JP3506088B2 - Martensitic stainless steel with excellent fatigue resistance for coiled tubing and its production method - Google Patents
Martensitic stainless steel with excellent fatigue resistance for coiled tubing and its production methodInfo
- Publication number
- JP3506088B2 JP3506088B2 JP2000026615A JP2000026615A JP3506088B2 JP 3506088 B2 JP3506088 B2 JP 3506088B2 JP 2000026615 A JP2000026615 A JP 2000026615A JP 2000026615 A JP2000026615 A JP 2000026615A JP 3506088 B2 JP3506088 B2 JP 3506088B2
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- Prior art keywords
- fatigue
- stainless steel
- coiled tubing
- steel
- corrosion resistance
- Prior art date
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、硫化水素や炭酸ガ
スを含有する石油、天然ガスを生産・輸送する際に、使
用できるシームレス鋼管、電縫管、レーザー溶接鋼管等
の配管用鋼およびそれを使った鋼管の製造方法に関す
る。もちろん、本発明は、炭酸ガスを含有する他の産業
分野、例えば、脱炭酸ガス設備の配管、地熱発電用の配
管および炭酸ガス含有液のタンクを構成する材料にも適
用できる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to seamless steel pipes, electric resistance welded pipes, laser welded steel pipes, and other pipe steels that can be used when producing and transporting petroleum and natural gas containing hydrogen sulfide and carbon dioxide. The present invention relates to a method for manufacturing a steel pipe. Of course, the present invention can also be applied to other industrial fields containing carbon dioxide gas, for example, the materials for forming piping for decarbonation equipment, piping for geothermal power generation, and tanks for carbon dioxide-containing liquid.
【０００２】[0002]
【従来の技術】油井のフィールドでの油井敷設に伴う経
費は、油井の掘削からケーシング、チュービングの敷設
までのフィールド現地での作業時間に依存している。そ
こで、経費削減のために、掘削時間やケーシング、チュ
ービングの敷設時間の低減が望まれている。2. Description of the Related Art The cost of laying an oil well in the field of an oil well depends on the work time in the field from the drilling of the oil well to the laying of casing and tubing. Therefore, in order to reduce costs, it is desired to reduce excavation time and casing and tubing laying time.
【０００３】掘削時間の低減については、コイル状に巻
いた管を連続的に油井内に挿入するコイルドチュービン
グという技術が採用され始めている。To reduce the excavation time, a technique called coiled tubing in which a coiled tube is continuously inserted into an oil well has begun to be adopted.
【０００４】一方、近年、石油または天然ガスを採取す
るための井戸の環境がますます過酷なものになってお
り、これらの流体を生産・輸送する配管やチュービング
およびケーシングの腐食が大きな問題となっている。On the other hand, in recent years, the environment of wells for collecting oil or natural gas has become more and more severe, and the corrosion of pipes, tubing and casing for producing and transporting these fluids has become a serious problem. ing.
【０００５】これらの耐食性を必要とするチュービング
にコイルドチュービング技術を用い、敷設時間の低減を
図ることは、下記理由により実現されていない。コイル
ドチュービングというのは、工場で成形した管を周溶接
で繋ぐことにより、この管の長さを予め使用長さにして
おき、それを外径４ｍ程度のリールで巻き取り、現地で
リール巻きされた管をのばして使用するチュービングの
ことである。従って、コイルドチュービングに用いる管
には、曲げと曲げ戻しという塑性変形を受け、加工硬化
する。このため、耐食性が低下し、従来のコイルドチュ
ービングでは、石油または天然ガスの流体を生産する鋼
管として十分な耐食性が得られないという問題があっ
た。The use of the coiled tubing technique for the tubing requiring corrosion resistance has not been realized for the following reasons because of the following reason. Coiled tubing means that the pipe formed at the factory is connected by circumferential welding to make the length of this pipe into a working length in advance, which is then wound on a reel with an outer diameter of about 4 m and wound on the reel. It is a tubing that is used by extending the cut tube. Therefore, the pipe used for coiled tubing undergoes plastic deformation such as bending and unbending, and is work hardened. Therefore, there is a problem that the corrosion resistance is lowered, and the conventional coiled tubing cannot obtain sufficient corrosion resistance as a steel pipe for producing a fluid of oil or natural gas.
【０００６】さらに、コイルドチュービングには、曲げ
のばしの塑性変形が数回加えられるため、優れた疲労特
性も同時に要求される。Further, the coiled tubing is required to have excellent fatigue properties at the same time, because the plastic deformation of the bending extension is applied several times.
【０００７】コイルドチュービングには、塑性変形を伴
った疲労が付加されるため、比較的少ないサイクル数、
すなわち低サイクルの疲労でコイルドチュービングは破
断する。従って、コイルドチュービングに望まれる疲労
特性は、優れた低サイクル疲労特性である。ここで、１
サイクルの疲労とは、１回の曲げと１回の曲げ戻しのこ
とである。Coiled tubing has a relatively small number of cycles because fatigue accompanied by plastic deformation is added.
That is, the low-cycle fatigue causes the coiled tubing to break. Therefore, the fatigue property desired for coiled tubing is excellent low cycle fatigue property. Where 1
Cycle fatigue is one bend and one bend back.
【０００８】コイルドチュービングの製造方法として
は、特開平７−214143号公報にCr−Ni合金鋼と炭素鋼の
二重管の製造方法が開示されているが、耐食性と疲労特
性について具体的に説明されていない。As a method for producing coiled tubing, Japanese Patent Application Laid-Open No. 7-214143 discloses a method for producing a double pipe of Cr-Ni alloy steel and carbon steel. Not explained.
【０００９】一方、海水中下での耐食性と疲労特性を向
上させた高強度マルテンサイト圧延鋼板が特許第266753
8 号公報に開示されているが、ここでは高サイクルで、
低サイクル疲労特性についての開示はなされていない。On the other hand, a high-strength martensitic rolled steel sheet with improved corrosion resistance and fatigue characteristics in seawater is disclosed in Japanese Patent No. 266753.
Although disclosed in Japanese Patent Publication No. 8, here, in a high cycle,
There is no disclosure of low cycle fatigue properties.
【００１０】[0010]
【発明が解決しようとする課題】本発明の課題は、上述
の事情を考慮して、石油または天然ガスの流体を生産・
輸送する配管やコイルドチュービングとして使用できる
ように耐疲労特性と疲労が加わったときの耐食性とに優
れた耐力550MPa以上のマルテンサイト系ステンレス鋼お
よびそれからの製管法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to produce a fluid of oil or natural gas in consideration of the above circumstances.
It is intended to provide a martensitic stainless steel having a fatigue strength of 550 MPa or more, which is excellent in fatigue resistance and corrosion resistance when fatigue is added, and a method for producing a pipe from the martensite stainless steel, which can be used as piping for transportation or coiled tubing.
【００１１】[0011]
【課題を解決するための手段】本発明者等が鋼の添加元
素を変化させて、疲労特性と疲労が加わったときの耐食
性能 (耐炭酸ガス腐食性能と耐硫化物応力腐食割れ性
能) を調査した結果、Ｃ、Cr、Ni、Al、Mn、Ｎ等の特定
の元素を適切なバランスで添加することにより組織のフ
ェライト率を５％以下にすることが重要であることを新
たに見出し、本発明に至った。[Means for Solving the Problems] The inventors of the present invention changed the additive elements of steel to determine fatigue characteristics and corrosion resistance performance when fatigue was added (carbon dioxide corrosion resistance and sulfide stress corrosion cracking resistance). As a result of the investigation, it was newly found that it is important to reduce the ferrite ratio of the structure to 5% or less by adding specific elements such as C, Cr, Ni, Al, Mn and N in an appropriate balance. The present invention has been completed.
【００１２】さらに、本発明の範囲で疲労が加わったと
きの耐食性能を疲労が加わっていない状態の耐食性能と
同等にするためには、数サイクル以上の低サイクル疲労
を加える必要があることも新たに見出し、本発明に至っ
た。これからも分かるように本発明に言う疲労特性は特
に低サイクルでの耐疲労性である。Further, in order to make the corrosion resistance performance under fatigue within the scope of the present invention equal to the corrosion resistance performance under no fatigue, it is necessary to add low cycle fatigue of several cycles or more. The present invention has been newly found and has led to the present invention. As will be understood from the above, the fatigue property referred to in the present invention is fatigue resistance particularly in low cycles.
【００１３】 ここに本発明は次の通りである。
(1) 質量％で、
Ｃ：0.001 〜0.04％、 Si: 1.0 ％以下、 Mn：0.1
〜3.0 ％、
Ｐ: 0.04％以下、 Ｓ: 0.005 ％以下、 Cr：９〜
15％、
Ni：0.7 〜８％、 Al：0.001 〜0.20％、Ｎ: 0.05
％以下
を含有し、さらに、下記式を満足し、
ME＝Cr＋12Al−40(C+N) −４Ni−２Mn≦9.0 残部が鉄および不可避的不純物よりなる鋼組成を有し、
焼戻し後の組織のマルテンサイト率が95％以上であるこ
とを特徴とする、耐疲労特性と耐食性に優れたコイルド
チュービング用マルテンサイト系ステンレス鋼。
(2) 前記鋼組成が、質量％で、
Nb：0.005 〜0.10％、Ｖ：0.005 〜0.10％、Ti：0.005
〜0.10％、Zr：0.005 〜0.10％のうちから選ばれた１
種または２種以上をさらに含有し、Mo+W/2：0.2 〜3.0
％を満たすようにMoおよびＷのうちから選ばれた１種ま
たは２種を含有し、さらに下記式を満足し、
ME＝Cr+4(Mo+W/2)+11V+5Nb+12Al+8Ti-40(C+N)-4Ni-2Mn
≦9.0
焼戻し後の組織のマルテンサイト率が95％以上であるこ
とを特徴とする、上記(1) 記載の耐疲労特性と耐食性に
優れたコイルドチュービング用マルテンサイト系ステン
レス鋼。
(3) 前記鋼組成が、質量％で、Ca：0.001 〜0.05％、M
g：0.001 〜0.05％、La：0.001 〜0.05％、およびCe：
0.001 〜0.05％のうちから選ばれた１種または２種以
上をさらに含有し、さらに、さらに下記式を満足し、
ME＝Cr+4(Mo+W/2)+11V+5Nb+12Al+8Ti-40(C+N)-4Ni-2Mn
≦9.0
焼戻し後の組織のマルテンサイト率が95％以上であるこ
とを特徴とする上記(1) または(2) 記載の耐疲労特性と
耐食性に優れたコイルドチュービング用マルテンサイト
系ステンレス鋼。
(4) 上記(1) 〜(3) のいずれかに記載のマルテンサイト
系ステンレス鋼から製造した鋼管に繰り返し疲労を３サ
イクル以上加える耐疲労特性と耐食性に優れたコイルド
チュービング用マルテンサイト系ステンレス鋼管の製造
方法。The present invention is as follows. (1)% by mass, C: 0.001 to 0.04%, Si: 1.0% or less, Mn: 0.1
~ 3.0%, P: 0.04% or less, S: 0.005% or less, Cr: 9 ~
15%, Ni: 0.7-8%, Al: 0.001-0.20%, N: 0.05
% Or less, further satisfying the following formula, ME = Cr + 12Al-40 (C + N) -4Ni-2Mn≤9.0 having a steel composition in which the balance is iron and inevitable impurities,
Coiled with excellent fatigue resistance and corrosion resistance, characterized by a martensite ratio of 95% or more in the structure after tempering
Martensitic stainless steel for tubing . (2) The steel composition is, by mass%, Nb: 0.005 to 0.10%, V: 0.005 to 0.10%, Ti: 0.005
~ 0.10%, Zr: 0.005 ~ 0.10% selected from 1%
, Or 2 or more, Mo + W / 2: 0.2-3.0
%, Containing 1 or 2 selected from Mo and W, and further satisfying the following formula, ME = Cr + 4 (Mo + W / 2) + 11V + 5Nb + 12Al + 8Ti -40 (C + N) -4Ni-2Mn
≦ 9.0 Martensite stainless steel for coiled tubing excellent in fatigue resistance and corrosion resistance as described in (1) above, characterized in that the structure has a martensite ratio of 95% or more after tempering. (3) The steel composition is, by mass%, Ca: 0.001 to 0.05%, M
g: 0.001 to 0.05%, La: 0.001 to 0.05%, and Ce:
It further contains one or more selected from 0.001 to 0.05%, and further satisfies the following formula, ME = Cr + 4 (Mo + W / 2) + 11V + 5Nb + 12Al + 8Ti -40 (C + N) -4Ni-2Mn
≦ 9.0 Martensite stainless steel for coiled tubing excellent in fatigue resistance and corrosion resistance according to the above (1) or (2), wherein the martensite ratio of the structure after tempering is 95% or more. (4) A coiled product having excellent fatigue resistance and corrosion resistance in which the steel pipe manufactured from the martensitic stainless steel according to any one of (1) to (3) above is subjected to repeated fatigue for 3 cycles or more.
A method for manufacturing a martensitic stainless steel pipe for tubing .
【００１４】[0014]
【発明の実施の形態】本発明において、成分組成を前述
のように数値限定した理由を以下に説明する。なお、本
明細書において「％」は特にことわりがないかぎり、
「質量％」である。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the reason why the component composition is numerically limited as described above will be explained below. In the present specification, "%" is unless otherwise specified,
It is "mass%".
【００１５】Ｃ：その含有量が0.04％を越えると、焼き
戻し後の硬度が高くなり過ぎ、硫化物応力腐食割れ感受
性が高くなる。また、炭化物の析出量が増加し、疲労強
度が低下するため、その上限を0.04％と定めた。Ｃ％は
低ければ低いほうがいいが、経済的に製造容易なことを
考慮して、0.001 ％を下限とした。そこで、Ｃ添加量を
0.001 〜0.04％とした。なお、Ｃ％が低いほど溶接まま
での熱影響部の靱性が良好となるため、好ましくは0.00
1 〜0.025 ％、より好ましくは0.001 〜0.015 ％であ
る。C: If the content exceeds 0.04%, the hardness after tempering becomes too high and the susceptibility to sulfide stress corrosion cracking becomes high. Further, since the precipitation amount of carbide increases and the fatigue strength decreases, the upper limit was set to 0.04%. C% should be as low as possible, but 0.001% was made the lower limit in consideration of economical production. Therefore, the amount of C added
It was set to 0.001 to 0.04%. The lower the C%, the better the toughness of the heat-affected zone in the as-welded state.
It is 1 to 0.025%, more preferably 0.001 to 0.015%.
【００１６】Cr：Cr は耐炭酸ガス腐食性を向上させる
成分である。９％未満では十分な耐炭酸ガス腐食性を得
られない。また、15％超では、焼入れままでマルテンサ
イト相を得ることが難しいのでCr含量は９〜15％とし
た。Cr: Cr is a component that improves carbon dioxide corrosion resistance. If it is less than 9%, sufficient carbon dioxide corrosion resistance cannot be obtained. Further, if it exceeds 15%, it is difficult to obtain a martensite phase as it is quenched, so the Cr content is set to 9 to 15%.
【００１７】Ni：Ni は焼入れままの組織をマルテンサ
イト率95％以上とするために必要である。焼入れままの
組織は、Ni添加量が0.7 ％未満ではフェライト、8 ％を
超えるとオーステナイトとなるため、Niの添加範囲を0.
7 〜8 ％とした。より好ましくは、0.7 〜7 ％である。Ni: Ni is necessary for the as-quenched structure to have a martensite ratio of 95% or more. The as-quenched structure becomes ferrite when the Ni content is less than 0.7%, and becomes austenite when the Ni content exceeds 8%.
It was set to 7 to 8%. More preferably, it is 0.7 to 7%.
【００１８】Si：脱酸剤として必要である。但し、1.0
％を超えると靱性が低下すると共に、熱間加工性を低下
させるので、その上限を1.0 ％とした。Si: Necessary as a deoxidizer. However, 1.0
%, The toughness decreases and the hot workability decreases, so the upper limit was made 1.0%.
【００１９】Mn：熱間加工性を改善するために0.1 ％以
上の含有が必要である。3.0 ％超の添加ではその効果が
飽和する。Mn: To improve hot workability, the content of Mn must be 0.1% or more. Addition of more than 3.0% saturates the effect.
【００２０】Ｓ：熱間加工性からは少なければ少ないほ
ど良い。脱硫コストとのかねあいで上限を0.005 ％とし
た。S: From the viewpoint of hot workability, the smaller the better, the better. The upper limit was set to 0.005% in consideration of the desulfurization cost.
【００２１】Ｐ：Ｐは0.04％を超えると硫化物応力腐食
割れ性が著しく低下する。P: When P exceeds 0.04%, the sulfide stress corrosion cracking property is significantly reduced.
【００２２】Al：脱酸剤として使用する0.001 ％未満で
はその効果がなく、0.20％を超えると介在物が多くなっ
て耐食性が損なわれる。Al: When used as a deoxidizing agent, less than 0.001% has no effect, and when more than 0.20%, inclusions increase and corrosion resistance is impaired.
【００２３】Ｎ：Ｎは0.05％を超えると強度が上昇しす
ぎ硫化物応力腐食割れ感受性が高くなる。N: If N exceeds 0.05%, the strength is excessively increased and the susceptibility to sulfide stress corrosion cracking is increased.
【００２４】Nb、Ti、Zr、Ｖ：これらの元素は、Ｃを固
定し、強度ばらつきを少なくするために、所望により、
少なくとも１種添加するが、いずれも過剰に添加すると
焼入れまま組織のマルテンサイト率を95％以上とするこ
とができず、更に、焼入れままの硬度も高くなりすぎ、
却ってカソード防食性能を低下させるため、Nb：0.005
〜0.10％、Ti：0.005 〜0.10％、Zr：0.005 〜0.10％、
Ｖ：0.005 〜0.10％とした。Nb, Ti, Zr, V: These elements are used, if desired, in order to fix C and reduce variations in strength.
At least one kind is added, but if both are added excessively, the martensite ratio of the structure as quenched cannot be 95% or more, and the hardness as quenched is too high,
On the contrary, Nb: 0.005 to reduce the cathodic protection performance.
~ 0.10%, Ti: 0.005-0.10%, Zr: 0.005-0.10%,
V: 0.005 to 0.10%.
【００２５】Mo、Ｗ：Mo、Ｗは、Crの共存下で炭酸ガス
環境での局部腐食を防止する元素である。本発明の好適
態様にあっては、Mo＋Ｗ／２：0.2 〜3.0 ％を満たす様
にMo、Ｗの内から１種または２種を含有する。Mo＋Ｗ／
２が3.0 ％超となるように添加しても局部腐食を防止す
る効果は飽和するため、Mo＋Ｗ／２を0.2 〜3.0 ％まで
添加することにした。Mo, W: Mo and W are elements that prevent local corrosion in a carbon dioxide environment in the presence of Cr. In a preferred embodiment of the present invention, one or two of Mo and W are contained so as to satisfy Mo + W / 2: 0.2 to 3.0%. Mo + W /
Even if 2 is added to exceed 3.0%, the effect of preventing local corrosion is saturated, so Mo + W / 2 was added to 0.2-3.0%.
【００２６】Ca、Mg、La、Ce：これらの元素は、いずれ
も鋼の熱間加工性を向上させるのに有効な元素である。
従って、その効果を得たい場合には、これらの内１種ま
たは２種以上を選んで添加できる。しかし、いずれの元
素もその含有量が0.001 ％未満では上記効果が得られな
い。一方、0.05％を超えて添加含有させると、粗大な酸
化物が生成し、却って耐食性が低下する。Ca, Mg, La, Ce: All of these elements are effective elements for improving the hot workability of steel.
Therefore, in order to obtain the effect, one or more of these can be selected and added. However, if the content of any element is less than 0.001%, the above effect cannot be obtained. On the other hand, if it is added and contained in excess of 0.05%, a coarse oxide is generated and the corrosion resistance is rather deteriorated.
【００２７】よって、Ca：0.001 〜0.05％、Mg：0.001
〜0.05％、La：0.001 〜0.05％およびCe：0.001 〜0.05
％とした。これらの元素の内で特に好ましい添加元素
は、Ca、Laである。Therefore, Ca: 0.001 to 0.05%, Mg: 0.001
~ 0.05%, La: 0.001-0.05% and Ce: 0.001-0.05
%. Of these elements, particularly preferable additive elements are Ca and La.
【００２８】また、耐食性および疲労特性を向上させる
ためには、上記成分限定に加え、焼き戻し後の組織のマ
ルテンサイト率を95％以上とする。In order to improve the corrosion resistance and fatigue properties, the martensite ratio of the structure after tempering is set to 95% or more in addition to the above component limitation.
【００２９】焼き戻し後の組織のマルテンサイト率を95
％以上にするには、下記(1) 式または(2) 式を満足すれ
ば良い。
ME＝Cr＋12Al− 40(C ＋N)−４Ni−２Mn≦9.0 ・・・・・・・(1)
ME＝Cr＋4(Mo＋W/2)＋11V ＋５Nb＋12Al＋8Ti −40(C＋N)−4Ni −2Mn ≦9.0
・・・・・・・(2)
更に、上記の成分系で慣用法にしたがって製造した鋼管
に、予め、３回以上、より好ましくは５サイクル以上の
繰り返し疲労を加えることにより、疲労を受けた部分の
耐食性能、特に硫化物応力腐食性能が低下しないように
することができる。The martensite ratio of the structure after tempering was set to 95
In order to make it more than%, the following formula (1) or (2) should be satisfied. ME = Cr + 12Al-40 (C + N) -4Ni-2Mn ≦ 9.0 ・ ・ ・ ・ (1) ME = Cr + 4 (Mo + W / 2) ＋ 11V + 5Nb + 12Al + 8Ti-40 (C + N) -4Ni-2Mn ≦ 9.0 ・ ・ ・ ・... (2) Furthermore, the steel pipe manufactured according to the conventional method using the above component system is subjected to repeated fatigue at least 3 times, more preferably at least 5 cycles, in advance, so that the corrosion resistance performance of the fatigued portion is increased. In particular, the sulfide stress corrosion performance can be prevented from deteriorating.
【００３０】具体的には、適宜手段で製管した後に、得
られた管をリールに巻き付け、巻き戻すことを繰り返す
ことで繰り返し疲労を与えてもよい。ここで、耐食性と
は、耐炭酸ガス腐食性能および耐硫化物応力腐食割れ性
能をいい、繰り返し疲労とは、管に曲げ・曲げ戻しの塑
性変形を加えた時に、管に付加される疲労のことであ
る。Specifically, fatigue may be repeatedly given by repeating the process of producing the pipe by an appropriate means, winding the obtained pipe around a reel, and rewinding. Here, corrosion resistance refers to carbon dioxide gas corrosion resistance and sulfide stress corrosion cracking resistance, and repeated fatigue refers to fatigue added to a pipe when it is subjected to plastic deformation by bending and unbending. Is.
【００３１】３サイクル以上の繰り返し疲労を加えるこ
とにより安定した耐硫化物応力腐食割れ性能が得られる
原因としては、未だ明らかではない。しかし、繰り返し
疲労回数が少ない場合は、転位が材料に蓄積されて、そ
の蓄積された転位が水素のトラップサイトとなり、耐硫
化物応力腐食割れ性能が低下するが、繰り返し疲労回数
が３サイクル以上となると、材料に蓄積されていた転位
が、開放され、転位密度が少なくなるため、水素のトラ
ップサイトが少なくなり、疲労を受ける前と同等の耐硫
化物応力腐食割れ性能が得られると考えられる。The reason why stable sulfide stress corrosion corrosion cracking performance is obtained by applying repeated fatigue for 3 cycles or more is not yet clear. However, when the number of repeated fatigues is small, dislocations are accumulated in the material, and the accumulated dislocations become hydrogen trap sites, and the sulfide stress corrosion cracking resistance performance is deteriorated, but the number of repeated fatigues is 3 cycles or more. Then, the dislocations accumulated in the material are released, and the dislocation density is reduced, so that the number of hydrogen trap sites is reduced, and the sulfide stress corrosion cracking resistance equivalent to that before fatigue is considered to be obtained.
【００３２】本発明にかかるマルテンサイト系ステンレ
ス鋼は、すでに述べたように、石油または天然ガスの採
取・生産・輸送用の配管、ケーシング、およびチュービ
ング材料として用いることができるが、炭酸ガスを含有
する他の産業分野、例えば、脱炭酸ガス設備の配管、地
熱発電用の配管および炭酸ガス含有液のタンクを構成す
る材料にも使用できる。As described above, the martensitic stainless steel according to the present invention can be used as a pipe, a casing, and a tubing material for collecting, producing and transporting petroleum or natural gas, but contains carbon dioxide gas. It can also be used in other industrial fields such as, for example, piping for decarbonation equipment, piping for geothermal power generation, and materials constituting tanks for carbon dioxide-containing liquid.
【００３３】本発明において管を製造する方法として、
シームレス製管ばかりでなく、鋼帯をパイプ状に成型し
て、シーム溶接する方法があるが、この溶接管にも本発
明にかかる材料は適用可能である。In the present invention, as a method for producing a pipe,
In addition to seamless pipes, there is a method of forming a steel strip into a pipe shape and performing seam welding, and the material according to the present invention can be applied to this welded pipe.
【００３４】本発明による製管に際しては、まず、圧
延、押出、電気抵抗溶接、レーザ溶接等の通常手段によ
って製管を行ってから、前述のような繰り返し疲労を加
えるのであるが、その具体的態様としては、製管後にリ
ールへの巻き取り、巻き戻しを繰り返えして疲労を付加
する。次に、実施例によって本発明の作用効果をさらに
具体的に説明する。In producing the pipe according to the present invention, first, the pipe is produced by a usual means such as rolling, extrusion, electric resistance welding, laser welding and the like, and the above-mentioned repeated fatigue is applied. As a mode, fatigue is added by repeating winding on a reel and rewinding after pipe making. Next, the working effects of the present invention will be described more specifically by way of examples.
【００３５】[0035]
【実施例】表１、表２に示される成分組成をもった溶湯
を通常の電気炉、並びに脱硫の目的でAr−酸素脱炭炉
(AOD 炉) を使用して溶製した後、直径：500 mmのイン
ゴットを鋳造し、ついでこのインゴットに温度：1200℃
で熱間鍛造を施して直径：191 mmのビレットを成形し、
引き続いてこのビレットよりシームレス製管の１つであ
るマンネスマン製管法により直径：60.3mm×肉厚：4.83
mmの管とした。EXAMPLE A molten metal having the composition shown in Tables 1 and 2 was used for an ordinary electric furnace and an Ar-oxygen decarburizing furnace for the purpose of desulfurization.
After melting using the (AOD furnace), cast an ingot with a diameter of 500 mm, and then heat this ingot at a temperature of 1200 ° C.
By hot forging to form a billet with a diameter of 191 mm,
Subsequently, from this billet, according to the Mannesmann pipe manufacturing method, which is one of the seamless pipes, diameter: 60.3 mm × wall thickness: 4.83
mm tube.
【００３６】そして、各成分の材料について、焼入れ焼
き戻した供試管を作製し、以下に示す試験片に加工し、
引張試験、実体疲労試験、炭酸ガス腐食試験および硫化
物応力腐食割れ性能を評価するために微量硫化水素環境
での低歪速度試験をそれぞれ行った。Then, with respect to each component material, a quench-tempered test tube was prepared and processed into the following test pieces,
Tensile tests, physical fatigue tests, carbon dioxide corrosion tests, and low strain rate tests in a trace amount of hydrogen sulfide environment were performed to evaluate the sulfide stress corrosion cracking performance.
【００３７】(1) 実体疲労試験
直径60.3mm×厚さ4.83mm×長さ2000mmの管を曲げ半径12
20mm(48") 、内圧10.3MPa(1500psi)の条件で、本発明鋼
と比較鋼の疲労特性を比較するためにパイプが破断する
まで疲労を加えた。図１の試験機にパイプをセットし、
パイプを曲げ・曲げ戻しという疲労を加えて、疲労特性
を評価した。(1) Entity fatigue test Diameter 60.3 mm × thickness 4.83 mm × length 2000 mm Pipe bending radius 12
Fatigue was applied until the pipe broke under the conditions of 20 mm (48 ") and an internal pressure of 10.3 MPa (1500 psi) to compare the fatigue properties of the steel of the present invention and the comparative steel. ,
Fatigue characteristics were evaluated by adding fatigue of bending and unbending the pipe.
【００３８】図１は本例における実体疲労試験の要領の
説明図であり、図中、供試管10は、一端がクランプ止め
12され、他端はローラ14によって挟持されている。ロー
ラ14は適宜駆動体16に取り付けられていて、供給管10を
移動自在に支持する。直線部18と曲げ部20とによって拘
束される領域に沿って供試管10の曲げ・曲げ戻しが繰り
返されて疲労が与えられるのである。FIG. 1 is an explanatory view of the procedure of the actual fatigue test in this example, in which the test tube 10 is clamped at one end.
12 and the other end is held by the roller 14. The roller 14 is appropriately attached to the driving body 16 and movably supports the supply pipe 10. The test tube 10 is repeatedly bent and unbent along the region constrained by the straight portion 18 and the bent portion 20 to give fatigue.
【００３９】更に、疲労を受けた部分の耐硫化物応力腐
食割れ性能が低下しなくなる条件を示すために、本発明
鋼について、同じ条件で１、２、３、５、10サイクルの
繰り返し疲労を加えた。Further, in order to show the condition that the sulfide stress corrosion cracking resistance of the fatigued part does not deteriorate, the steel of the present invention was subjected to repeated fatigue of 1, 2, 3, 5, 10 cycles under the same conditions. added.
【００４０】(2) 引張り試験
試験温度：常温
試験片：疲労前の母材から、19mm幅で平行部長さ50.8mm
の弧状試験片を採取
(3) マルテンサイト率
焼き戻し後のパイプの長手方向に垂直の断面を切り出
し、100 倍のミクロを10視野観察して、平均値としてマ
ルテンサイト率を測定した。(2) Tensile test Test temperature: Room temperature Test piece: From base material before fatigue, 19 mm width and 50.8 mm parallel part length
(3) Martensite ratio After tempering, a cross section perpendicular to the longitudinal direction of the pipe was cut out, and a 100 × microscopic view was observed in 10 fields of view to measure the martensite ratio as an average value.
【００４１】(4) 炭酸ガス腐食試験
試験片は、疲労前の母材から22mm巾×３mm厚×76mm長さ
を切り出し、600 番エメリー紙にて研磨後、脱脂、乾燥
したものを用いた。この試験片を３気圧Co2 ガスを飽和
させた５％NaCl水溶液 (液温60℃、流速１m/s)に720h浸
漬した。その後、試験片の腐食減量 (試験前の試験片の
重量から試験後の試験片の重量を引く) 測定と目視によ
り試験片表面の局部腐食の有無を確認した。(4) Carbon Dioxide Corrosion Test As a test piece, a 22 mm width × 3 mm thickness × 76 mm length was cut out from the pre-fatigue base material, polished with No. 600 emery paper, degreased and dried. The test piece was immersed in a 5% NaCl aqueous solution (liquid temperature 60 ° C., flow rate 1 m / s) saturated with Co 2 gas at 3 atm for 720 h. Then, the presence or absence of localized corrosion on the surface of the test piece was confirmed by measuring the corrosion weight loss of the test piece (subtracting the weight of the test piece after the test from the weight of the test piece before the test) and visually.
【００４２】(5) 微量硫化水素環境下での低歪み速度試
験
試験ガス：大気と0.1atmH2S (CO2bal.)[試験環境]
試験溶液：５％NaCl＋0.84g/１CH3COONa＋0.31g/１NaHC
O3、pH＝4.7
試験温度：25℃
歪み速度：４×10-6s -1
試験片：２mm幅×４mm厚×平行部20mm長 (弧状試験片)
。
試験片はパイプ疲労前の母材部または疲労後の母材部か
ら切り出した。これらの試験結果を、表１、表２に示
す。(5) Low strain rate test under trace hydrogen sulfide environment Test gas: Atmosphere and 0.1atmH 2 S (CO 2 bal.) [Test environment] Test solution: 5% NaCl ＋ 0.84g / 1CH 3 COONa ＋ 0.31g / 1NaHC
O 3 , pH = 4.7 Test temperature: 25 ℃ Strain rate: 4 × 10 -6 s -1 Specimen: 2mm width × 4mm thickness × parallel part 20mm length (arc shaped specimen)
. The test piece was cut out from the base material before pipe fatigue or the base material after fatigue. The test results are shown in Tables 1 and 2.
【００４３】なお、炭酸ガス腐食にては、0.5 mm/y以下
の腐食速度を示し局部腐食を生じなかったものを "○"
、0.5 mm/y以上で局部腐食を生じたものを "×" とし
た。In the case of carbon dioxide gas corrosion, those having a corrosion rate of 0.5 mm / y or less and no local corrosion were evaluated as "○".
, 0.5 mm / y or more that caused local corrosion was marked as "x".
【００４４】耐硫化物応力腐食割れ性能は低歪み速度試
験の大気中と試験環境中での塑性伸びの比より評価し、
塑性伸び (試験環境中)/塑性伸び (大気中)95 ％超えの
ものを "◎" 、90〜95％のものを "○" 、90％より小さ
いものを "×" でそれぞれ示した。表１、表２に示した
結果の内、試験No. 1 〜11が本発明鋼である。The sulfide stress corrosion corrosion cracking performance was evaluated from the ratio of plastic elongation in the atmosphere in the low strain rate test and in the test environment,
Plastic elongation (in the test environment) / plastic elongation (in air) 95% or more is indicated by "◎", 90 to 95% is indicated by "○", and less than 90% is indicated by "x". Of the results shown in Tables 1 and 2, Test Nos. 1 to 11 are the steels of the present invention.
【００４５】本発明の範囲の化学成分をもち、かつマル
テンサイト率が95％以上である0.2％耐力が550MPa以上
を有する本発明鋼は、疲労特性、耐炭酸ガス腐食性能、
更に、耐硫化物応力腐食割れ性能にも優れていることが
明らかである。The steel of the present invention having the chemical composition within the range of the present invention and having the martensite ratio of 95% or more and the 0.2% proof stress of 550 MPa or more has fatigue properties, carbon dioxide gas corrosion resistance,
Further, it is clear that the sulfide stress corrosion cracking resistance is also excellent.
【００４６】一方、鋼の成分元素が本発明で規定する条
件からはずれた比較合金 (試験No.12〜16) は、十分な
疲労特性および耐食性を示さない。On the other hand, the comparative alloys (test Nos. 12 to 16) in which the constituent elements of the steel deviate from the conditions specified in the present invention do not show sufficient fatigue characteristics and corrosion resistance.
【００４７】また、図２に示すように成分元素の範囲は
本発明内でも、マルテンサイト率が95％未満 (1)または
(2) 式を満足しない試験No. 17、18は、本発明鋼に比べ
十分な疲労特性および耐食性を示さない。Further, as shown in FIG. 2, the range of the constituent elements is within the scope of the present invention, the martensite ratio is less than 95% (1) or
Test Nos. 17 and 18 that do not satisfy the formula (2) do not show sufficient fatigue properties and corrosion resistance as compared with the steels of the present invention.
【００４８】また、表3 には、本発明鋼である試験No.
4 について、1 、2 、3 、5 、10サイクル、と破断にい
たるまでの繰り返し疲労を加えた後の耐硫化物応力腐食
割れ性能を示した。Further, Table 3 shows the test No. of the steel of the present invention.
For No. 4, sulfide stress corrosion cracking resistance after 1, 2, 3, 5, 5 and 10 cycles and repeated fatigue until fracture was added.
【００４９】図３には、試験No. 1 について、1 、2 、
3 、5 、10サイクルの繰り返し疲労を加えた後の耐硫化
物応力腐食割れ性能を示した。In FIG. 3, for test No. 1, 1, 2,
The sulfide stress corrosion cracking resistance after repeated fatigue cycles of 3, 5, and 10 cycles was shown.
【００５０】本発明の代表的な例である焼き戻し後組織
のマルテンサイト率が95％以上を有する13％Cr鋼 (表
１、表２中の試験No. 4)の耐硫化物応力腐食割れ性能と
疲労回数の関係を示したものである。疲労部の耐硫化物
応力腐食割れ性能が低下しないためには、３サイクル以
上、より好ましくは５サイクル以上の繰り返し疲労を加
える。Sulfide-resistant stress corrosion cracking of 13% Cr steel (test No. 4 in Tables 1 and 2) having a martensite ratio of the structure after tempering of 95% or more, which is a typical example of the present invention. It shows the relationship between performance and the number of fatigues. In order to prevent deterioration of the sulfide stress corrosion cracking performance of the fatigued portion, repeated fatigue of 3 cycles or more, more preferably 5 cycles or more is applied.
【００５１】[0051]
【表１】 [Table 1]
【００５２】[0052]
【表２】 [Table 2]
【００５３】[0053]
【表３】 [Table 3]
【００５４】[0054]
【発明の効果】以上に説明したごとく、本発明によれ
ば、疲労特性および耐食性に優れた550MPa以上の耐力を
有する高耐食マルテンサイト系ステンレス鋼が実現でき
た。As described above, according to the present invention, a highly corrosion resistant martensitic stainless steel having excellent fatigue characteristics and corrosion resistance and a proof stress of 550 MPa or more can be realized.
【図１】本発明における実体疲労試験の要領の説明図で
ある。FIG. 1 is an explanatory view of the procedure of a physical fatigue test in the present invention.
【図２】実施例の結果を示すグラフである。FIG. 2 is a graph showing the results of Examples.
【図３】実施例の結果を示すグラフである。FIG. 3 is a graph showing the results of Examples.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平９−111345（ＪＰ，Ａ) 特開 平６−306551（ＪＰ，Ａ) 特開 平９−262685（ＪＰ，Ａ) 特開 昭61−106747（ＪＰ，Ａ) 特開2001−220652（ＪＰ，Ａ) 特開2001−59143（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 38/00 - 38/60 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-111345 (JP, A) JP-A-6-306551 (JP, A) JP-A-9-262685 (JP, A) JP-A-61- 106747 (JP, A) JP 2001-220652 (JP, A) JP 2001-59143 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C22C 38/00-38/60
Claims (4)
〜3.0 ％、 Ｐ: 0.04％以下、 Ｓ: 0.005 ％以下、 Cr：９〜
15％、 Ni：0.7 〜８％、 Al：0.001 〜0.20％、Ｎ: 0.05
％以下 を含有し、さらに、下記式を満足し、 ME＝Cr＋12Al−40(C+N) −４Ni−２Mn≦9.0 残部が鉄および不可避的不純物よりなる鋼組成を有し、
焼戻し後の組織のマルテンサイト率が95％以上であるこ
とを特徴とする、耐疲労特性と耐食性に優れたコイルド
チュービング用マルテンサイト系ステンレス鋼。1. In mass%, C: 0.001 to 0.04%, Si: 1.0% or less, Mn: 0.1
~ 3.0%, P: 0.04% or less, S: 0.005% or less, Cr: 9 ~
15%, Ni: 0.7-8%, Al: 0.001-0.20%, N: 0.05
% Contained the following, further adding satisfy the following formula, having a steel composition which ME = Cr + 12Al-40 ( C + N) -4Ni-2Mn ≦ 9.0 the balance of iron and unavoidable impurities,
Coiled with excellent fatigue resistance and corrosion resistance, characterized by a martensite ratio of 95% or more in the structure after tempering
Martensitic stainless steel for tubing .
〜0.10％、Zr：0.005 〜0.10％のうちから選ばれた１
種または２種以上をさらに含有し、 Mo+W/2：0.2 〜3.0 ％を満たすようにMoおよびＷのうち
から選ばれた１種または２種を含有し、さらに下記式を
満足し、 ME＝Cr+4(Mo+W/2)+11V+5Nb+12Al+8Ti-40(C+N)-4Ni-2Mn
≦9.0 焼戻し後の組織のマルテンサイト率が95％以上であるこ
とを特徴とする、請求項１記載の耐疲労特性と耐食性に
優れたコイルドチュービング用マルテンサイト系ステン
レス鋼。2. The steel composition, in% by mass, Nb: 0.005 to 0.10%, V: 0.005 to 0.10%, Ti: 0.005
~ 0.10%, Zr: 0.005 ~ 0.10% selected from 1%
1 or 2 selected from Mo and W so as to satisfy Mo + W / 2: 0.2 to 3.0%, and further satisfy the following formula: ME = Cr + 4 (Mo + W / 2) + 11V + 5Nb + 12Al + 8Ti-40 (C + N) -4Ni-2Mn
≦ 9.0 Martensite stainless steel for coiled tubing having excellent fatigue resistance and corrosion resistance according to claim 1 , characterized in that the structure has a martensite ratio of 95% or more after tempering.
〜0.05％、およびCe： 0.001 〜0.05％のうちから選ば
れた１種または２種以上をさらに含有し、 さらに、さらに下記式を満足し、 ME＝Cr+4(Mo+W/2)+11V+5Nb+12Al+8Ti-40(C+N)-4Ni-2Mn
≦9.0 焼戻し後の組織のマルテンサイト率が95％以上であるこ
とを特徴とする請求項１または２記載の耐疲労特性と耐
食性に優れたコイルドチュービング用マルテンサイト系
ステンレス鋼。3. The steel composition, in mass%, Ca: 0.001 to 0.05%, Mg: 0.001 to 0.05%, La: 0.001
To 0.05% and Ce: 0.001 to 0.05%, and further contains one or more selected, and further satisfies the following formula, ME = Cr + 4 (Mo + W / 2) + 11V + 5Nb + 12Al + 8Ti-40 (C + N) -4Ni-2Mn
≦ 9.0 Martensite stainless steel for coiled tubing having excellent fatigue resistance and corrosion resistance according to claim 1 or 2, wherein the martensite ratio of the structure after tempering is 95% or more.
ンサイト系ステンレス鋼から製造した鋼管に繰り返し疲
労を３サイクル以上加える耐疲労特性と耐食性に優れた
コイルドチュービング用マルテンサイト系ステンレス鋼
管の製造方法。4. A steel pipe manufactured from the martensitic stainless steel according to claim 1 is excellent in fatigue resistance and corrosion resistance in which repeated fatigue is applied for 3 cycles or more.
A method for producing a martensitic stainless steel pipe for coiled tubing .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000026615A JP3506088B2 (en) | 2000-02-03 | 2000-02-03 | Martensitic stainless steel with excellent fatigue resistance for coiled tubing and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000026615A JP3506088B2 (en) | 2000-02-03 | 2000-02-03 | Martensitic stainless steel with excellent fatigue resistance for coiled tubing and its production method |
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| JP2001220653A JP2001220653A (en) | 2001-08-14 |
| JP3506088B2 true JP3506088B2 (en) | 2004-03-15 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1661655B1 (en) * | 2003-09-05 | 2011-12-28 | Sumitomo Metal Industries, Ltd. | Welded structure excellent in resistance to stress corrosion cracking |
| CA2661655C (en) | 2006-08-31 | 2014-05-27 | Sumitomo Metal Industries, Ltd. | Martensitic stainless steel for welded structures |
| US9163296B2 (en) | 2011-01-25 | 2015-10-20 | Tenaris Coiled Tubes, Llc | Coiled tube with varying mechanical properties for superior performance and methods to produce the same by a continuous heat treatment |
| US9803256B2 (en) | 2013-03-14 | 2017-10-31 | Tenaris Coiled Tubes, Llc | High performance material for coiled tubing applications and the method of producing the same |
| KR102197204B1 (en) | 2013-06-25 | 2021-01-04 | 테나리스 커넥션즈 비.브이. | High-chromium heat-resistant steel |
| CN104451427B (en) * | 2014-12-11 | 2016-08-24 | 宝鸡石油钢管有限责任公司 | A kind of welding defect coiled tubing and manufacture method |
| US11124852B2 (en) | 2016-08-12 | 2021-09-21 | Tenaris Coiled Tubes, Llc | Method and system for manufacturing coiled tubing |
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| JP2001220653A (en) | 2001-08-14 |
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