CN1836056A - High strength stainless steel pipe excellent in corrosion resistance for use in oil well and method for production thereof - Google Patents

High strength stainless steel pipe excellent in corrosion resistance for use in oil well and method for production thereof Download PDF

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CN1836056A
CN1836056A CN 200480023557 CN200480023557A CN1836056A CN 1836056 A CN1836056 A CN 1836056A CN 200480023557 CN200480023557 CN 200480023557 CN 200480023557 A CN200480023557 A CN 200480023557A CN 1836056 A CN1836056 A CN 1836056A
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stainless steel
steel pipe
strength stainless
high strength
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CN100451153C (en
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木村光男
玉利孝德
山崎义男
望月亮辅
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杰富意钢铁株式会社
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Priority to JP016076/2004 priority
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Priority to JP135974/2004 priority
Priority to JP210904/2004 priority
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Abstract

提出一种耐腐蚀性优良的高强度油井用不锈钢管,具有YS超过654MPa的高强度,并且,即使在含有CO It provides a excellent corrosion resistance of high strength steel for oil well pipe having high strength YS of more than 654MPa, and even if containing CO

Description

耐腐蚀性优良的油井用高强度不锈钢管及其制造方法 Excellent corrosion resistance with high strength stainless steel of the oil well pipe and method for manufacturing

技术领域 FIELD

本发明涉及一种原油或天然气的油井、气井所使用的油井用钢管。 The present invention relates to a crude oil or natural gas wells, gas wells used with steel. 特别涉及一种适合含有二氧化碳气体(CO2)、氯离子(Cl-)等非常严重腐蚀环境的油井、气井用的、具有优良的耐腐蚀性的油井用高强度不锈钢管。 Particularly to a carbon dioxide gas for (CO2), a very severe corrosive environment well chloride ions (of Cl-) and the like, with the wells having excellent corrosion resistance of high strength stainless steel for oil well pipes. 另外,在本发明中所谓的“高强度不锈钢管”,是指具有屈服强度在654MPa(95ksi)以上强度的不锈钢管。 Further, in the present invention, the term "high-strength stainless steel pipe" refers to a stainless steel having a yield strength of 654MPa (95ksi) or more tube strength.

背景技术 Background technique

近年来,为了应对原油价格的上涨和在不远的将来所预想的石油资源的枯竭,对于以往从未打算开采的深层油田和曾放弃开发的腐蚀性较强的含硫化氢天然气田等的开发,在世界范围内盛行。 In recent years, in response to rising crude oil prices and depletion in the near future envisioned oil resources, the past never intended for the exploitation of deep oil and had to abandon the development of highly corrosive hydrogen sulfide gas fields such as the development , popular in the world. 这样的油田气田一般是非常深,并且其气氛也是高温状态,而且含有CO2、Cl-等的严重的腐蚀环境。 This oil field is generally very deep, and its atmosphere is a high temperature, and contains CO2, Cl- and other severe corrosive environments. 因而,这样的油田、气田开采所使用的油井用钢管,要求其钢管具有较高的强度且具有优良的耐腐蚀性。 Thus, this oil, gas extraction wells used steel tube, which requires a high strength steel and having excellent corrosion resistance.

以往,在含有CO2、Cl-等环境下的油田、气田,作为油井用钢管,一般使用耐CO2腐蚀性优良的13%Cr马氏体类不锈钢管。 Conventionally, containing CO2, and the like of Cl- oil, gas at ambient, as OCTG, the general use of excellent corrosion resistance to CO2 13% Cr martensitic stainless steel pipe. 可是,通常的马氏体类不锈钢在大量含有Cl-且超过100℃的高温环境下,有不耐用的问题。 However, conventional martensitic stainless steel in a large amount and Cl- than 100 ℃ high temperature environment, there is no problem of durability. 因此,在要求耐腐蚀的井中使用二相不锈钢管。 Thus, two-phase stainless steel pipe in the well requires corrosion resistance. 可是,二相不锈钢管合金元素量较多,热加工性较差,只能用特殊的热加工方法制造,存在其成本价格高的问题。 However, two-phase stainless steel pipe large amounts of alloying elements, hot workability is poor, can only be manufactured with a special thermal processing method, there is a problem of high cost price. 并且,以往的13%Cr马氏体类不锈钢管,当其屈服强度超过654MPa时,钢管的韧性明显降低,也有不耐用的问题。 Further, the conventional 13% Cr martensitic stainless steel pipe, when it exceeds the yield strength of 654MPa, the toughness of steel decreases significantly, there are problems not durable.

另外,近年来,在寒冷地区的油田开发也活跃起来,多数要求其钢管具有高强度和优良的低温韧性。 In recent years, the development of oil fields in cold regions are also active, most of the steel required to have high strength and excellent low-temperature toughness.

从上述情况,更希望有如下的油井用高强度13Cr马氏体类不锈钢管,其以热加工性优良、廉价的13%Cr马氏体类不锈钢作为基底,具有屈服强度超过654MPa(95ksi)的高强度,并且具有优良的耐CO2腐蚀性和高韧性。 From the above, the following wells more desirable high strength 13Cr martensitic stainless steel pipe, which is excellent in hot workability, low-cost 13% Cr martensitic stainless steel as a base, having a yield strength of more than 654MPa (95ksi) of high strength, and excellent CO2 corrosion resistance and high toughness.

对于这样的要求,例如在专利文献1、专利文献2、专利文献3、专利文献4、专利文献5中提出了改善13%Cr马氏体类不锈钢或钢管的耐腐蚀性的改良型马氏体类不锈钢或钢管。 For such requirements, for example, in Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5 proposes an improved 13% Cr martensitic stainless steel pipe or improved martensitic corrosion resistance stainless steel or steel.

专利文献1记载的技术是一种具有优良的耐腐蚀性的马氏体类不锈钢无缝钢管的制造方法。 Technique described in Patent Document 1 is an excellent corrosion resistance of the martensitic stainless steel seamless steel pipe production method. 对将C限制在0.005%以上、0.05%以下,复合添加Ni:2.4%以上、6%以下,Cu:0.2%以上、4%以下,再添加Mo:0.5%以上、3%以下,进一步将Nieq调整为10.5以上的组成的13%Cr马氏体类不锈钢管原材料,在热加工后用空冷以上的速度进行冷却之后,或者进而加热至(Ac3相变点+10℃)以上、(Ac3相变点+200℃)以下的温度,或者再加热到Ac1相变点以上、Ac3相变点以下的温度,接着以空冷以上的冷却速度冷却到室温,进行回火。 Of C is limited to 0.005%, 0.05%, composite addition of Ni: more than 2.4%, 6% or less, Cu: 0.2% or more, 4% or less, further adding Mo: 0.5% or more and 3% or less, further Nieq adjusting the composition of 13% Cr martensitic stainless steel pipe of 10.5 or more raw materials, followed by air cooling or more cooling rate after hot working or further heated (the Ac3 transformation point + 10 ℃) above, (the Ac3 phase transformation point temperature + 200 ℃) or less, or reheated to Ac1 transformation point or higher, the temperature of the Ac3 transformation point or lower, followed by a cooling rate of air cooling or more cooled to room temperature, tempering. 根据专利文献1中所记载的技术,可以制造兼具API-C95级以上的高强度、在180℃以上的含有CO2的环境下的耐腐蚀性和耐SCC性的马氏体类不锈钢无缝钢管。 According to the technique described in Patent Document 1 can be produced both API-C95 and above a high strength, corrosion resistance in an environment containing at least 180 [deg.] C CO2 and SCC resistance of martensitic stainless steel seamless pipe .

专利文献2记载的技术是一种具有耐硫化物应力腐蚀裂纹性优良的马氏体类不锈钢无缝钢管的制造方法。 Technology described in Patent Document 2 is a method of manufacturing having resistance to sulfide stress cracking resistance of the martensitic stainless steel seamless steel pipe excellent in corrosion. 对含有C:0.005%以上、0.05%以下,N:0.005%以上、0.1%以下,调整为Ni:3.0%以上、6.0%以下,Cu:0.5%以上、3%以下,Mo:0.5%以上、3%以下的组成的13%Cr马氏体类不锈钢进行热加工,自然放置冷却到室温之后,加热到(Ac1点+10℃)以上、(Ac1点+40℃)以下的温度,保持30分钟至60分钟,冷却到Ms点以下温度,在Ac1点以下的温度下进行回火,对组织进行回火,形成马氏体和20体积%以上的γ相混合存在的组织。 Containing C: 0.005%, 0.05%, N: 0.005% or more, 0.1% or less, adjusting the Ni: 3.0% or more, 6.0% or less, Cu: 0.5% to 3%, Mo: not more than 0.5%, 3% or less of the 13% Cr martensitic stainless steel hot working temperature after cooling to room temperature, heated at (the Ac1 point + 10 ℃) above, (the Ac1 point + 40 ℃) below the natural place for 30 minutes to 60 minutes, cooled to a temperature below Ms point, tempering at a temperature below the Ac1 point, tempering the tissue, forming martensite and 20 vol% of the γ phase are mixed. 根据专利文献2记载的技术,通过形成含有20体积%以上的γ相的回火马氏体组织,耐硫化物应力腐蚀裂纹性得到明显改善。 According to the technique disclosed in Patent Document 2, is formed by a tempered martensitic structure containing 20 vol% γ phase, resistance to sulfide stress corrosion cracking resistance are improved.

在专利文献3中所记载的技术是耐腐蚀性、耐硫化物应力腐蚀裂纹性优良的马氏体类不锈钢。 In the technique described in Patent Document 3 is a corrosion resistance to sulfide stress corrosion cracking resistance of the martensitic stainless steel excellent. 其组成是含有10%以上、15%以下Cr的马氏体类不锈钢的组成,限制C在0.005%以上、0.05%以下,复合添加Ni:4.0%以上,Cu:0.5%以上、3%以下,再添加Mo 1.0%以上、3.0%以下,进一步调整Nieq至-10以上,其组织由回火马氏体相、马氏体相、残余奥氏体相构成,其中回火马氏体相、马氏体相的总百分比为60%以上、90%以下。 Wherein the composition is 10% or more, 15% or less of Cr martensitic stainless steel composition to limit 0.005% or more C, 0.05% or less, the composite add Ni: more than 4.0%, Cu: 0.5% or more, 3% or less, add more Mo 1.0%, 3.0% or less, and further adjusted to -10 Nieq above, its organization phase, martensite, residual austenite phase is composed of tempered martensite, tempered martensite phase wherein, horses the total percentage of martensitic phase is 60% or more, 90% or less. 由此,使在湿润的二氧化碳环境下和湿润的硫化氢环境下的耐腐蚀性和耐硫化物应力腐蚀裂纹性提高。 Thereby, in a wet carbon dioxide environment and corrosion resistance in a wet hydrogen sulfide environment and the sulfide stress corrosion cracking resistance is improved.

在专利文献4中所记载的技术是具有优良的硫化物应力裂纹性的油井用马氏体类不锈钢材料,该钢材料组成为:含有Cr:超过15%、19%以下,C:0.05%以下,N:0.1%以下,Ni:3.5%以上、8.0%以下,进而含有Mo:0.1%以上、4.0%以下,同时满足30Cr+36Mo+14Si-28Ni≤455(%)、21Cr+25Mo+17Si+35Ni≤731(%)。 In the technique described in Patent Document 4 is excellent in sulfide stress cracking resistance of the martensitic stainless steel material for oil well, the steel consisting of: containing Cr: more than 15%, 19% or less, C: 0.05% or less , N: 0.1% or less, Ni: 3.5% or more, 8.0% or less, and further containing Mo: 0.1% or more, 4.0% or less, while meeting 30Cr + 36Mo + 14Si-28Ni≤455 (%), 21Cr + 25Mo + 17Si + 35Ni≤731 (%). 由此得到即使在氯化物离子、二氧化碳、和微量的硫化氢气体存在的严酷的油井环境中,也具有优良的耐腐蚀性的钢材。 Even in the thus obtained chloride ions, carbon dioxide, and traces of hydrogen sulfide gas in the presence of severe oil well environment, have excellent corrosion resistance of the steel.

在专利文献5中所记载的技术是一种具有优良的强度和韧性的析出固化型马氏体类不锈钢。 In the technique described in Patent Document 5 is an excellent strength and toughness of the precipitation hardening type martensitic stainless steel. 其钢组成含有Cr为10.0%以上、17%以下,并含有C:0.08%以下,N:0.015%以下,Ni:6.0%以上、10.0%以下,Cu:0.5%以上、2.0%以下,而且含有Mo:0.5%以上、3.0%以下,其通过35%以上的冷加工和退火,得到具有平均结晶粒径在25μm以下,析出于基体上的粒径5×10-2μm以上的析出物抑制在6×106个/mm2以下的组织。 Which steel composition containing Cr of 10.0% or more, 17% or less, and contains C: 0.08% or less, N: 0.015% or less, Ni: 6.0% or more, 10.0% or less, Cu: 0.5% or more, 2.0% or less, and comprising Mo: 0.5% or more, 3.0% or less, 35% or more by cold working and annealing, to obtain precipitates having an average grain size of 25μm or less, deposited on the base particle diameter is more than 5 × 10-2μm suppressed to 6 × 106 mm2 or less tissue /. 根据专利文献5所记载的技术,通过形成微细的结晶粒和析出物少的组织,可以提供高强度的不会引起韧性降低的析出固化型马氏体类不锈钢。 According to the technique described in Patent Document 5, with a small crystal grains and fine precipitates tissue formation, high strength can be provided without causing precipitation hardening type martensitic stainless steel reduction in toughness.

专利文献1:特开平8-120345号公报专利文献2:特开平9-268349号公报专利文献3:特开平10-1755号公报专利文献4:特许第2814528号公报专利文献5:特许第3251684号公报发明内容然而,用专利文献1、专利文献2、专利文献3、专利文献4、专利文献5中所记载的技术制造的改良型13%马氏体类不锈钢管,在含有CO2、Cl-等,超过180℃高温的严酷的腐蚀环境下,存在不能稳定地显示期望的耐腐蚀性的问题。 Patent Document 1: JP 8-120345 A Patent Document 2: Laid-Open No. 9-268349 Patent Document 3: Japanese Patent Publication No. 10-1755 Patent Document 4: JP Patent No. 2814528 Patent Document 5: Patent No. 3251684 SUMMARY oF tHE iNVENTION However, with Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, 13% martensitic improved manufacturing technique described in Patent Document 5, a stainless steel tube, containing CO2, Cl-, etc. , at a high temperature exceed 180 ℃ severe corrosive environment, corrosion resistance can not be stably present problems desired display.

本发明是基于目前的技术情况完成的。 The present invention is based on the current technology situation completed. 本发明的目的在于提供一种具有优良的耐腐蚀性的油井用高强度不锈钢管及其制造方法。 Object of the present invention is to provide an excellent corrosion resistance of high-strength stainless steel pipe oil well and a manufacturing method. 该钢管廉价、具有优良的热加工性,具有屈服强度超过654MPa的高强度,并且,即使在含有CO2、Cl-等230℃高温的严酷腐蚀环境下,也能显示出优良的耐CO2腐蚀性。 In this steel inexpensive, excellent in hot workability, having a yield strength of more than 654MPa high strength, and even if containing CO2, 230 ℃ temperature of Cl- and other severe corrosive environment, but also show excellent CO2 corrosion resistance.

本发明者为完成上述课题,对涉及热加工性、耐腐蚀性的各种因素进行了专心研究。 The present inventors to accomplish the above object, a variety of factors involved in hot workability, corrosion resistance intensively studied.

在目前的制造马氏体类不锈钢无缝钢管的方面,在生成铁素体相,其组织不为马氏体单相的情况下,由于其强度降低,热加工性降低,一般认为在钢管的制造上有困难。 In the current manufacturing martensitic stainless steel seamless pipe, and in the case where the ferrite phase, the organization is not a single phase of martensite, the strength due to the reduction, decrease hot workability, the steel pipe is generally considered there are difficulties in manufacturing. 所以,如在特开平8-246107号公报中所记载的,一般情况下,可以调整为抑制铁素体的生成以使组织为马氏体单相的组成,来制造油井用13%Cr类马氏体类不锈钢无缝钢管。 Therefore, as in JP 8-246107 as described, under normal circumstances, the composition may be adjusted to generate a martensite single phase of ferrite is suppressed to the tissue, producing a 13% Cr-based oil horse martensitic stainless steel seamless pipe.

因此,本发明者对涉及热加工性的成分的影响,进一步进行了详细的研究。 Therefore, the influence on the composition of the present inventors relates to the hot workability, and further detailed studies. 其结果发现:通过调整钢管组成使其满足下列式(2),热加工性明显得到改善,可以防止热加工时发生裂纹。 As a result, it found: by adjusting the steel composition so as to satisfy, hot workability is significantly gave the following formula (2) improvement can prevent the occurrence of cracks during hot working.

Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ………(2)(其中,Cr、Ni、Mo、Cu、C、Si、Mn、N为各元素的含量(质量%))(2)式左边的值和热加工时(即,制造无缝钢管时)在13%Cr类不锈钢无缝钢管的端面发生的裂纹长度的关系如图1所示。 Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ......... (2) (wherein, Cr, Ni, Mo, Cu, C, Si, Mn, N is the contents of the elements relationship between crack length (mass%)) (2) and the left-hand side value of thermal processing (i.e., the production of seamless steel tubes) in the 13% Cr stainless steel seamless pipe of the end surface occurs as shown in FIG. 从图1可以看出,(2)式左边的值在8.0以下时,或者(2)式左边的值在11.5以上、优选12.0以上时,可以防止发生裂纹。 As it can be seen from Figure 1, at 8.0 or less, or a value (2) the value of the left side of the formula (2) left-hand side in the above 11.5, preferably 12.0 or more time, the occurrence of cracks can be prevented. (2)式左边的值在8.0以下时,相当于完全不产生铁素体的区域,此区域是不生成铁素体相的以往认为提高热加工性的区域。 Value (2) at the left side of Formula 8.0 or less, equivalent to totally ferrite generation region, this region is a region to improve the workability of the heat that the conventional ferrite phase is not generated. 另一方面,随着(2)式左边的值变大,生成的铁素体的量增加,可是(2)式左边的值在11.5以上的区域是较多生成铁素体的区域。 On the other hand, as the value of (2) left-hand side increases, the amount of generation of ferrite increases, but the value of (2) in the left-hand side is more than 11.5 area generation region ferrite. 即,本发明者初次发现,调整组成以使(2)式左边值为11.5以上,形成制管时铁素体较多生成的组织,通过采用这种与以往完全不同的观点,可以使热加工性得到明显改善。 That is, the present inventors have found for the first time, to allow adjustment of the composition (2) value of 11.5 or more left-hand side, forming a tissue pipe more ferrite generated by the use of such a completely different point of view, the hot workability can of significant improvement.

热加工时,在13%Cr类不锈钢无缝钢管的端面发生的裂纹的长度,用其与铁素体量的关系进行整理,表示在图2中。 Thermal processing, the length of cracks occurring end faces 13% Cr stainless steel seamless pipe, and finishing with the relationship of the amount of ferrite, is shown in FIG. 从图2看出,按照以往的观点,铁素体的量以体积百分比计为0%时不发生裂纹,而在生成铁素体的同时发生裂纹。 Seen from Figure 2, according to the conventional view, an amount of ferrite volume percentage of 0% no cracking occurs, and the formation of ferrite in the occurrence of cracks simultaneously. 可是,进一步增加生成铁素体的量,使其体积率在10%以上,优选生成15%以上的铁素体相时,与目前的观点不同,可以防止发生裂纹。 However, further increase the amount of ferrite, so that a volume fraction of 10% or more, preferably 15% or more to generate a ferrite phase, the current opinion, the occurrence of cracks can be prevented. 即,调整其成分以满足式(2),使其生成适当范围的铁素体相,形成铁素体—马氏体的二相组织,由此其热加工性提高,可以防止发生裂纹。 That is, its composition adjusted to satisfy the formula (2), so as to generate an appropriate range of a ferrite phase, the ferrite formation - two-phase structure of martensite, thereby improving hot workability which can prevent the occurrence of cracks. 并且,通过形成铁素体—马氏体的二相组织,也可以确保油井管所需要的强度。 Further, by forming the ferrite - martensite two-phase structure, the strength can be secured OCTG need.

可是,调整其成分满足式(2),当其组织成为铁素体—马氏体的二相组织时,担心由于在热处理中产生的元素分配使其耐腐蚀性劣化。 However, adjusting its composition satisfies the following formula (2), when it is organized as a ferrite - when the two-phase structure of martensite, since fear of element distribution in the heat treatment so as to generate deterioration in corrosion resistance. 当成为二相组织时,C、Ni、Cu等的奥氏体生成元素扩散于马氏体相中,Cr、Mo等的铁素体生成元素扩散于铁素体相中,热处理后的最终产品中,作为结果,在各相之间发生成分的偏差。 When the two-phase structure becomes austenite C, Ni, Cu, etc. in the martensite phase diffusion forming element, Cr, Mo and the like ferrite forming elements diffused in the ferrite phase, the final product after heat treatment , as a result, the deviation component takes place between the phases. 马氏体相中对耐腐蚀性有效的Cr量降低,使耐腐蚀性劣化的C量增加,与均匀的组织相比,恐怕其耐腐蚀性降低。 Corrosion resistance of the martensitic phase to reduce the effective amount of Cr, so that the amount of C deteriorates corrosion resistance increases, as compared with a uniform structure, probably reducing the corrosion resistance.

所以,本发明者,对涉及耐腐蚀性的成分的影响进行了专心研究。 Therefore, the present inventors, relates to influence the composition of the corrosion resistance intensively studied. 其结果发现:通过调整其成分以满足下列式(1),即使其组织成为铁素体—马氏体的二相组织,也可以确保其充分的耐腐蚀性。 As a result, it found: by adjusting its composition to satisfy the following formula (1), even if it is organized as a ferrite - martensite two-phase structure, which may ensure sufficient corrosion resistance.

Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)(其中,Cr、Ni、Mo、Cu、C为各元素的含量(质量%))式(1)左边的值和含有CO2和Cl-的230℃的高温环境下的腐蚀速度的关系如图3所示。 Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C≥19.5 ... (1) (wherein, Cr, Ni, Mo, Cu, C is the content of each element (mass%)) of the value of the left side of formula (1) containing CO2 corrosion rate and high temperature environment of 230 deg.] C Cl- a relationship as shown in FIG. 从图3可以看出,通过调整其成分满足式(1),即使使组织为铁素体—马氏体的二相组织,在含有CO2和Cl-的230℃的高温环境下,也可以确保其充分的耐腐蚀性。 As can be seen from Figure 3, by adjusting its composition satisfies the formula (1), even if the tissue is a ferrite - martensite two-phase structure, in a high temperature environment of 230 deg.] C containing CO2 and Cl-, and can be secured sufficient corrosion resistance thereof.

如从式(1)可知,为提高耐腐蚀性,增加Cr的含量是有效的。 As seen from the formula (1) can be seen, in order to improve the corrosion resistance, increasing the content of Cr is effective. 可是,Cr促进铁素体的生成。 However, Cr promote the formation of ferrite. 因此,为达到抑制生成铁素体的目的,以往需要使其含有与Cr含量相适合的Ni元素的量。 Thus, for the purpose of inhibiting the formation of ferrite, and containing a conventional amount is necessary that the Cr content of the Ni element suitable phase. 可是,当适应Cr元素的量使Ni元素的量增加时,奥氏体相就稳定化,存在不能确保油井管所需要的强度的问题。 However, when the amount of Cr element is adapted so that the amount of Ni element is increased, the austenite phase to stabilize the oil well pipes can not be ensured strength required for problem.

对于这种问题,本发明者发现,通过在维持含有适当量的铁素体相的铁素体—马氏体的二相组织的状态下增加Cr含量,可以较低抑制奥氏体相的残留量,可以确保作为油井管的充分的强度。 For this problem, the present inventors have found that by maintaining the appropriate amount of ferrite phase containing ferrite - Cr content increases, the martensite two-phase state, suppress the residual austenite may be lower phase amount, sufficient strength can be ensured as oil country tubular goods.

本发明者将所得到的具有铁素体—马氏体二相组织的13%Cr类不锈钢无缝钢管的热处理后的屈服强度YS和Cr含量的关系表示于图4。 The present inventors have obtained a ferrite - Relationship between the Cr content and the yield strength YS after heat treatment martensite dual-phase structure type 13% Cr stainless seamless steel tube 4 is shown in FIG. 并且,在图4中,也同时记录了组织为马氏体单相或马氏体—奥氏体二相组织时热处理后的YS和Cr含量的关系。 Further, in FIG. 4, also recorded the single phase of martensite or martensite - Cr content relationship between YS and after the heat treatment austenite two-phase structure. 由图3最新发现,通过使组织维持为包含适当量的铁素体相的铁素体—马氏体二相组织,增加Cr的含量,可以确保油井管充分的强度。 FIG 3 newly found, the tissue is maintained by a ferrite phase containing an appropriate amount of ferrite - martensite two-phase structure, the content of Cr is increased, sufficient strength can be ensured OCTG. 另一方面,使组织为马氏体单相或马氏体—奥氏体二相组织时,当增加Cr含量时,YS降低。 On the other hand, so that a single phase of martensite or martensite - austenite two-phase structure, when the Cr content is increased, decreased YS.

本发明是基于上述见解并进行了专心研究而完成的。 The present invention is based on these findings and completed the extensive studies. 即,本发明的要点如下:(1)一种耐腐蚀性优良的油井用高强度不锈钢管,其特征在于,其组成以质量%计含有:C:0.005%以上、0.05%以下、Si:0.05%以上、0.5%以下、Mn:0.2%以上、1.8%以下、P:0.03以下、S:0.005%以下、Cr:15.5%以上、18%以下、Ni:1.5%以上、5%以下、Mo:1%以上、3.5%以下、V:0.02%以上、0.2%以下、N:0.01%以上、0.15%以下、O:0.006%以下,且满足下列式(1)和式(2),余量由Fe和不可避免的杂质构成,Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)其中,Cr、Ni、Mo、Cu、C、Si、Mn、N为各元素的含量(质量%)。 That is, the gist of the present invention is as follows: (1) one kind excellent in corrosion resistance, high strength oil well steel pipe, characterized in that a composition containing, by mass%: C: 0.005%, 0.05% or less, Si: 0.05 % or more and 0.5% or less, Mn: 0.2%, 1.8% or less, P: 0.03 or less, S: 0.005% or less, Cr: more than 15.5%, 18% or less, Ni: 1.5% or 5% less, Mo: more than 1%, 3.5%, V: not more than 0.02%, 0.2% or less, N: 0.01%, 0.15% or less, O: 0.006% or less, and satisfies the following formula (1) and (2), the balance consisting of Fe and inevitable impurities, Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C≥19.5 ... (1) Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ... (2 ) where, Cr, Ni, Mo, Cu, C, Si, Mn, N is the content of each element (mass%).

(2)如(1)所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外以质量%计还含有Al:0.002%以上、0.05%以下的组成。 (2) (1) The high-strength stainless steel oil well pipe, characterized by having a composition outside of the mass%, further containing Al:, 0.05% or less than 0.002% composition.

(3)如(1)或(2)所述的油井用高强度不锈钢管,其特征在于,以质量%计,所述C的含量在0.03%以上、0.05%以下。 (3) (1) or (2) the high strength stainless steel for oil well pipes, characterized in that, in mass%, the C content is above 0.03%, 0.05% or less.

(4)如(1)~(3)中任一项所述的油井用高强度不锈钢管,其特征在于,所述Cr的含量在16.6%以上、不足18%。 (4) (1) to (3) according to any one of the high strength stainless steel for oil well pipes, characterized in that the Cr content is more than 16.6%, less than 18%.

(5)如(1)~(4)中任一项所述的油井用高强度不锈钢管,其特征在于,以质量%计,所述Mo的含量在2%以上、3.5%以下。 (5) (1) to (4) according to any one of the high strength stainless steel for oil well pipes, characterized in that, in mass%, the content of Mo is over 2%, 3.5% or less.

(6)如(1)~(5)中任一项所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外以质量%计还含有Cu:3.5%以下的组成。 (6) (1) to (5) according to any one of the high strength stainless steel for oil well pipe, comprising said composition having outside mass%, further containing Cu: 3.5% or less of the composition.

(7)如(6)所述的油井用高强度不锈钢管,其特征在于,以质量%计,所述Cu的含量在0.5%以上、1.14%以下。 (7) (6) of the high strength stainless steel for oil well pipes, characterized in that, in mass%, the content of Cu is 0.5% or more, 1.14% or less.

(8)如(1)~(7)中任一项所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外,以质量%计还含有选自Nb:0.2%以下,Ti:0.3%以下,Zr:0.2%以下,W:3%以下,B:0.01%以下中的1种或2种以上的组成。 (8) (1) to (7) according to any one of the well with a high strength stainless steel tube, wherein, said outside having a composition, in mass%, further contains selected from Nb: 0.2% or less , Ti: 0.3% or less, Zr: 0.2% or less, W: 3% or less, B: 0.01% or less of one or two or more compositions.

(9)如(1)~(8)中任一项所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外以质量%计还含有Ca:0.01%以下的组成。 (9) (1) to (8) according to any one of the high strength stainless steel for oil well pipe, characterized by having a composition outside said further contains by mass%, Ca: 0.01% or less of the composition.

(10)如(1)~(9)中任一项所述的油井用高强度不锈钢管,其特征在于,具有以马氏体相作为基相,还含有体积率为10%以上、60%以下的铁素体相的组织。 (10) (1) to (9) according to any one of the high strength stainless steel for oil well pipe, comprising a martensite phase having a matrix phase further contains at least 10% by volume, 60% the following organization ferrite phase.

(11)如(10)所述的油井用高强度不锈钢管,其特征在于,所述铁素体相的体积率为15%以上、50%以下。 (11) (10) of the high strength stainless steel for oil well pipes, characterized in that the ferrite phase volume fraction of 15% or more, 50% or less.

(12)如(10)或(11)所述的油井用高强度不锈钢管,其特征在于,所述组织还含有体积率为30%以下的奥氏体相。 (12) to (10) or (11) the high strength stainless steel for oil well pipes, wherein said tissue further comprises 30% or less by volume of austenite phase.

(13)一种耐腐蚀性优良的油井用高强度不锈钢管的制造方法,其特征在于,将具有以质量%计含有C:0.005%以上、0.05%以下,Si:0.05%以上、0.5%以下,Mn:0.2%以上、1.8%以下,P:0.03以下,S:0.005%以下,Cr:15.5%以上、18%以下,Ni:1.5%以上、5%以下,Mo:1%以上、3.5%以下,V:0.02%以上、0.2%以下,N:0.01%以上、0.15%以下,O:0.006%以下,且满足下列式(1)和式(2),余量由Fe和不可避免的杂质构成的组成的钢管原材料,制成规定尺寸的钢管,对该钢管再加热到850℃以上的温度后,用空冷以上的冷却速度冷却至100℃以下,然后,实施加热到700℃以下的温度的淬火—回火处理,Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)其中,Cr、Ni、Mo、Cu、C、Si、Mn、N为各元素的含量(质量%)。 (13) A high corrosion resistance, oil manufacturing method of a high strength stainless steel pipe, characterized in that, having a mass%, C: 0.005%, 0.05% or less, Si: 0.05%, 0.5% or less , Mn: 0.2%, 1.8% or less, P: 0.03 or less, S: 0.005% or less, Cr: more than 15.5%, 18% or less, Ni: 1.5% or more, 5% or less, Mo: 1% or more, 3.5% less, V: 0.02% or more, 0.2% or less, N: 0.01%, 0.15% or less, O: 0.006% or less, and satisfies the following formula (1) and (2), the balance being Fe and unavoidable impurities after the steel material composed of the composition, of predetermined size made of steel, the steel is reheated to a temperature above 850 deg.] C, cooled with a cooling rate of air cooling or more to 100 deg.] C or less, then subjected to heat to a temperature below 700 ℃ quenching - tempering, Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C≥19.5 ... (1) Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ... (2) wherein , Cr, Ni, Mo, Cu, C, Si, Mn, N is the content of each element (mass%).

(14)如(13)所述的油井用高强度不锈钢管的制造方法,其特征在于,对所述钢管原材料进行加热,通过热加工制成管,制成管后,用空冷以上的冷却速度冷却至室温,制成规定尺寸的无缝钢管,然后对该无缝钢管实施所述淬火—回火处理。 (14) (13) of the oil well, characterized in that the method for manufacturing a high strength stainless steel pipe, the steel tube material is heated, the tube is made by hot working, the tube is made, with a cooling rate of air cooling or more cooled to room temperature, made seamless pipe of a predetermined size, then the embodiment of the seamless steel pipe quenching - tempering.

(15)如(13)或(14)所述的油井用高强度不锈钢管的制造方法,其特征在于,代替所述的淬火—回火处理,实施加热至700℃以下的温度的回火处理。 (15) to (13) or (14) of the oil well, characterized in that the method for manufacturing a high strength stainless steel pipe, in place of the quenching - tempering treatment, a heat temperature of 700 deg.] C to a tempering .

(16)如(13)~(15)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外以质量%计还含有Al:0.002%以上、0.05%以下的组成。 (16) (13) to (15) according to any one of the well by the method of manufacturing a high strength stainless steel tube, wherein, said composition having outside mass%, further containing Al: 0.002% 0.05% or less of the composition.

(17)如(13)~(16)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,以质量%计,所述C的含量在0.03%以上、0.05%以下。 (17) (13) to (16) according to any one of the wells, characterized in that the method for manufacturing a high strength stainless steel pipe, by mass%, the C content is above 0.03%, 0.05% or less .

(18)如(13)~(17)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,所述Cr的含量在16.6%以上、不足18%。 (18) (13) to (17) the method for producing a high strength stainless steel for oil well pipe, characterized in that the Cr content is more than 16.6%, less than 18%.

(19)如(13)~(18)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,以质量%计,所述Mo的含量在2%以上、3.5%以下。 Oil (19) (13) to (18) according to any preceding claim, characterized in that the method for manufacturing a high strength stainless steel pipe, by mass%, the content of Mo is over 2%, 3.5% or less .

(20)如(13)~(19)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外以质量%计还含有Cu:3.5%以下的组成。 The wells (13) to (19) according to any one of (20), characterized in that the method for manufacturing a high strength stainless steel pipe, having a mass%, the composition further comprises in addition to Cu: 3.5% or less composition.

(21)如(20)所述的油井用高强度不锈钢管的制造方法,其特征在于,以质量%计,所述Cu的含量在0.5%以上、1.14%以下。 (21) (20) of the oil well, characterized in that the method for manufacturing a high strength stainless steel pipe, by mass%, the content of Cu is 0.5% or more, 1.14% or less.

(22)如(13)~(21)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外,以质量%计还含有选自Nb:0.2%以下,Ti:0.3%以下,Zr:0.2%以下,W:3%以下,B:0.01%以下中的1种或2种以上的组成。 (22) (13) to (21) production method according to any one of the well with a high-strength stainless steel pipe, characterized in that the outside having a composition, in terms of mass%, Nb: 0.2% or less, Ti: 0.3% or less, Zr: 0.2% or less, W: 3% or less, B: 0.01% or less of one or two or more compositions.

(23)如(13)~(22)中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外以质量%计还含有Ca:0.01%以下的组成。 (23) (13) to (22) the production method according to any one of the high strength stainless steel for oil well pipe, characterized by having a composition outside said further contains by mass%, Ca: 0.01% or less composition.

附图说明 BRIEF DESCRIPTION

图1是表示裂纹长度和式(2)左边值关系的图表。 FIG 1 is a diagram (2) of the left graph the relationship between the value of crack length and type.

图2是表示裂纹长度和铁素体量关系的图表。 FIG 2 is a graph of crack length and the relationship between the amount of ferrite.

图3是表示腐蚀速度和式(1)左边值关系的图表。 FIG 3 is a graph showing the relationship between the value of the left and the corrosion rate formula (1).

图4是表示涉及屈服强度YS和Cr含量关系的组织的影响的图表。 FIG 4 is a graph showing the yield strength YS involved in influencing the relationship between the Cr content and organization.

具体实施方式 Detailed ways

首先,对限定本发明中的油井用高强度不锈钢管组成的根据进行说明。 First, according to the present invention defines high strength stainless steel for oil well tubes will be described. 下面,表示组成的质量%只记作%。 The following, represents the mass% composed of only denoted%.

C:0.005%以上、0.05%以下C是关系到马氏体类不锈钢强度的重要元素,本发明中需要使其含有0.005%以上,可是当超过0.05%时,含有Ni导致的回火时的灵敏化增大。 Sensitive 0.005% to 0.05% C is an important element related to the strength of martensitic stainless steel, the present invention is necessary to contain 0.005% or more, but when it exceeds 0.05%, Ni containing lead during tempering: C of the increase. 为达到防止这种回火时灵敏化的目的,在本发明中限定C元素的量在0.005%以上、0.05%以下的范围。 An amount of time to achieve such sensitivity to prevent tempering object, defining element C in the present invention is 0.005%, 0.05% or less. 而且,从耐腐蚀性的观点看,C元素越少越好,而从确保其强度的观点看,C元素越多越好,考虑其平衡优选0.03%以上、0.05%以下。 Further, from the viewpoint of corrosion resistance, C elements as possible, from the viewpoint of ensuring the strength thereof, C elements as possible, considering the balance thereof is preferably 0.03% or more, 0.05% or less.

Si:0.05%以上、0.5%以下Si是起脱氧剂作用的元素,在本发明中使其含有0.05%以上,超过0.5%时使其耐CO2腐蚀性降低,并且热加工性也降低。 Si: 0.05% or more, 0.5% or less Si is an element from the deoxidizer, in the present invention to contain 0.05% or more, it is more than 0.5% of CO2 corrosion resistance decreases, and the hot workability is also lowered. 因此,限定Si在0.05%以上、0.5%以下的范围。 Thus, defining the 0.05%, 0.5% or less Si. 而且,优选0.1%以上、0.3%以下。 Further, preferably 0.1% or more, 0.3% or less.

Mn:0.2%以上、1.8%以下Mn是使其强度增加的元素,在本发明中为确保所要求的强度,需要使其含有0.2%以上,可是当超过1.8%时,使其韧性受到坏的影响。 Mn: 0.2%, 1.8% or less Mn is an element increasing the strength thereof, the present invention in order to ensure desired strength, it is necessary to contain 0.2% or more, but when it exceeds 1.8%, toughness being so bad influences. 所以限定Mn在0.2%以上、1.8%以下的范围。 Therefore defined in 0.2%, 1.8% or less Mn. 而且优选0.2%以上、1.0%以下。 And more preferably 0.2%, 1.0% or less. 更优选0.2%以上、0.8%以下。 More preferably 0.2%, 0.8% or less.

P:0.03%以下P是使耐CO2腐蚀性、耐CO2应力腐蚀裂纹性、耐点腐蚀性和耐硫化物应力腐蚀裂纹性共同劣化的元素。 P: 0.03% or less P is an CO2 corrosion resistance, resistance to CO2 stress corrosion cracking, pitting corrosion resistance and sulfide stress corrosion cracking resistance deteriorates common elements. 在本发明中希望其尽可能降低,而极端降低会导致制造成本上升。 Which is desirable in the present invention to minimize, reduce and cause an extreme increase in manufacturing cost. 将P限定在0.03%以下,此范围是工业上比较廉价的且可能实施的范围,也是不使其耐CO2腐蚀性、耐CO2应力腐蚀裂纹性、耐点腐蚀性和耐硫化物应力腐蚀裂纹性共同劣化的范围。 Will be limited to 0.03% or less P, this range is the range of relatively inexpensive and industrially possible embodiment, it is not CO2 corrosion resistance, resistance to CO2 stress corrosion cracking, pitting corrosion resistance and sulfide stress corrosion cracking resistance joint deterioration range. 而且优选在0.02%以下。 And preferably 0.02% or less.

S:0.005%以下 S: 0.005% or less

S是在钢管的制造过程中,使其热加工性明显劣化的元素,希望其尽可能的少,由于降低至0.005%以下时可以以常规工序制造钢管,所以限定S在0.005%以下。 S in the steel manufacturing process, so that the hot workability deteriorates significantly element, it is desirable that as little as possible, due to the reduction step may be manufactured in a conventional steel pipe when 0.005% or less, S 0.005% or less in defining. 优选0.002%以下。 Preferably 0.002% or less.

Cr:15.5%以上、18%以下Cr是形成保护被膜、提高耐腐蚀性的元素,特别是有助于提高耐CO2腐蚀性、耐CO2应力腐蚀裂纹性的元素。 Cr: 15.5% or more, 18% or less Cr is a protective film is formed, improves corrosion resistance, particularly help to improve CO2 corrosion resistance, resistance to CO2 stress corrosion cracking resistance of the element. 在本发明中,特别是从提高高温下的耐腐蚀性的观点看,需要使其含有15.5%以上。 In the present invention, in particular to improve the corrosion resistance as seen from the viewpoint at a high temperature is required to contain more than 15.5%. 另一方面,当其超过18%时,热加工性劣化,同时强度也降低。 On the other hand, when it exceeds 18%, hot workability deteriorates, while strength is reduced. 因此,在本发明中,将Cr限定在15.5%以上、18%以下范围。 Accordingly, in the present invention, Cr is limited more than 15.5%, 18% or less range. 而且,优选16.5%以上、18%以下,更优选16.6%以上、不到18%。 Further, more preferably 16.5%, 18% or less, more preferably 16.6%, less than 18%.

Ni:1.5%以上、5%以下Ni是具有使保护被膜坚固、提高耐CO2腐蚀性、耐CO2应力腐蚀裂纹性、耐点腐蚀性和耐硫化物应力腐蚀裂纹性的作用,并通过固溶强化增加钢强度的元素。 Ni: 1.5% or more, it is 5% or less Ni has a strong protective film to improve CO2 corrosion resistance, resistance to CO2 stress corrosion cracking, pitting corrosion resistance effect cracking resistance and sulfide stress corrosion, solid solution strengthening and increase the strength of the steel elements. 认为在含有1.5%以上时才有这种效果,可是,当超过5%时马氏体组织的稳定性降低,强度降低。 That have such an effect, however, reduce the stability of the martensite structure when it exceeds 5% when the content is 1.5% or more, a decrease in strength. 因此,将Ni限定在1.5%以上、5%以下的范围内。 Thus, Ni is limited to 1.5% or more, a range of 5% or less. 且优选2.5%以上、4.5%以下。 And more preferably 2.5%, 4.5% or less.

Mo:1%以上、3.5%以下Mo是增加对Cl-的点腐蚀的抵抗性的元素,在本发明中需要含有1%以上。 Mo: 1% or more, 3.5% or less Mo is an element to increase Cl- resistance to pitting corrosion in the present invention needs to contain 1% or more. 若不足1%,可以说在严酷的高温腐蚀环境下的耐腐蚀性不充分。 If less than 1%, can be said that high temperature corrosion in the harsh environment of insufficient corrosion resistance. 另一方面,其含量超过3.5%时,强度降低,同时成本增大。 On the other hand, when the content thereof exceeds 3.5%, strength decreases, while the cost increases. 因此,将Mo限定在1%以上、3.5%以下的范围内。 Therefore, Mo is limited to 1% or more within the range of 3.5% or less. 且优选超过2%、3.5%以下。 And preferably more than 2%, 3.5% or less.

V:0.02%以上、0.2%以下V具有使强度增大,同时提高耐应力腐蚀裂纹性的效果。 V: 0.02% or more, 0.2% or less V has increased strength, while improving the stress corrosion cracking resistance effect. 这种效果在其含量为0.02%以上时较明显,可是当超过0.2%时,韧性劣化。 This effect is more pronounced when the content is 0.02% or more, but when it exceeds 0.2%, toughness is deteriorated. 因此,将V限定在0.02%以上、0.2%以下。 Thus, in defining the V 0.02%, 0.2% or less. 优选0.02%以上、0.08%以下。 Preferably 0.02% or more, 0.08% or less.

N:0.01%以上、0.15%以下N是使耐点腐蚀性得到明显提高的元素,在本发明中使其含有0.01%以上,可是其含量超过0.15%时,形成各种氮化物,韧性劣化。 N: 0.01%, 0.15% or less N is significantly improved pitting corrosion resistance element, to contain 0.01% or more in the present invention, but the content thereof exceeds 0.15%, various nitrides are formed, the toughness deteriorates. 因此,将N限定在0.01%以上、0.15%以下的范围,且优选0.02%以上、0.08%以下。 Therefore, the N content is limited to 0.01% or more, 0.15% or less, and preferably 0.02% or more, 0.08% or less.

O:0.006%以下O在钢中作为氧化物存在,使各种特性受到坏的影响,为了使特性得到提高,其含量越低越好。 O: 0.006% or less O is present in steel as an oxide, so that bad influence by various characteristics, characteristics are improved in order to make the content thereof as low as possible. 特别是当O含量超过0.006%时而较多时,热加工性、耐CO2应力腐蚀裂纹性、耐点腐蚀性和耐硫化物应力腐蚀裂纹性和韧性都明显降低。 In particular, when O content exceeds 0.006% and sometimes more, hot workability, resistance to CO2 stress corrosion cracking resistance, pitting resistance, and resistance to sulfide stress corrosion cracking resistance and toughness are decreased. 因此,在本发明中将O限定在0.006%以下。 Thus, in the present invention is limited to 0.006% or less O.

本发明中,在上述基本组织之外还可以含有Al:0.002%以上、0.05%以下。 In the present invention, in addition to the above ground tissue may further contain Al: 0.002% or more, 0.05% or less. Al是具有很强的脱氧作用的元素,为达到这种效果最好使其含有0.002%以上,可是,其含量超过0.05%时使其韧性受到坏的影响。 Al is a strong deoxidizing element acting, to achieve this effect it is preferably 0.002% or more, however, that it be adversely affected the toughness if the content exceeds 0.05%. 因此,含有Al时,优选将其限定在0.002%以上、0.05%以下的范围。 Thus, when containing Al, it is preferably limited to 0.002% or more, 0.05% or less. 更优选0.03%以下。 More preferably 0.03% or less. 在不添加Al时,其作为不可避免的杂质允许含有不到0.002%左右。 When not adding Al, which allow containing less than about 0.002% as an unavoidable impurity. 若把Al限制在不到0.002%左右,则具有低温韧性得到明显提高的优点。 If the Al limited to approximately less than 0.002%, there is the advantage of significantly improved low-temperature toughness.

并且,本发明中在上述各组成之外还可以含有3.5%以下的Cu。 The present invention, in addition to the above-described composition may further contain 3.5% or less of Cu. Cu是使保护被膜坚固,抑制氢进入钢中,提高耐硫化物应力腐蚀裂纹性的元素。 Cu is solid protective film, suppressing hydrogen enters the steel, improving the sulfide stress corrosion cracking resistance of the element. 当含量在0.5%以上时其效果明显。 When the content is less than 0.5%, its effect is obvious. 可是,含量超过3.5%时,导致CuS的晶界析出,热加工性降低。 However, when the content exceeds 3.5%, leading to grain boundary precipitation of CuS, hot workability deteriorates. 因此,优选将Cu限定在3.5%以下。 Therefore, Cu is preferably limited to 3.5% or less. 且优选0.8%以上、2.5%以下,更优选0.5%以上、1.14%以下。 And preferably less than 0.8%, 2.5% or less, more preferably 0.5% or more, 1.14% or less.

另外,本发明中在上述各种组成之外还可以含有从Nb:0.2%以下,Ti:0.3%以下,Zr:0.2%以下,W:3%以下,B:0.01%以下中选择的1种或2种以上。 Further, in addition to the above the present invention may further contain various components from Nb: 0.2% or less, Ti: 0.3% or less, Zr: 0.2% or less, W: 3% or less, B: 0.01% or less of one kind selected or two or more kinds.

Nb、Ti、Zr、W、B都是使强度增加的元素,可以根据需要选择,并且,Ti、Zr、W、B也是提高耐应力腐蚀裂纹性的元素。 Nb, Ti, Zr, W, B is an element increasing the strength can be selected as desired, and, Ti, Zr, W, B is an element to improve the stress corrosion cracking resistance. 这种效果在含有Nb:0.03%以上,Ti:0.03%以上,Zr:0.03%以上,W:0.2%以上,B:0.0005%以上时显著。 This effect of Nb: more than 0.03%, Ti: more than 0.03%, Zr: more than 0.03%, W: more than 0.2%, B: 0.0005% or more when significant. 另一方面,当各元素分别超出以下含量Nb:0.2%,Ti:0.3%,Zr:0.2%,W:3%,B:0.01%时,韧性劣化。 On the other hand, when the content of each element exceeds the respective Nb: 0.2%, Ti: 0.3%, Zr: 0.2%, W: 3%, B: 0.01%, the toughness is deteriorated. 因此,优选限定为以下各元素含量:Nb:0.2%以下,Ti:0.3%以下,Zr:0.2%以下,W:3%以下,B:0.01%以下。 Thus, preferably limited to the following element contents: Nb: 0.2% or less, Ti: 0.3% or less, Zr: 0.2% or less, W: 3% or less, B: 0.01% or less.

并且,本发明中,在上述各组成之外还可以含有Ca:0.01%以下。 The present invention, in addition to the above-described composition may further contain Ca: 0.01% or less. Ca作为CaS将S固定,具有使硫化物类夹杂物球化的作用,这样可使夹杂物周围的基体的晶格畸变缩小,具有使夹杂物的氢捕获能降低的效果。 Ca fixing S as CaS, sulfide inclusions having a ball effect, this allows the substrate lattice distortions around inclusions shrink, has a hydrogen capture inclusions can reduce the effect. 这种效果在其含量为0.0005%以上时显著。 This effect is remarkable when the content is 0.0005% or more. 可是其含量超过0.01%时,导致CaO增加,耐CO2腐蚀性、耐点腐蚀性降低。 However, when the content thereof exceeds 0.01%, resulting in an increase CaO, CO2 corrosion resistance, pitting corrosion resistance decrease. 因此,优选将Ca限定在0.01%以下的范围。 Accordingly, Ca is preferably limited to a range of 0.01% or less.

本发明中,调整上述各成分,使其在上述范围内,且满足下式(1)和下式(2)。 In the present invention, adjusting the respective components, it is within the above range, and satisfies (1) and the formula of the formula (2).

Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)其中,Cr、Ni、Mo、Cu、C、Si、Mn、N为各元素的含量(质量%)在计算式(1)和式(2)左边的值时,不含有的元素按零%计算。 Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C≥19.5 ... (1) Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ... (2) where, Cr, Ni, Mo , Cu, C, Si, Mn, N is the content of each element (mass%) in the calculation of the value of the left side of formula (1) and (2), calculated as the element is not contained zero%.

通过调整Cr、Ni、Mo、Cu、C的含量,使其满足式(1),在230℃高温的含有CO2、Cl-的高温腐蚀环境下,其耐腐蚀性得到明显提高。 By adjusting the Cr, the content of Ni, Mo, Cu, C so as to satisfy the formula (1), at a high temperature containing CO2 230 ℃, Cl- high temperature corrosive environment, which corrosion resistance is significantly improved. 并且,从含有CO2、Cl-的高温腐蚀环境下的耐腐蚀性提高的观点看,式(1)左边的值优选为20.0以上。 And, from the viewpoint of containing CO2, the corrosion resistance at a high temperature corrosive environment Cl- improved look, the value of formula (1) is preferably 20.0 or more left.

另外,通过调整Cr、Mo、Si、C、Mn、Ni、Cu、N的含量,使其满足式(2),热加工性得到提高。 Further, by adjusting the Cr, Mo, Si, C, Mn, Ni, Cu, N contents so as to satisfy the formula (2), the hot workability is improved. 在本发明中,为使热加工性得到提高,要明显降低P、S、O的含量,可是,只是分别降低P、S、O的含量不能确保为了制造马氏体类不锈钢无缝钢管所需要的充分的热加工性。 In the present invention, the hot workability is improved, to significantly reduce the content of P, S, O, but only decreased the content of P, S, O can not be secured in order to manufacture a martensitic stainless steel seamless pipe required full of hot workability. 为了确保制造无缝钢管所需要的充分的热加工性,在明显降低P、S、O的含量的基础上,关键在于调整Cr、Mo、Si、C、Mn、Ni、Cu、N的含量,使其满足式(2)。 In order to ensure seamless steel pipe sufficient hot workability required, significantly decreased on the basis of the content of P, S, O is on, the key is to adjust the Cr, the content of Mo, Si, C, Mn, Ni, Cu, N, and so as to satisfy the formula (2). 并且,从热加工性提高的观点看,式(2)左边的值优选为12.0以上。 And, to improve the hot workability viewpoint, the formula (2) value is preferably 12.0 or more to the left.

上述成分以外的余量是Fe和不可避免的杂质。 The balance other than the above components is Fe and unavoidable impurities.

本发明的油井用高强度不锈钢管,在上述组成之外,优选具有将马氏体相作为基相,含有体积率在10%以上、60%以下、优选超过10%、60%以下的铁素体相的组织。 Well according to the present invention is high strength stainless steel tube, in addition to the above composition, preferably has a martensite phase as a matrix phase, at a volume ratio of 10%, 60% or less, preferably more than 10%, 60% or less of ferrite the bulk of the organization.

本发明的钢管,为确保其高强度,将马氏体组织作为基本组织。 Steel pipe of the present invention, a high strength to ensure that the martensite structure as the basic organization. 为不降低其强度而使其韧性得到提高,优选形成将马氏体相作为基相,含有作为第二相的体积率在10%以上、60%以下、优选超过10%、60%以下的铁素体相的组织。 Not reduce its strength so as to improve the toughness, the martensite phase is preferably formed as a matrix phase, as the volume fraction of the second phase comprises at least 10%, 60%, preferably more than 10%, 60% iron the tissues of the element body. 铁素体相的体积率不足10%或在10%以下时不能达到所期望的目的。 Ferrite phase volume fraction of 10% or less than the intended purpose can not be achieved when 10% or less. 另一方面,当铁素体相超过60体积%时,其强度降低。 On the other hand, when the ferrite phase exceeds 60 vol%, the strength thereof is lowered. 因此,铁素体相的体积率限定在10%以上、60%以下,优选限定在超过10%、60%以下的范围。 Accordingly, the ferrite phase is limited to a volume fraction of 10% or more, 60% or less, preferably limited to the range of more than 10%, 60% or less. 而且,更优选15%以上、50体积%。 Further, more preferably 15% or more, 50% by volume. 作为铁素体相以外的第二相,即使含有30体积%以下的奥氏体相也没有任何问题。 As the second phase other than the ferrite phase, austenite phase even 30 vol% or less without any problem.

下面,对本发明钢管的制造方法,以无缝钢管为例子进行说明。 Next, a method for producing a steel pipe of the present invention, seamless steel pipe will be described as an example.

首先,优选对具有上述组成的钢水,用转炉、电炉、真空熔化炉等的通常公知的熔炼方法进行熔炼,用连续铸造法,铸锭—开坯轧钢法等的通常公知的方法,制成坯段等的钢管原材料。 First, preferably having a molten steel having the above composition is smelted by a conventional known converter, electric furnace, a vacuum melting furnace or the like smelting process, by continuous casting, ingot - blooming rolling method or the like is generally known method to prepare a blank steel and other raw materials segment. 然后,把这些钢管原材料加热,用通常的曼内斯曼—蕊棒轧管机方式或者用曼内斯曼—芯棒式无缝管轧机方式,通过热加工制造钢管,得到规定尺寸的无缝钢管,制成管后的无缝钢管优选用空冷以上的冷却速度冷却到室温。 Then, these steel tube material is heated by a usual Mannesmann - core rod or tube mill by way Mannesmann - mandrel mill method, for producing steel by hot working, to obtain a predetermined size seamless steel, seamless steel pipe is preferably formed after cooling to room temperature with a cooling rate of air cooling or more. 并且,也可以用冲压方式的热压制造无缝钢管。 Further, seamless steel pipe can be manufactured by the hot press method.

具有上述本发明范围内的组成的无缝钢管,通过热加工后,用空冷以上的冷却速度冷却到室温,可以形成将马氏体相作为基相的组织。 Seamless steel pipe having a composition within the scope of the present invention, by the thermal processing, cooling more air cooling to room temperature, cooling rate, the tissue may be formed martensite phase as a group. 可是,优选在制造钢管后,用空冷以上的冷却速度冷却,接着进行如下的淬火处理:再加热至850℃的温度,用空冷以上的冷却速度冷却到100℃以下,优选冷却到室温。 However, preferably after manufacturing steel, a cooling rate of air cooling or more, followed by quenching follows: reheated to a temperature of 850 deg.] C, cooled with a cooling rate of air cooling or more to 100 deg.] C or less, preferably cooled to room temperature. 通过上述处理,优选可以形成含有适当量的铁素体相的微细的高韧性马氏体组织。 Through the above process, preferably a high-toughness martensitic may be formed of ferrite phase containing appropriate quantities of the fine.

淬火加热温度若不到850℃,马氏体部分未充分淬火,其强度有降低的倾向。 If the quenching temperature to 850 ℃, part of martensite is not sufficiently quenched, the strength tends to decrease. 因此,淬火处理的加热温度优选850℃以上的温度。 Accordingly, the heating temperature is more preferably quenching temperature of 850 deg.] C.

实施淬火处理的无缝钢管,优选接着实施如下的回火处理:加热至700℃以下的温度,用空冷以上的冷却速度进行冷却,通过加热至700℃以下、优选400℃以上的温度并进行回火,其组织成为由回火马氏体相或少量的铁素体相以及奥氏体相构成的组织,从而成为具有所期望的高强度、高韧性和优良的耐腐蚀性的无缝钢管。 Seamless steel tube quenching treatment, tempering treatment is preferably followed by the following embodiments: heated to a temperature of 700 deg.] C, cooled by a cooling rate of air cooling or more, by heating to 700 deg.] C or less, more preferably a temperature of 400 deg.] C and back fire, which organized into a tempered martensite phase or a small amount of ferrite phase and austenite phase configuration, thus becoming having the desired high strength, high toughness and excellent corrosion resistance of the seamless steel pipe.

并且,可以不进行回火处理的,只实施上述的回火处理。 Further, the tempering treatment may not be performed, the above-described embodiment only tempering process.

至此,是以无缝钢管为例的说明,本发明的钢管并不限定于此。 Thus, described is an example of seamless steel pipe, steel pipe of the present invention is not limited thereto. 使用具有上述本发明范围内的组成的钢管原材料,按照通常工序,可以制造电焊钢管、UOE钢管作为油井用钢管。 Steel material having the above composition within the scope of the present invention, according to the usual procedure, welded steel pipes can be manufactured, the UOE steel pipe as OCTG.

使用具有上述本发明范围内组成的钢管原材料,按照通常制造工序得到的无缝钢管以外的钢管,如电焊钢管、UOE钢管,对于所制成的钢管,优选进行上述的淬火—回火处理:再加热至850℃的温度后,用空冷以上的冷却速度冷却到100℃以下,优选冷却到室温的淬火处理、和接着加热至700℃以下、优选400℃以上的温度,用空冷以上的冷却速度进行冷却的回火处理。 Steel materials having compositions within the scope of the present invention, other than the steel according to the manufacturing process of seamless steel pipe is usually obtained, such as welded steel pipes, the UOE steel pipe, made of steel to preferably perform the quenching - tempering treatment: then after heating to a temperature of 850 deg.] C, and cooling or more air-cooled cooling rate to less 100 deg.] C, preferably cooled quenched to room temperature, and then heated to less than 700 deg.] C, more preferably 400 deg.] C of temperature, using the above air-cooled cooling rate cooling tempering treatment.

实施例下面是按照实施例更详细地说明本发明。 Example The following embodiment of the present invention is described in more detail according to an embodiment.

实施例1把具有表1中所示的组成的钢水脱气后,铸成100kg的钢锭(钢管原材料),利用模型无缝轧机通过热加工制造钢管,制成钢管后进行空冷或水冷,制成外径838mm×壁厚12.7mm(3.3in×壁厚0.5in)的无缝钢管。 Example 1 having the composition shown in Table degassing molten steel 1, 100kg cast ingot (steel raw material), using the model by hot rolling seamless steel pipe manufacturing, air cooling or water cooling the steel pipe, made an outer diameter of 838mm × thickness 12.7mm (3.3in × thickness 0.5in) seamless steel pipe.

对得到的无缝钢管,在制成钢管后进行空冷的状态下,目视研究内外表面有无裂纹的发生,评价热加工性。 The resulting seamless steel pipe, in a state after air cooling steel pipe, the occurrence of cracks was visually study, evaluation of hot workability inner and outer surfaces. 在管子前后端面存在长5mm以上的裂纹时,规定为有裂纹,把除此以外的情况规定为无裂纹。 When there is more than 5mm in length before and after the cracking tube end, defined as a crack, is defined as the other cases no cracks.

并且,从得到的无缝钢管上切出试样原材料,在920℃的温度下加热30min后,进行水冷(从800%以上冷却到500℃的平均冷却速度为10℃/s)。 And, cutting the seamless steel pipe from a sample material obtained after 30min heated at a temperature of 920 ℃, cooled with water (cooling from 800% to 500 ℃ average cooling rate of 10 ℃ / s). 再实施580℃×30min的回火处理。 Another embodiment 580 ℃ × 30min tempering treatment. 从如上所述实施淬火—回火处理后的试样原材料上,采取观察组织用的试样,把观察组织用的试样在王水中腐蚀,用扫描电子显微镜(1000倍)对组织进行摄像,使用图像分析装置计算铁素体相的组织百分比(体积%)。 As described above the quenching - tempering the sample material after treatment, taking samples of tissues were observed, with the observed tissue sample in aqua regia etching, the tissue imaging using a scanning electron microscope (1,000 times), tissue percentage (vol%) is calculated using image analysis apparatus ferrite phase.

另外,残余奥氏体相的组织百分比,使用X射线衍射法测定。 Further, the percentage of retained austenite phase was determined using X-ray diffractometry. 从实施了淬火—回火处理后的试样原材料上,采取测定用的试样,通过X射线衍射测定γ的(220)面、α的(221)面的X射线衍射积分强度,用下式进行换算。 Quenching the embodiment - the sample material after tempering, taking a sample of the measurement, X-ray diffraction integrated intensity of (221) plane of γ measured by X-ray diffraction (220) plane, the [alpha], by the following formula for conversion.

γ(体积率)=100/{1+(IαRγ/IγRα)}其中,Iα:α的积分强度Iγ:γ的积分强度Rα:α的结晶学理论计算值Rγ:γ的结晶学理论计算值并且,马氏体相的百分比作为这些相以外的余量计算出。 gamma] (volume ratio) = 100 / {1+ (IαRγ / IγRα)} wherein, Iα: integrated intensity Iγ α: the integrated intensity of Rα γ: Theory crystalline calcd Ry of [alpha]: Calculated for gamma] crystalline Theory and , as a percentage of the martensite phase other than the phase margin is calculated.

而且,从实施淬火—回火处理的试样原材料上,采取API弧形拉伸试样,实施拉伸试验,求出拉伸特性(屈服强度YS、拉伸强度TS)。 Furthermore, the quenching - tempering the sample materials, tensile specimens taken arcuate API, tensile test, to determine the tensile properties (yield strength YS, tensile strength TS).

进一步,从实施淬火—回火处理的试样原材料上,通过机械加工,制作厚3mm×宽30mm×长40mm的腐蚀试样,实施腐蚀试验。 Further, the quenching - tempering of the sample material, by machining, making a thickness of 3mm 30mm width × 40mm length × corrosion coupons of the corrosion test.

腐蚀试验是在保持于高压釜中的试验液:20%的NaCl水溶液(液温:230℃、100大气压下的CO2气体气氛中)中,浸泡腐蚀试样,浸泡期间为2周。 Corrosion tests were held in an autoclave test solution: 20% NaCl aqueous solution (liquid temperature: 230 ℃, CO2 gas atmosphere at 100 atmospheric pressure), the corrosion coupons immersed, immersion period of 2 weeks. 对于腐蚀试验后的试样,测定其重量,根据腐蚀试验前后的试样重量的减少量,计算求出腐蚀速度。 For the sample after the corrosion test, the weight was measured, according to the weight of the sample before and after the reduced amount of the corrosion test, corrosion rate is calculated is obtained. 并且,对于试验后的试样,用倍率为10倍的放大镜,观察试样表面有无点腐蚀发生。 Then, to the sample after the test, at a magnification of 10 times magnifying glass, the surface of the specimen was observed whether or pitting occurs. 把观察到直径在0.2mm以上的点腐蚀规定为有点腐蚀,把除此以外的情况规定为无点腐蚀。 The observed diameter above 0.2mm pitting corrosion is defined as a bit, defined as the other cases no pitting. 所得结果如表2所示。 The results are shown in Table 2.

表1 Table 1

*)式(1)左边:Cr+0.65Ni+0.6Mo+0.55Cu-20C**)式(2)左边:Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N *) Of formula (1) Left: Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C **) formula (2) left: Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N

表2 Table 2

*)M:马氏体,F:铁素体,γ:残余奥氏体本发明例都未发现钢管表面发生裂纹,并且,形成的钢管其具有屈服强度YS在654MPa以上的高强度,腐蚀速度也小,没有点腐蚀发生,热加工性和在含有CO2且温度为230℃的严酷的高温腐蚀环境下的耐腐蚀性优良。 *) M: martensite, F: ferrite, γ: residual austenite steel of the present invention the surface cracks was not observed, and the formed steel tube having a high strength at yield strength YS 654MPa or more, the corrosion rate is also small, no pitting occurred in hot workability and containing CO2 and a temperature of excellent corrosion resistance under severe high-temperature corrosive environment of 230 deg.] C. 而且由于含有5%以上的铁素体相,在含有CO2且温度为230℃的严酷的高温腐蚀环境下具有优良的耐腐蚀性,且具有屈服强度YS在654MPa以上的高强度。 And because it contains more than 5% of ferrite phase, containing CO2 and a temperature having excellent corrosion resistance under severe high-temperature corrosive environment of 230 deg.] C, it has a yield strength YS and a high strength of 654MPa or more.

与此相反,本发明的范围以外的比较例,其表面发生裂纹,热加工性降低,或腐蚀速度增大,发生点腐蚀,耐腐蚀性降低。 In contrast, Comparative Examples outside the scope of the present invention, the surface cracks, hot workability decreases, or increases the corrosion rate, the occurrence of pitting corrosion, corrosion resistance. 特别是不满足式(2)的比较例,其热加工性降低,钢管表面产生损伤。 Comparative Example particular does not satisfy the formula (2), the hot workability, the steel surface damaged. 并且,铁素体的量在本发明的适合范围以外的情况下,其强度降低,不能满足屈服强度YS在654MPa以上的高强度。 Further, the amount of ferrite in the case outside the scope of the present invention is suitable, the reduction in strength, yield strength YS not meet the high strength of 654MPa or more.

实施例2把具有表1所表示的组成(钢No.B、No.S)的钢管原材料,通过热加工制成钢管,制成钢管后进行空冷,成为外径83.8mm×壁厚12.7mm(3.3in×壁厚0.5in)的无缝钢管。 Example 2 Steel material having tables (steel No.B, No.S) 1 of the embodiment represented, is made of steel pipe by hot working, air cooling the steel pipe, the wall thickness to become the outer diameter of 83.8mm × 12.7mm ( 0.5in 3.3in × thickness) of the seamless steel pipe. 从得到的无缝钢管上切出试样原材料,实施如表3所示的淬火—回火处理、或回火处理。 From the obtained seamless steel pipe material sample was cut out, hardened embodiment shown in Table 3 - tempering or tempering.

从实施淬火—回火处理的试样原材料上,同实施例1一样采取观察组织用的试样、测定用的试样,计算出铁素体相的组织百分比(体积%)、残余奥氏体的组织百分比(体积%)、马氏体相的组织百分比(体积%)。 From quenching - tempering of the sample material, the same as Example 1 by taking a sample of tissue was observed, the measurement sample to calculate the percentage of ferrite phase (% by volume), residual austenite percentage (vol%), the percentage of martensite phase (% by volume) tissue.

而且,从实施淬火—回火处理的试样原材料上,采取API弧形拉伸试样,与实施例1相同,实施拉伸试验,求出拉伸特性(屈服强度YS、拉伸强度TS)。 Furthermore, the quenching - tempering of the sample material, adopt the same API arcuate tensile test as in Example 1, tensile test, to determine the tensile properties (yield strength YS, tensile strength TS) . 进一步,从实施淬火—回火处理的试样原材料上,与实施例1相同,通过机械加工,制作厚3mm×宽30mm×长40mm的腐蚀试样,实施腐蚀试验,求出腐蚀速度。 Further, the quenching - tempering of the sample material, the same as in Example 1, by machining, the corrosion specimens produced 3mm thick × 30mm width × 40mm in length, the corrosion test, corrosion rate is obtained. 并且,与实施例1相同,观察试样表面有无点腐蚀发生,评价标准与实施例1相同。 And, as in Example 1, the specimen was observed whether the surface point corrosion, the same evaluation criteria as in Example 1. 所得结果如表3所示。 The obtained results are shown in Table 3.

表3 table 3

*)M:马氏体,F:铁素体,γ:残余奥氏体本发明例都是具有屈服强度YS在654MPa以上的高强度,腐蚀速度也小,没有点腐蚀发生,热加工性和在含有CO2且温度为230℃的严酷的高温腐蚀环境下的耐腐蚀性优良的钢管。 *) M: martensite, F: ferrite, γ: embodiment of the present invention are retained austenite having a high yield strength YS strength above 654MPa, the etching rate is small, no pitting occurred, hot workability and under severe high temperature corrosion environment containing CO2 and a temperature of 230 deg.] C of the steel pipe excellent in corrosion resistance. 在本发明例中,在本发明的适合范围以外的情况下,其强度或耐腐蚀性、热加工性有降低的倾向。 In the embodiment of the present invention, in the case outside the scope of the present invention is suitable in its strength and corrosion resistance, hot workability tends to decrease.

实施例3把具有表4中所表示的组成的钢水去气后,铸成100kg的钢锭,利用模型无缝轧机通过热加工制成钢管,制成钢管后进行冷却(空冷),使其成为外径83.8mm×壁厚12.7mm(3.3in×壁厚0.5in)的无缝钢管。 Example 3 the molten steel having a composition in Table 4, represented in to gas, the cast ingot 100kg, using a model mill seamless steel pipe by hot working, cooling (air cooling) After the steel pipe, making the outer thickness diameter 83.8mm × 12.7mm (3.3in × thickness 0.5in) seamless steel pipe.

对得到的无缝钢管,在制成钢管后冷却(空冷)的状态下,与实施例1相同,目视研究钢管内外表面有无裂纹的发生,评价热加工性。 The resulting seamless steel pipe, steel pipe at the state of the cooling (air cooling), the same as in Example 1, the presence of cracks was visually study the occurrence of internal and external pipe surfaces, hot workability evaluation. 并且,评价标准与实施例1相同。 Further, the same evaluation criteria as in Example 1.

并且,从得到的无缝钢管上切出试样原材料,在900℃的温度下加热30min后,进行水冷。 And, cutting the seamless steel pipe from a sample material obtained after 30min heated at a temperature of 900 deg.] C, water-cooled. 再实施580℃×30min的回火处理。 Another embodiment 580 ℃ × 30min tempering treatment. 从这样的实施了淬火—回火处理后的试样上,采取观察组织用的试样、测定用试样,把观察组织用的试样在王水中使其腐蚀,用扫描电子显微镜(1000倍)对组织进行摄像,使用图像分析装置计算出铁素体相的组织百分比(体积%)。 From such embodiments quenching - tempering the sample after treatment, tissue was observed to take a sample, the measurement sample, a tissue sample to observe it in aqua regia etching, a scanning electron microscope (1,000 times ) imaging the tissue, calculate the percentage of ferrite phase (% by volume) using an image analysis apparatus. 从实施了淬火—回火处理后的试样原材料上,采取测定用试样,与实施例1相同,测定残余奥氏体、马氏体相的组织百分比(体积%)。 Quenching the embodiment - the sample material after tempering, take sample, the same measurement as in Example 1, measurement of residual austenite, martensite tissue percentage (% by volume).

而且,从实施淬火—回火处理的试样原材料上,采取API弧形拉伸试样,实施拉伸试验,求出拉伸特性(屈服强度YS、拉伸强度TS)。 Furthermore, the quenching - tempering the sample materials, tensile specimens taken arcuate API, tensile test, to determine the tensile properties (yield strength YS, tensile strength TS). 进一步,从实施淬火—回火处理的试样原材料上,按照JIS Z 2202的规定采取V缺口试样(厚度:5mm),按照JIS Z 2242的规定实施查夏比冲击试验,求在-40℃时的吸收能vE-40(J)。 Further, the quenching - tempering taken on a sample material in accordance with JIS Z 2202 V-notch specimens (thickness: 5mm), check the Charpy impact test was implemented in accordance with JIS Z 2242, the seek at -40 ℃ absorbed energy vE-40 (J) when.

进一步,从实施淬火—回火处理的试样原材料上,通过机械加工,制作厚3mm×宽30mm×长40mm的腐蚀试样,实施腐蚀试验。 Further, the quenching - tempering of the sample material, by machining, making a thickness of 3mm 30mm width × 40mm length × corrosion coupons of the corrosion test. 并且,一部分钢管不实行淬火处理,只实行回火处理。 And, not implementation of part of the steel pipe quenching, tempering implementation only.

腐蚀试验是在保持于高压釜中的试验液:20%的NaCl水溶液(液温:230℃、100大气压下的CO2气体气氛)中,浸泡腐蚀试样,浸泡期间为2周。 Corrosion test is a test liquid held in the autoclave: 20% NaCl aqueous solution (liquid temperature: 230 ℃, CO2 gas atmosphere at 100 atm), the corrosion coupons immersed, immersion period of 2 weeks. 对于腐蚀试验后的试样,测定其重量,根据腐蚀试验前后的试样重量的减少量,计算求出腐蚀速度。 For the sample after the corrosion test, the weight was measured, according to the weight of the sample before and after the reduced amount of the corrosion test, corrosion rate is calculated is obtained. 另外,关于耐点腐蚀性,将钢管浸泡于40%的CaCl2(液温:70℃)溶液中,浸泡24小时,研究有无点腐蚀的发生。 Further, regarding the pitting corrosion resistance, the steel tube immersed in a 40% of CaCl2 (liquid temperature: 70 ℃) solution, soak for 24 hours, Studies on the occurrence or absence of pitting. 把观察到直径在0.1mm以上的点腐蚀规定为有点腐蚀,把除此之外的情况规定为无点腐蚀。 The observed diameter of 0.1mm or more is defined as a bit pitting corrosion, in addition to the case where no pitting is predetermined. 所得结果如表5所示。 The obtained results are shown in Table 5.

表4 Table 4

*)式(1)左边:Cr+0.65Ni+0.6Mo+0.55Cu-20C**)式(2)左边:Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N *) Of formula (1) Left: Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C **) formula (2) left: Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N

表5 table 5

M:马氏体,F:铁素体,γ:残余奥氏体本发明例都未发现钢管表面发生裂纹,并且是具有屈服强度YS在654MPa以上的高强度,腐蚀速度也小,没有点腐蚀发生,热加工性和在含有CO2且温度为230℃的严酷的高温腐蚀环境下的耐腐蚀性优良的钢管。 M: martensite, F: ferrite, γ: residual austenite steel of the present invention the surface cracks was not observed, and having a high yield strength YS strength above 654MPa, the etching rate is small, no pitting occurs, hot workability and containing CO2 and a temperature of excellent corrosion resistance in a severe corrosive environment of high temperature of 230 deg.] C steel. 由于含有5%以上的铁素体相,在含有CO2且温度为230℃的严酷的高温腐蚀环境下,具有优良的耐腐蚀性,且具有屈服强度YS在654MPa以上的高强度和具有在-40℃时的吸收能在50J以上的高韧性。 Since 5% or more of ferrite phase, containing CO2 at a temperature and under severe high-temperature corrosive environment of 230 deg.] C, having excellent corrosion resistance and having high strength at yield strength YS 654MPa or more and having at -40 can absorb high toughness above 50J during deg.] C. 并且,钢管No.13、No.14中Al含量较高,韧性有一些降低,发生点腐蚀,可是其程度轻微,直径不足0.2mm。 Furthermore, steel No.13, No.14 higher Al content, the toughness slightly decreased, the occurrence of pitting corrosion, but a slight degree, diameter of less than 0.2mm.

与此相反,本发明范围以外的比较例,其表面发生裂纹,热加工性降低,或腐蚀速度增大,发生点腐蚀,耐腐蚀性降低。 In contrast, Comparative Examples outside the scope of the present invention, the surface cracks, hot workability decreases, or increases the corrosion rate, the occurrence of pitting corrosion, corrosion resistance. 特别是不满足式(2)的比较例,其热加工性降低,钢管表面发生损伤。 Comparative Example particular does not satisfy the formula (2), the hot workability, the steel surface being damaged. 并且,铁素体的量在本发明的适合范围以外的情况下,其强度降低,不能满足屈服强度YS在654MPa以上的高强度。 Further, the amount of ferrite in the case outside the scope of the present invention is suitable, the reduction in strength, yield strength YS not meet the high strength of 654MPa or more.

产业上利用的可能性根据本发明,可以廉价且稳定地制造在含有CO2、Cl-的严酷的高温腐蚀的环境下具有良好的耐腐蚀性,具有高强度、或者还具有高韧性的油井用不锈钢管。 POSSIBILITY OF INDUSTRIAL APPLICABILITY According to the present invention, can be manufactured inexpensively and stably has good corrosion resistance under severe high temperature corrosion environment containing CO2, Cl-, and having high strength, or further a high toughness stainless steel for oil wells tube. 在产业上特别奏效。 Particularly effective in the industry. 根据本发明,还具有如下优点:在制成钢管后,只进行热处理就可以得到作为油井钢管的足够强度。 According to the present invention, further it has the following advantages: in the steel pipe, heat treatment can be obtained only as an oil well steel pipe of sufficient strength.

Claims (23)

1.一种耐腐蚀性优良的油井用高强度不锈钢管,其特征在于,其组成以质量%计含有:C:0.005%以上、0.05%以下、Si:0.05%以上、0.5%以下、Mn:0.2%以上、1.8%以下、P:0.03以下、S:0.005%以下、Cr:15.5%以上、18%以下、Ni:1.5%以上、5%以下、Mo:1%以上、3.5%以下、V:0.02%以上、0.2%以下、N:0.01%以上、0.15%以下、O:0.006%以下,且满足下列式(1)和式(2),余量由Fe和不可避免的杂质构成,Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)其中,Cr、Ni、Mo、Cu、C、Si、Mn、N为各元素的含量(质量%)。 An oil well with excellent corrosion resistance with high strength stainless steel pipe, characterized in that a composition containing, by mass%: C: 0.005%, 0.05% or less, Si: 0.05%, 0.5% or less, Mn: 0.2%, 1.8% or less, P: 0.03 or less, S: 0.005% or less, Cr: more than 15.5%, 18% or less, Ni: 1.5%, 5%, Mo: not more than 1%, 3.5% or less, V : 0.02% or more, 0.2% or less, N: 0.01%, 0.15% or less, O: 0.006% or less, and satisfies the following formula (1) and (2), the balance being Fe and unavoidable impurities, Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C≥19.5 ... (1) Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ... (2) where, Cr, Ni, Mo, Cu, C, Si, Mn, N is the content of each element (mass%).
2.如权利要求1所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外以质量%计还含有Al:0.002%以上、0.05%以下的组成。 2. Well according to claim 1 of high strength stainless steel pipe, comprising said composition having outside mass%, further containing Al:, 0.05% or less than 0.002% composition.
3.如权利要求1或2所述的油井用高强度不锈钢管,其特征在于,以质量%计,所述C的含量在0.03%以上、0.05%以下。 It said oil or claim 12 with a high strength stainless steel tube, wherein, in mass%, the C content is above 0.03%, 0.05% or less.
4.如权利要求1~3中任一项所述的油井用高强度不锈钢管,其特征在于,所述Cr的含量在16.6%以上、不足18%。 4. Well according to any one of claims 1 to 3, a high strength stainless steel tube, wherein the Cr content is more than 16.6%, less than 18%.
5.如权利要求1~4中任一项所述的油井用高强度不锈钢管,其特征在于,以质量%计,所述Mo的含量在2%以上、3.5%以下。 5. Well according to any one of claims 1 to 4, wherein the high-strength stainless steel pipe, characterized in that, in mass%, the content of Mo is over 2%, 3.5% or less.
6.如权利要求1~5中任一项所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外以质量%计还含有Cu:0.5%以上、3.5%以下的组成。 6. The oil of any one of claims 1 to 5, wherein the high-strength stainless steel pipe, characterized by having a composition outside said further contains by mass%, Cu:, 3.5% or less 0.5% of the composition .
7.如权利要求6所述的油井用高强度不锈钢管,其特征在于,以质量%计,所述Cu的含量在0.5%以上、1.14%以下。 7. The well according to claim 6, wherein the high-strength stainless steel pipe, characterized in that, in mass%, the content of Cu is 0.5% or more, 1.14% or less.
8.如权利要求1~7中任一项所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外,以质量%计还含有选自Nb:0.03%以上、0.2%以下,Ti:0.03%以上、0.3%以下,Zr:0.03%以上、0.2%以下,W:0.2%以上、3%以下,B:0.0005%以上、0.01%以下中的1种或2种以上的组成。 8. The oil of any one of claims 1 to 7, wherein the high-strength stainless steel pipe, comprising said composition having outside, further mass%, Nb: 0.03% to 0.2% less, Ti: 0.03% to 0.3% or less, Zr: 0.03% or more, 0.2% or less, W: more than 0.2%, 3% or less, B: 0.0005% or more, 0.01% or less of one or more kinds of composition.
9.如权利要求1~8中任一项所述的油井用高强度不锈钢管,其特征在于,具有在所述组成之外以质量%计还含有Ca:0.0005%以上、0.01%以下的组成。 9. The oil of any one of claims 1 to 8, wherein the high-strength stainless steel pipe, characterized by having a composition outside said further contains by mass%, Ca:, 0.01% or less of the composition of 0.0005% .
10.如权利要求1~9中任一项所述的油井用高强度不锈钢管,其特征在于,具有以马氏体相作为基相,还含有体积率为10%以上、60%以下的铁素体相的组织。 10. A well as claimed in any one of claims 1 to 9, high strength stainless steel pipe, characterized in that, with 60% of the iron is martensitic phase as a group, also contains at least 10% by volume, the tissues of the element body.
11.如权利要求10所述的油井用高强度不锈钢管,其特征在于,所述铁素体相的体积率为15%以上、50%以下。 11. The well according to claim 10 with a high strength stainless steel pipe, characterized in that the ferrite phase volume fraction of 15% or more, 50% or less.
12.如权利要求10或11所述的油井用高强度不锈钢管,其特征在于,所述组织还含有体积率为30%以下的奥氏体相。 12. The oil of claim 10 or claim 11 with a high strength stainless steel tube, wherein said tissue further comprises 30% or less by volume of austenite phase.
13.一种耐腐蚀性优良的油井用高强度不锈钢管的制造方法,其特征在于,将具有以质量%计含有C:0.005%以上、0.05%以下,Si:0.05%以上、0.5%以下,Mn:0.2%以上、1.8%以下,P:0.03以下,S:0.005%以下,Cr:15.5%以上、18%以下,Ni:1.5%以上、5%以下,Mo:1%以上、3.5%以下,V:0.02%以上、0.2%以下,N:0.01%以上、0.15%以下,O:0.006%以下,且满足下列式(1)和式(2),余量由Fe和不可避免的杂质构成的组成的钢管原材料,制成规定尺寸的钢管,对该钢管再加热到850℃以上的温度后,用空冷以上的冷却速度冷却至100℃以下,然后,实施加热到700℃以下的温度的淬火—回火处理,Cr+0.65Ni+0.6Mo+0.55Cu-20C≥19.5 …(1)Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 …(2)其中,Cr、Ni、Mo、Cu、C、Si、Mn、N为各元素的含量(质量%)。 An excellent corrosion resistance in oil well, characterized in that the method for manufacturing a high strength stainless steel pipe, having, by mass%, C: 0.005%, 0.05% or less, Si: 0.05%, 0.5% or less, mn: 0.2%, 1.8% or less, P: 0.03 or less, S: 0.005% or less, Cr: more than 15.5%, 18% or less, Ni: 1.5% or more, 5% or less, Mo: 1% or more and 3.5% or less , V: 0.02% or more, 0.2% or less, N: 0.01%, 0.15% or less, O: 0.006% or less, and satisfies the following formula (1) and (2), the balance being Fe and unavoidable impurities after the steel material consisting of a predetermined size made from steel, the steel is reheated to a temperature above 850 deg.] C, cooled with a cooling rate of air cooling or more to 100 deg.] C or less, then subjected to heat to a temperature below 700 ℃ quenching - tempering, Cr + 0.65Ni + 0.6Mo + 0.55Cu-20C≥19.5 ... (1) Cr + Mo + 0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N≥11.5 ... (2) wherein, cr, Ni, Mo, Cu, C, Si, Mn, N is the content of each element (mass%).
14.如权利要求13所述的油井用高强度不锈钢管的制造方法,其特征在于,对所述钢管原材料进行加热,通过热加工制成管,制成管后,用空冷以上的冷却速度冷却至室温,制成规定尺寸的无缝钢管,然后对该无缝钢管实施所述淬火—回火处理。 14. The well of claim 13, characterized in that the method for manufacturing a high strength stainless steel pipe, the steel tube material is heated, the tube is made by hot working, the pipe is made, air cooling with a cooling rate of more than to room temperature, the seamless steel pipe having a predetermined size, then the embodiment of the seamless steel pipe quenching - tempering.
15.如权利要求13或14所述的油井用高强度不锈钢管的制造方法,其特征在于,代替所述的淬火—回火处理,实施加热至700℃以下的温度的回火处理。 15. A method of manufacturing an oil well according to claim 13 or 14 with a high strength stainless steel pipe, characterized in that, in place of the quenching - tempering treatment, a heat temperature of 700 deg.] C to a tempering treatment.
16.如权利要求13~15中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外以质量%计还含有Al:0.002%以上、0.05%以下的组成。 16. A method of manufacturing an oil well according to any one of claims 13 to 15, said high-strength stainless steel pipe, characterized by having a composition outside of the mass%, further containing Al: 0.002%, 0.05% the following components.
17.如权利要求13~16中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,以质量%计,所述C的含量在0.03%以上、0.05%以下。 17. The method of producing 13 to 16 according to any one of claims high strength stainless steel for oil well pipes, characterized in that, in mass%, the C content is above 0.03%, 0.05% or less.
18.如权利要求13~17中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,所述Cr的含量在16.6%以上、不足18%。 18. The oil according to any one of claims 13 to 17, wherein a method for manufacturing a high strength stainless steel pipe, wherein the Cr content is more than 16.6%, less than 18%.
19.如权利要求13~18中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,以质量%计,所述Mo的含量在2%以上、3.5%以下。 19. A method for producing 13 to 18 in any one of claims high strength stainless steel for oil well pipes, characterized in that, in mass%, the content of Mo is over 2%, 3.5% or less.
20.如权利要求13~19中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外以质量%计还含有Cu:0.5%以上、3.5%以下的组成。 20. The oil according to a method of any one of 13 to 19 high strength stainless steel tube manufactured as claimed in claim wherein, said composition having outside mass%, further containing Cu: 0.5% to 3.5% the following components.
21.如权利要求20所述的油井用高强度不锈钢管的制造方法,其特征在于,以质量%计,所述Cu的含量在0.5%以上、1.14%以下。 21. The well according to claim 20 The method for manufacturing a high strength stainless steel pipe, characterized in that, in mass%, the content of Cu is 0.5% or more, 1.14% or less.
22.如权利要求13~21中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外,以质量%计还含有选自Nb:0.03%以上、0.2%以下,Ti:0.03%以上、0.3%以下,Zr:0.03%以上、0.2%以下,W:0.2%以上、3%以下,B:0.0005%以上、0.01%以下中的1种或2种以上的组成。 22. claimed in any one of claims 13 to 21 wells, characterized in that the method for manufacturing a high strength stainless steel pipe having outside of the composition, in terms of mass%, Nb: 0.03% , 0.2%, Ti: not more than 0.03%, 0.3% or less, Zr: 0.03% or more, 0.2% or less, W: more than 0.2%, 3% or less, B: 0.0005% or more, 0.01% or less of one or two or more kinds of components.
23.如权利要求13~22中任一项所述的油井用高强度不锈钢管的制造方法,其特征在于,具有在所述组成之外以质量%计还含有Ca:0.0005%以上、0.01%以下的组成。 23. The oil well 22 in any one of claims 13 to claim a method of manufacturing a high strength stainless steel pipe, characterized by having a composition outside said further contains by mass%, Ca: 0.0005% or more, 0.01% the following components.
CN 200480023557 2003-08-19 2004-08-11 High strength stainless steel pipe excellent in corrosion resistance for use in oil well and method for production thereof CN100451153C (en)

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