属塩の皮膜を形成する。
▲2▼その皮膜の上にS含有量が3質量%以下で、粘度が4×10−4〜10−3m2/s(400〜1000cSt)の潤滑油を塗布する。
▲3▼潤滑油を塗布した素管を冷間引抜き加工する。
▲4▼前記加工後の素管を、炉内に1時間当たり炉容積に対して0.5倍以上のCO含有ガスを供給しながら650℃以下で熱処理する。A method for producing a cold drawn steel pipe comprising the following steps (1) to (4).
(1) The tube is immersed in an aqueous solution containing an alkali metal salt of boric acid to form a film of an alkali metal salt of boric acid on the inner and outer surfaces of the tube.
{Circle over (2)} A lubricating oil having an S content of 3% by mass or less and a viscosity of 4 × 10 −4 to 10 −3 m 2 / s (400 to 1000 cSt) is applied on the film.
{Circle around (3)} Cold drawing the tube coated with lubricating oil.
{Circle over (4)} The heat-treated raw tube is heat-treated at 650 ° C. or lower while supplying a CO-containing gas in the furnace at a rate of 0.5 times or more the furnace volume per hour.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002181869A JP3770211B2 (en) | 2002-06-21 | 2002-06-21 | Manufacturing method of cold drawn steel pipe |
| TW92136560A TWI275641B (en) | 2002-06-21 | 2003-12-23 | Cold-drawn lubricating oil, lubrication film and method of producing cold-drawn steel tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002181869A JP3770211B2 (en) | 2002-06-21 | 2002-06-21 | Manufacturing method of cold drawn steel pipe |
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| Publication Number | Publication Date |
|---|---|
| JP2004025201A true JP2004025201A (en) | 2004-01-29 |
| JP3770211B2 JP3770211B2 (en) | 2006-04-26 |
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|---|---|---|---|
| JP2002181869A Expired - Fee Related JP3770211B2 (en) | 2002-06-21 | 2002-06-21 | Manufacturing method of cold drawn steel pipe |
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| TW (1) | TWI275641B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005061141A1 (en) * | 2003-12-22 | 2005-07-07 | Sumitomo Metal Industries, Ltd. | Lubricating oil for cold drawing and lubricating coating film, and method for producing cold-drawn steel pipe |
| KR100777495B1 (en) * | 2006-06-21 | 2007-11-20 | 수미도모 메탈 인더스트리즈, 리미티드 | Method for manufacturing cold drawn lubricant, lubricating film and cold drawn steel pipe |
-
2002
- 2002-06-21 JP JP2002181869A patent/JP3770211B2/en not_active Expired - Fee Related
-
2003
- 2003-12-23 TW TW92136560A patent/TWI275641B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005061141A1 (en) * | 2003-12-22 | 2005-07-07 | Sumitomo Metal Industries, Ltd. | Lubricating oil for cold drawing and lubricating coating film, and method for producing cold-drawn steel pipe |
| KR100777495B1 (en) * | 2006-06-21 | 2007-11-20 | 수미도모 메탈 인더스트리즈, 리미티드 | Method for manufacturing cold drawn lubricant, lubricating film and cold drawn steel pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200521221A (en) | 2005-07-01 |
| JP3770211B2 (en) | 2006-04-26 |
| TWI275641B (en) | 2007-03-11 |
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