JPH02247360A - Martensitic stainless steel having high strength and excellent corrosion resistance and stress corrosion cracking resistance and its manufacture - Google Patents
Martensitic stainless steel having high strength and excellent corrosion resistance and stress corrosion cracking resistance and its manufactureInfo
- Publication number
- JPH02247360A JPH02247360A JP6871589A JP6871589A JPH02247360A JP H02247360 A JPH02247360 A JP H02247360A JP 6871589 A JP6871589 A JP 6871589A JP 6871589 A JP6871589 A JP 6871589A JP H02247360 A JPH02247360 A JP H02247360A
- Authority
- JP
- Japan
- Prior art keywords
- less
- stainless steel
- resistance
- martensitic stainless
- steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 85
- 230000007797 corrosion Effects 0.000 title claims abstract description 85
- 238000005336 cracking Methods 0.000 title claims abstract description 32
- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 36
- 239000010959 steel Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 39
- 238000001816 cooling Methods 0.000 abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 23
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 23
- 238000005496 tempering Methods 0.000 abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 6
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract 2
- 235000011089 carbon dioxide Nutrition 0.000 abstract 1
- 229910052721 tungsten Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910000734 martensite Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- -1 for example Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Landscapes
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Articles (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高強度かつ耐食性、耐応力腐食割れ性の優れた
マルテンサイト系ステンレス鋼に係り、さらに詳しくは
例えば石油・天然ガスの掘削、輸送および貯蔵において
湿潤炭酸ガスや湿潤硫化水素を含む環境中で高い腐食抵
抗および割れ抵抗を有し強度の高い鋼に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to martensitic stainless steel with high strength, excellent corrosion resistance, and stress corrosion cracking resistance. and relates to high-strength steels with high corrosion resistance and cracking resistance in environments containing wet carbon dioxide and wet hydrogen sulfide during storage.
（従来の技術）
近年生産される石油・天然ガス中には、湿潤な炭酸ガス
を多く含有する場合が増加している。こうした環境中で
炭素鋼や低合金鋼は著しく腐食することがよく知られて
いる。このため、掘削に使用される油井管や輸送に使用
されるラインパイプなどの防食対策として、腐食抑制剤
の添加が従来より行なわれてきた。゛しかじ、腐食抑制
剤は高温ではその効果が失われる場合が多いことに加え
て、海洋油井や海底バイブラインでは腐食抑制剤の添加
・回収処理に要する費用は膨大なものとなり、適用でき
ない場合が多い。従って、腐食抑制剤を添加する必要の
ない耐食材料に対するニーズが最近とみに高まっている
。(Prior Art) Oil and natural gas produced in recent years increasingly contain a large amount of wet carbon dioxide. It is well known that carbon steel and low alloy steel corrode significantly in such environments. For this reason, corrosion inhibitors have traditionally been added to prevent corrosion of oil country tubular goods used for drilling, line pipes used for transportation, and the like. However, in addition to the fact that corrosion inhibitors often lose their effectiveness at high temperatures, the cost of adding and recovering corrosion inhibitors in offshore oil wells and undersea vibrating lines is enormous, so there are cases where they cannot be applied. There are many. Therefore, the need for corrosion-resistant materials that do not require the addition of corrosion inhibitors has recently increased.
炭酸ガスを多く含む石油・天然ガス用の耐食材料として
は、耐食性の良好なステンレス鋼の適用がまず検討され
、例えばり、 Ｊ、 クライン。As a corrosion-resistant material for petroleum and natural gas containing a large amount of carbon dioxide gas, the application of stainless steel with good corrosion resistance was first considered; for example, J. Klein et al.
コロージョン゛８４．ペーパーナンバー２１１にあるよ
うに、高強度で比較的コストの安い鋼としてＡｌ５Ｉ４
ＬＯあるいは４２０といった、１２〜１３％のＣｒを含
有するマルテンサイト系ステンレス鋼が広く使用され始
めている。しかしながら、これらの鋼は湿潤炭酸ガス環
境ではあっても高温、たとえば１３０℃以上での環境や
ＣＩ！ イオン濃度の高い環境では耐食性が充分ではな
くなり、腐食速度が大きいという難点を有する。さらに
これらの鋼は、石油・天然ガス中に硫化水素が含まれて
いる場合には著しく耐食性が劣化し、全面腐食や局部腐
食、さらには応力腐食割れ（この場合には硫化物応力割
れ、以下ＳＳＣと称する）を生ずるという難点を有【２
ている。このため上記のマルテンサイト系ステンレス鋼
の使用は、例えばＨ２Ｓ分圧が０．００１気圧とい−・
た極微量のＨ２Ｓを含むか、あるいは全＜ Ｈ２Ｓ ｆ
２よない場合に限られてきた。Corrosion 84. As stated in paper number 211, Al5I4 is a high-strength and relatively low-cost steel.
Martensitic stainless steels containing 12-13% Cr, such as LO or 420, are beginning to be widely used. However, even if these steels are used in a humid carbon dioxide environment, they are exposed to high temperatures such as 130°C or higher, and CI! In an environment with high ion concentration, corrosion resistance is insufficient and the corrosion rate is high. Furthermore, when hydrogen sulfide is contained in oil or natural gas, the corrosion resistance of these steels deteriorates significantly, causing general corrosion, localized corrosion, and even stress corrosion cracking (in this case, sulfide stress cracking). It has the disadvantage of causing SSC (referred to as SSC) [2
ing. Therefore, when using the above martensitic stainless steel, the H2S partial pressure is, for example, 0.001 atm.
contains trace amounts of H2S, or total < H2S f
It has been limited to cases where there is no 2.
これに対し、硫化水素による割れに対する抵抗を増した
マルテンサイト系ステンレス鋼として、例えば特開昭８
０−１７４８５９号公報、特開昭６２−５４０６３号公
報にみられる鋼が提案されている。しか（２、これらの
鋼も硫化水素による割れを完全に防ｉｆ＝、 ｔ。On the other hand, as a martensitic stainless steel with increased resistance to cracking due to hydrogen sulfide, for example,
Steels disclosed in Japanese Patent Application Laid-open No. 0-174859 and Japanese Patent Application Laid-Open No. 62-54063 have been proposed. However, (2, these steels also completely prevent cracking due to hydrogen sulfide if =, t.
た訳ではなく、また高価な合金元素であるニッケルを多
量に使用するためコストが高いという難点を有している
。However, it also has the disadvantage of high cost because it uses a large amount of nickel, which is an expensive alloying element.
（発明が解決しようとする課題）
本発明はこうした現状に鑑み、高温や高Ｃ，９濃度の炭
酸ガス環境でも充分な耐食性を有し、硫化水素を含む場
合においてもＳＳＣに対して高い割れ抵抗を有する安価
なマルテンサイト系ステンレス鋼を提供することを目的
としている。(Problems to be Solved by the Invention) In view of the current situation, the present invention has sufficient corrosion resistance even in high temperature and carbon dioxide environments with high C and 9 concentrations, and has high cracking resistance against SSC even when hydrogen sulfide is contained. The purpose of the present invention is to provide an inexpensive martensitic stainless steel having the following characteristics.
（課題を解決するための手段）
本発明者らは、上記の目的を達成すべくマルテンサイト
系ステンレス鋼の成分を種々検討してきた結果、ついに
以下の知見を見出すに至った。(Means for Solving the Problem) The present inventors have studied various components of martensitic stainless steel in order to achieve the above object, and as a result, they have finally found the following knowledge.
まず、Ｃ「を８〜１４％含有する鋼中にＣυを添加する
と湿潤炭酸ガス環境中における腐食速度が著しく小さく
なることを見出した。そしてこのＣｕの添加効果は、添
加量を１．２％とすると顕著であり、湿潤炭酸ガス環境
中に１８０℃以上まで実用的に使用できるようになるこ
とを見出した。また、Ｃｕを１．２％以上添加した場合
には、（Ｊｔを０．１％以下に低減しても高温で完全に
オーステナイト化させることができることも見出した。First, we found that when Cυ was added to steel containing 8 to 14% C, the corrosion rate in a wet carbon dioxide environment was significantly reduced. It has been found that it can be used practically at temperatures above 180°C in a humid carbon dioxide environment.Furthermore, when Cu is added in an amount of 1.2% or more, (Jt becomes 0.1 It has also been found that complete austenitization can be achieved at high temperatures even when the content is reduced to % or less.
ＣｕはＮｌに比べるとはるかに安価な元素であるので、
１．２％以上を添加しても材料コストの上昇は少ないの
である。一方、Ｃｕを１．２％以上添加しＣを０．１％
以下に低減させた鋼にＮを０．００５％以上含有させる
と一段と高強度が得られ、かつ耐食性も改善されること
がわかった。このときかかる成分を有する鋼は硫化水素
を含む環境においてもＳＳＣに対して高い割れ抵抗を有
するという新知見も得られた。Since Cu is a much cheaper element than Nl,
Even if 1.2% or more is added, the increase in material cost is small. On the other hand, 1.2% or more of Cu is added and 0.1% of C is added.
It has been found that when the N content is reduced to below 0.005% or more, even higher strength can be obtained and corrosion resistance is also improved. At this time, new findings were also obtained that steel with such components has high cracking resistance against SSC even in environments containing hydrogen sulfide.
さらに本発明者らは検討をすすめ、Ｃｕを１．２％以上
添加し、Ｃを０．１％以下に低減し、Ｎを０．００５％
以上添加した鋼中のＰを０．０２５％以下に低減しＳを
０．０１５％以下に低減すると硫化水素を含む環境にお
ける割れ抵抗が一段と改善されることを明らかにした。Furthermore, the present inventors conducted further studies and added 1.2% or more of Cu, reduced C to 0.1% or less, and added 0.005% of N.
It has been revealed that by reducing the P content in the steel added above to 0.025% or less and the S content to 0.015% or less, the cracking resistance in an environment containing hydrogen sulfide is further improved.
一方、これらの鋼にＮｉおよびＭｏを添加すれば高温あ
るいは高Ｃ９−イオン濃度の湿潤炭酸ガス環境での腐食
速度を一段と減少できることも見出した。On the other hand, we have also found that the corrosion rate can be further reduced by adding Ni and Mo to these steels at high temperatures or in a humid carbon dioxide environment with a high C9- ion concentration.
本発明は上記の知見に基づいてなされたものであり、
第１発明の要旨とするところは、重量％で、Ｃ０，０２
〜０．１％、Ｓｉ１％以下、Ｍｎ２％以下、Ｃｒ８〜１
４％、Ｃｕ １．２〜４．５％、Ａｌ ０．００５〜０
．２％、Ｎ ０．００５〜０．１５％を含有し、残部Ｆ
ｅおよび不可避不純物からなることを特徴２′、する高
強度かつ耐食性、耐応力腐食割れ性の優れたマルテンサ
イト系ステンレス鋼にあり、
第２発明の要旨とするところは、第１発明の鋼において
不可避不純物のうち、重量％で、Ｐを０．０２５％以下
、Ｓを０．０１５％以下に低減したことを特徴とする高
強度かつ耐食性、耐応力腐食割れ性の優れたマルテンサ
イト系ステンレス鋼にあり、第３発明の要旨とするとこ
ろは、第１発明および第２発明の６鋼において、重量％
で、Ｎｉ４％以下、Ｍｏ ２％以下、Ｗ４％以下のうち
１種または２種以上を含有すること、を特徴とする高強
度かつ耐食性、耐応力腐食割れ性の優れたマルテンサイ
ト系ステンレス鋼にあり、
第４発明の要旨とするところは、第１発明、第２発明お
よび第３発明の６鋼において、重量％で、Ｖ ０．５％
以下、７１ ０．２％以下、Ｎｂ ０．５％以下、Ｔ
ａ ０．２％以下、Ｚｒ ０．２％以下、Ｈｒ
０．２５％以下、のうち１８または２種以上を含有する
ことを特徴とする高強度かつ耐食性、耐応力腐食割れ性
の優れたマルテンサイト系ステンレス鋼にあり、第５発
明の要旨とするところは、第１発明、第２発明、第３発
明および第４発明の６鋼において、重量％で、Ｃａ０．
００８％以下、希土類元素０．０２％以下、のうち１種
または２種を含有することを特徴とする高強度かつ耐食
性、耐応力腐食割れ性の優れたマルテンサイト系ステン
レス鋼にあり、第６発明の要旨とするところは、第１発
明、第２発明、第３発明、第４発明および第５発明の６
鋼において、９２０℃〜１１００℃でオーステナイト化
した後、空冷以上の冷却速度で冷却し、次いで５８０℃
以上Ａ ＣＬ温度以下の温度で焼戻し処理を施した後、
空冷以上の冷却速度で冷却することを特徴とする高強度
かつ耐食性、耐応力腐食割れ性の優れたマルテンサイト
系ステンレス鋼の製造方法にある。The present invention has been made based on the above knowledge, and the gist of the first invention is that C0.02
~0.1%, Si1% or less, Mn2% or less, Cr8~1
4%, Cu 1.2-4.5%, Al 0.005-0
．． 2%, N 0.005-0.15%, balance F
Characteristic 2' is a martensitic stainless steel that has high strength, corrosion resistance, and stress corrosion cracking resistance, and is composed of e and unavoidable impurities. A martensitic stainless steel with high strength, excellent corrosion resistance, and stress corrosion cracking resistance, characterized by reducing P to 0.025% or less and S to 0.015% or less by weight among unavoidable impurities. The gist of the third invention is that in the six steels of the first invention and the second invention, the weight %
A martensitic stainless steel with high strength, excellent corrosion resistance, and stress corrosion cracking resistance, which is characterized by containing one or more of Ni 4% or less, Mo 2% or less, and W 4% or less. Yes, the gist of the fourth invention is that in the six steels of the first invention, second invention, and third invention, V 0.5% in weight%.
Below, 71 0.2% or less, Nb 0.5% or less, T
a 0.2% or less, Zr 0.2% or less, Hr
The fifth aspect of the invention resides in a martensitic stainless steel with high strength, excellent corrosion resistance, and stress corrosion cracking resistance, characterized by containing 18 or 2 or more of the following: 0.25% or less In the six steels of the first invention, second invention, third invention and fourth invention, Ca0.
It is a martensitic stainless steel with high strength, excellent corrosion resistance, and stress corrosion cracking resistance, characterized by containing one or two of the following: The gist of the invention is the six aspects of the first invention, second invention, third invention, fourth invention, and fifth invention.
In steel, after austenitizing at 920°C to 1100°C, cooling at a cooling rate higher than air cooling, then 580°C
After performing tempering treatment at a temperature below the ACL temperature,
The present invention provides a method for producing martensitic stainless steel having high strength, excellent corrosion resistance, and stress corrosion cracking resistance, which is characterized by cooling at a cooling rate higher than that of air cooling.
（作 用）
以下に本発明で成分および熱処理条件を限定した理由を
述べる。(Function) The reasons for limiting the components and heat treatment conditions in the present invention will be described below.
Ｃ：Ｃはマルテンサイト系ステンレス鋼の強度を上昇さ
せる元素としでもっとも安定的かつ低コストであるから
、必要な強度を確保するために０．０２％以上の添加が
必要であるが、０．１％を超えて添加すると耐食性をＭ
Ｌ、 ＜低下させることから、上限含有量は０．１％
とずべきである。C: Since C is the most stable and low-cost element that increases the strength of martensitic stainless steel, it is necessary to add 0.02% or more to ensure the necessary strength. If added in excess of 1%, corrosion resistance may be reduced.
L, <Since it lowers, the upper limit content is 0.1%
It should be done.
Ｓｉ ：脱酸のために必要な元素であるが、１％を超え
て添加すると耐食性を著り、＜低トさせることから、上
限含有量は１％と１べきである。Si: This is an element necessary for deoxidation, but if it is added in an amount exceeding 1%, the corrosion resistance will be markedly reduced and the upper limit content should be 1%.
Ｍｎ：脱酸および強度確保のために有効な元素であるが
、２％を超えて添加するとその効果は飽和するので、上
限含有量は２％とする。Mn: An effective element for deoxidizing and ensuring strength, but if added in an amount exceeding 2%, the effect is saturated, so the upper limit content is set to 2%.
Ｃｒ：Ｃｒはマルテンサイト系ステンレス鋼を構成する
もっとも基本的かつ必須の元素であって耐食性を付与す
るために必要な元素であるが、含有量が８％未満では耐
食性が充分ではなく、一方１４％を超えて添加すると他
の合金元素をいかに調整しても高温に加熱したときにオ
ーステナイト単相になり難く強度確保が困難になるので
上限含有量は１４％とすべきである。Cr: Cr is the most basic and essential element constituting martensitic stainless steel and is necessary to impart corrosion resistance, but if the content is less than 8%, corrosion resistance is insufficient; %, no matter how you adjust the other alloying elements, it will be difficult to form a single austenite phase when heated to a high temperature, making it difficult to ensure strength, so the upper limit content should be 14%.
Ｃｕ：Ｃｕは湿潤炭酸ガス環境におけるマルテンサイト
系ステンレス鋼の腐食速度を著しく減少させ、Ｃおよび
Ｎの含有量を調整することによって硫化水素を含む環境
におけるＳＳＣ感受性を顕著に添加させる極めて有用な
元素であるが、含有量が１．２％未満ではこれらの効果
が不充分であり、４．５％を超えて添加してもその効果
は飽和するばかりか熱間加工性を著しく低下させるよう
になるので、１，２〜４．５％の範囲に限定する。Cu: Cu is an extremely useful element that significantly reduces the corrosion rate of martensitic stainless steel in a humid carbon dioxide environment and significantly increases SSC susceptibility in an environment containing hydrogen sulfide by adjusting the C and N contents. However, if the content is less than 1.2%, these effects are insufficient, and if it is added in excess of 4.5%, the effects not only become saturated but also significantly reduce hot workability. Therefore, it is limited to a range of 1.2 to 4.5%.
Ａｇ：脱酸のために必要な元素であって含有量が０．０
０５％未満ではその効果が充分ではなく、０．２％を超
えて添加すると粗大な酸化物系介在物が鋼中に残留して
硫化水素中での割れ抵抗を低下させるので、含有量範囲
は０．００５〜０．２％とした。Ag: An element necessary for deoxidation and the content is 0.0
If it is less than 0.05%, the effect is not sufficient, and if it is added more than 0.2%, coarse oxide inclusions will remain in the steel and reduce the cracking resistance in hydrogen sulfide, so the content range is The content was set at 0.005 to 0.2%.
Ｎ ：ＮはＣと同様にマルテンサイト系ステンレス鋼の
強度を上昇させる元素として有効であるが、０．００５
％未満ではその効果が充分ではなく、０．１５％を超え
るとＣｒ窒化物を生成して耐食性を低下させ、また、割
れ抵抗をも低下させるので、含有量範囲は０．００５〜
０．１５９（ｉとした。N: Like C, N is effective as an element for increasing the strength of martensitic stainless steel, but 0.005
If the content is less than 0.15%, the effect will not be sufficient, and if it exceeds 0.15%, Cr nitrides will be produced, reducing corrosion resistance and cracking resistance. Therefore, the content range is from 0.005 to
It was set as 0.159 (i).
以上が本発明における基本的成分であるが、本発明にお
いては必要に応じてさらに以下の元素を添加して特性を
一段と向上させることができる。The above are the basic components in the present invention, but in the present invention, the following elements can be further added as necessary to further improve the characteristics.
Ｐ ：ＰはＳＳＣ感受性を増加させる元素であるので少
ないほうが好ましいがあまりに少ないレベルにまで低減
させることはいたずらにカストを上昇させるのみで特性
の改善効果は飽和するものであるから、本発明の目的と
する耐食性、耐応力腐食割れ性を確保するのに必要充分
なほど少ない含有量として０．０２５％以下に低減する
と耐応力腐食割れ性が一段と改善される。P: Since P is an element that increases SSC susceptibility, it is preferable to reduce it to a low level, but reducing it to too low a level will only unnecessarily increase cast and the effect of improving properties will be saturated, which is the purpose of the present invention. When the content is reduced to 0.025% or less, which is sufficiently small to ensure the desired corrosion resistance and stress corrosion cracking resistance, the stress corrosion cracking resistance is further improved.
Ｓ ：ＳはＰと同様にＳＳＣ感受性を増加させる元素で
あるので少ないほうが好ましいがあまりに少ないレベル
にまで低減させることはいたずらにコストを上昇させる
のみで特性の改善効果は飽和するものであるから、本発
明の目的とする耐食性、耐応力腐食割れ性を確保するの
に必要充分なほど少ない含有量として０．０１５％以下
に低減すると耐応力腐食割れ性が一段と改善される。S: Like P, S is an element that increases SSC sensitivity, so it is preferable to have less S, but reducing it to too low a level will only unnecessarily increase costs and the effect of improving properties will be saturated. When the content is reduced to 0.015% or less, which is sufficiently small to ensure the corrosion resistance and stress corrosion cracking resistance that are the objectives of the present invention, the stress corrosion cracking resistance is further improved.
ＮＩ：ＮＩは１，２％以上のＣｕと共存して湿潤炭酸ガ
ス環境の耐食性をさらに改善するのに効果があるが、４
％を超えて添加してもその効果は飽和するばかりか、逆
に硫化水素含有環境におけるＳＳＣ抵抗を低下させるよ
うになるので上限含有量は４％とする。NI: NI is effective in coexisting with 1.2% or more of Cu to further improve corrosion resistance in a wet carbon dioxide environment, but 4
If it is added in excess of 4%, the effect will not only be saturated, but it will also reduce the SSC resistance in an environment containing hydrogen sulfide, so the upper limit content is set at 4%.
Ｍｏ：Ｍｏは１．２％以上のＣｕと共存して湿潤炭酸ガ
ス環境の耐食性を改善するのに効果があるが、２％を超
えて添加してもその効果は飽和するばかりか、靭性など
他の特性を低下させるようになるので上限含有量は２％
とする。Mo: Mo coexists with 1.2% or more of Cu and is effective in improving corrosion resistance in a wet carbon dioxide environment, but adding more than 2% not only saturates the effect but also improves toughness, etc. The upper limit content is 2% as it reduces other properties.
shall be.
Ｗ ：Ｗも１．２％以上のＣｕと共存して湿潤炭酸ガス
環境の耐食性を改善するのに効果があるが、４％を超え
て添加して、もその効果は飽和するばかりか、靭性など
他の特性を低下させるようになるので上限含有量は４％
とする。W: W also coexists with 1.2% or more of Cu and is effective in improving corrosion resistance in a wet carbon dioxide environment, but when added in excess of 4%, not only does the effect become saturated, but the toughness also decreases. The upper limit of content is 4% because it reduces other properties such as
shall be.
Ｖ、ＴＩ、Ｎｂ、Ｔａ、Ｚｒ、Ｈｆ’ ：Ｖ、ＴＩ。V, TI, Nb, Ta, Zr, Hf': V, TI.
Ｎｂ、Ｔａ、Ｚｒ、Ｈｆ’は耐食性を一段と向上させる
のに有効な元素であるが、ＴＩ 、Ｚｒ、Ｔａ。Nb, Ta, Zr, and Hf' are effective elements for further improving corrosion resistance, but TI, Zr, and Ta.
Ｈｒでは０．２％、Ｎｂ、Ｖでは０．５％をそれぞれ超
えて添加すると粗大な析出物・介在物を生成して硫化水
素含有環境におけるＳＳＣ抵抗を低下させるようになる
ので上限含有量は７１．Ｚｒ。If Hr is added in excess of 0.2% and Nb and V are added in excess of 0.5%, coarse precipitates and inclusions will be generated and the SSC resistance will decrease in an environment containing hydrogen sulfide, so the upper limit content is 71. Zr.
Ｔａ、Ｈｒでは０．２％、Ｎｂ、Ｖでは０．５％とした
。Ta and Hr were set at 0.2%, and Nb and V were set at 0.5%.
Ｃａ、希土類元素：Ｃａおよび希土類元素（ＲＥＭ）は
熱間加工性の向上、耐食性の向上に効果のある元素であ
るが、Ｃａではｏ、ｏｏｇ％を超えて、希土類元素では
０．０２％を超えて添加すると、それぞれ粗大な非金属
介在物を生成して逆に熱間加工性および耐食性を劣化さ
せるので、上限含有量はＣａでは０．００８％、希土類
元素では０．０２％とした。なお、本発明において希土
類元素とは原子番号が５７〜７１番および８９〜１０３
番の元素およびＹを指す。Ca, rare earth elements: Ca and rare earth elements (REM) are elements that are effective in improving hot workability and corrosion resistance, but Ca exceeds o, oog%, and rare earth elements exceed 0.02%. If added in excess, coarse non-metallic inclusions will be formed and the hot workability and corrosion resistance will deteriorate, so the upper limit content was set to 0.008% for Ca and 0.02% for rare earth elements. In addition, in the present invention, rare earth elements include those having atomic numbers of 57 to 71 and 89 to 103.
Refers to the number element and Y.
上記の成分を存するステンレス鋼を熱処理してマルテン
サイト組織とし所定の強度を付与するに際し、オーステ
ナイト化温度を９２０〜１１００℃としたのは、９２０
℃より低い温度ではオーステナイト化が充分ではなく従
って必要な強度を得ることが困難だからであり、オース
テナイト化温度が１１００℃を超えると結晶粒が著しく
粗大化して硫化水素含有環境におけるＳＳＣ抵抗が低下
するようになるので、オーステナイト化温度は９２０〜
１１００℃とした。When heat-treating stainless steel containing the above components to form a martensitic structure and imparting a predetermined strength, the austenitizing temperature was set at 920 to 1100°C.
This is because at temperatures lower than 1100°C, austenitization is not sufficient and it is therefore difficult to obtain the necessary strength, and when the austenitization temperature exceeds 1100°C, the crystal grains become significantly coarsened and the SSC resistance in an environment containing hydrogen sulfide decreases. Therefore, the austenitizing temperature is 920 ~
The temperature was 1100°C.
オーステナイト化後の冷却における冷却速度を空冷以上
の冷却速度としたのは、空冷よりも遅い冷却速度ではマ
ルテンサイトが充分生成せず、所定の強度を確保するこ
とが困難になるからである。The reason why the cooling rate in cooling after austenitization is set to be higher than air cooling is because martensite is not sufficiently generated at a cooling rate slower than air cooling, making it difficult to secure a predetermined strength.
焼戻し温度を５８０℃以上Ａｃ１温度以下としたのは、
焼戻し温度が５８０℃未満では充分な焼戻しが行われず
、焼戻し温度がＡｃ１温度を超えると一部がオーステナ
イト化しその後の冷却時にフレッシュ・マルテンサイト
を生成し、いずれも充分に焼戻しされていないマルテン
サイトが残留するために硫化水素含有環境におけるＳＳ
Ｃ感受性を増加させるためである。The tempering temperature was set to 580°C or higher and Ac1 temperature or lower because
If the tempering temperature is less than 580°C, sufficient tempering will not be performed, and if the tempering temperature exceeds the Ac1 temperature, part of the part will turn into austenite and produce fresh martensite during subsequent cooling, and in both cases, martensite that has not been sufficiently tempered will become austenite. SS in hydrogen sulfide-containing environments to remain
This is to increase sensitivity to C.
焼戻し後の冷却における冷却速度を空冷以上の冷却速度
としたのは、空冷よりも遅い冷却速度では靭性が低下す
るためである。The reason why the cooling rate in cooling after tempering was set to be higher than air cooling is because toughness decreases at a cooling rate slower than air cooling.
本発明鋼は、通常の熱間圧延によって鋼板として使用す
ることが可能であるし、熱間押出あるいは熱間圧延によ
って鋼管として使用することも可能であるし、棒あるい
は線として使用することも勿論可能である。本発明鋼は
、油井管あるいはラインパイプとしての用途のほか、バ
ルブやポンプの部品としてなど多くの用途がある。The steel of the present invention can be used as a steel plate by ordinary hot rolling, can be used as a steel pipe by hot extrusion or hot rolling, and of course can be used as a bar or wire. It is possible. The steel of the present invention has many uses, such as as oil country tubular goods or line pipes, as well as parts for valves and pumps.
（実 施 例） 以下に本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
第１表に示す成分のステンレス鋼を溶製し、熱間圧延に
よって厚さ１２ｍｍの鋼板とした後、第１表に併せて示
す条件で焼入れ焼戻し処理を施していずれも０．２％オ
フセット耐力が８３ｋｇ／−以上の高強度ステンレス鋼
とした。次にこれらの鋼材から試験片を採取して湿潤炭
酸ガス環境における腐食試験、および硫化水素含有環境
におけるＳＳＣ試験を行なった。湿潤炭酸ガス環境にお
ける腐食試験としては、厚さ３龍、幅１５＋ｎ、長さ５
０ｍ＋ｓの試験片を用い、試験温度１５０℃および１８
０℃のオートクレーブ中で炭酸ガス分圧４０気圧の条件
で３％ＮａＣｊＪ水溶液中に３０日間浸漬して、試験前
後の重量変化から腐食速度を算出した。腐食速度の単位
はｎ＋ｍ／ｙで表示したが、−船釣にある環境における
ある材料の腐食速度が０．ｉｏ＋ｓ／ｙ以下の場合、材
料は充分耐食的であり使用可能であると考えられている
。硫化水素含有環境におけるＳＳＣ試験としては、ＮＡ
ＣＥ （米国腐食技術者協会）の定めている標準試験法
であるＮＡＣＥ規格ＴＭ０１７７に従って試験した。即
ち、１気圧の硫化水素を飽和させた５％ＮａＣ，９＋０
．５％酢酸水溶液中にセットした試験片に一定の単軸引
張応力を負荷し、７２０時間以内に破断するか否か、を
調べた。After melting stainless steel with the ingredients shown in Table 1 and hot rolling it into a steel plate with a thickness of 12 mm, it was quenched and tempered under the conditions shown in Table 1, resulting in a 0.2% offset yield strength. It is made of high-strength stainless steel with a weight of 83 kg/- or more. Next, test pieces were taken from these steel materials and subjected to a corrosion test in a humid carbon dioxide environment and an SSC test in a hydrogen sulfide-containing environment. For corrosion testing in a humid carbon dioxide environment, the thickness is 3mm, the width is 15+n, and the length is 5mm.
Using a 0 m+s test piece, the test temperature was 150°C and 18
The specimens were immersed in a 3% NaCjJ aqueous solution for 30 days at a carbon dioxide gas partial pressure of 40 atmospheres in an autoclave at 0°C, and the corrosion rate was calculated from the weight change before and after the test. The unit of corrosion rate is n+m/y, but - if the corrosion rate of a certain material in a boat fishing environment is 0. If io+s/y or less, the material is considered sufficiently corrosion resistant to be usable. For SSC testing in an environment containing hydrogen sulfide, NA
The test was conducted in accordance with NACE standard TM0177, which is a standard test method established by CE (American Society of Corrosion Engineers). That is, 5% NaC, 9+0 saturated with 1 atm hydrogen sulfide.
．． A constant uniaxial tensile stress was applied to a test piece set in a 5% acetic acid aqueous solution, and it was examined whether it would break within 720 hours.
試験応力は各鋼材の０．２％オフセット耐力の６０％の
値とした。The test stress was set to a value of 60% of the 0.2% offset proof stress of each steel material.
試験結果を第１表に併せて示した。第１表のうち、腐食
試験結果において◎は腐食速度が０．０５ｍｍ／ｙ未満
、Ｏは腐食速度が０．０５ｍｍ／ ７以上０，１０ｔａ
ｇ／’／未満、×は腐食速度が０．１ｍｍ／ｙ以上０．
５ｍｍ／）’未満、××は腐食速度が０．５ｍ＋＊／ｙ
以上、であったことをそれぞれ表わしており、ＳＳＣ試
験結果において◎は破断じなかったもの、×は破断した
ものをそれぞれ表わしている。なお、第１表において比
較鋼のＮｏ、２９はＡｌ５Ｉ４２０鋼であり、漱３０は
９Ｃｒ−ＩＭｏ鋼であって、いずれも従来から湿潤炭酸
ガス環境で使用されている従来鋼である。The test results are also shown in Table 1. In Table 1, in the corrosion test results, ◎ means the corrosion rate is less than 0.05mm/y, O means the corrosion rate is 0.05mm/7 or more 0.10ta
Less than g/'/, × indicates corrosion rate of 0.1 mm/y or more and 0.
Less than 5mm/)', XX indicates corrosion rate of 0.5m++/y
In the SSC test results, ◎ indicates that the sample did not break, and × indicates that it did. In Table 1, comparative steel No. 29 is Al5I420 steel, and No. 30 is 9Cr-IMo steel, both of which are conventional steels conventionally used in a humid carbon dioxide environment.
第１表から明らかなように本発明鋼である鋼Ｎｏ、１〜
２８は、湿潤炭酸ガス環境において１８０℃という従来
のマルテンサイト系ステンレス鋼では考えられないよう
な高温であっても、実用的に使用可能な腐食速度である
Ｏ、ｌ＋ａｍ／ｙよりも腐食速度が小さく、かつ硫化水
素含有環境におけるＳＳＣ試験においても破断していな
いことから、優れた耐食性と耐応力腐食割れ性を有して
いることがわかる。これに対して比較鋼である鋼Ｎｏ、
２９〜３４は湿潤炭酸ガス環境において１５０℃でも
既に腐食速度が０．１ｍｍ／ｙを大きく上回っており、
かつ硫化水素含有環境におけるＳＳＣ試験において破断
している。As is clear from Table 1, steel Nos. 1 to 1, which are the steels of the present invention,
28 has a corrosion rate that is higher than the practically usable corrosion rate of O, l + am/y, even at a high temperature of 180°C in a humid carbon dioxide environment, which is unthinkable for conventional martensitic stainless steel. It is small and did not break in the SSC test in an environment containing hydrogen sulfide, which indicates that it has excellent corrosion resistance and stress corrosion cracking resistance. On the other hand, steel No., which is a comparative steel,
29 to 34, the corrosion rate is already much higher than 0.1 mm/y even at 150°C in a wet carbon dioxide environment,
Moreover, it fractured in the SSC test in an environment containing hydrogen sulfide.
（発明の効果）
以上述べたように、本発明は湿潤炭酸ガス環境における
優れた耐食性と湿潤硫化水素による割れに対して高い割
れ抵抗を有する鋼およびその製造方法を提供することを
可能としたものであり、産業の発展に貢献するところ極
めて大である。(Effects of the Invention) As described above, the present invention makes it possible to provide a steel having excellent corrosion resistance in a wet carbon dioxide environment and high cracking resistance against cracking caused by wet hydrogen sulfide, and a method for manufacturing the same. Therefore, it is extremely important to contribute to the development of industry.
復代理人sub-agent
Claims (6)
高強度かつ耐食性、耐応力腐食割れ性の優れたマルテン
サイト系ステンレス鋼。(1) In weight%, C 0.02-0.1%, Si 1% or less, Mn 2% or less, Cr 8-14%, Cu 1.2-4.5%, Al 0.005-0. 2%, N 0.005 to 0.15%, and the remainder consisting of Fe and unavoidable impurities. A martensitic stainless steel with high strength, excellent corrosion resistance, and stress corrosion cracking resistance.
つ耐食性、耐応力腐食割れ性の優れたマルテンサイト系
ステンレス鋼。(2) High strength, corrosion resistance, and stress corrosion cracking resistance according to claim 1, characterized in that, among unavoidable impurities, P is reduced to 0.025% or less and S to 0.015% or less. Martensitic stainless steel with excellent properties.
請求項１または２に記載の高強度かつ耐食性、耐応力腐
食割れ性の優れたマルテンサイト系ステンレス鋼。(3) The high-quality steel according to claim 1 or 2, which contains one or more of Ni 4% or less, Mo 2% or less, and W 4% or less as an additional component. Martensitic stainless steel with excellent strength, corrosion resistance, and stress corrosion cracking resistance.
請求項１または２または３に記載の高強度かつ耐食性、
耐応力腐食割れ性の優れたマルテンサイト系ステンレス
鋼。(4) As additional components, in weight%, V 0.5% or less, Ti 0.2% or less, Nb 0.5% or less, Ta 0.2% or less, Zr 0.2% or less, Hf 0.2 % or less, high strength and corrosion resistance according to claim 1, 2 or 3, characterized in that it contains one or more of the following:
Martensitic stainless steel with excellent stress corrosion cracking resistance.
項１または２または３または４に記載の高強度かつ耐食
性、耐応力腐食割れ性の優れたマルテンサイト系ステン
レス鋼。(5) Claim 1 or 2 or 3 or 4, characterized in that it contains one or two of the following as an additional component: Ca 0.008% or less, rare earth element 0.02% or less. A martensitic stainless steel with high strength, corrosion resistance, and stress corrosion cracking resistance.
載のマルテンサイト系ステンレス鋼を、９２０℃〜１１
００℃でオーステナイト化した後、空冷以上の冷却速度
で冷却し、次いで５８０℃以上Ａｃ＿１温度以下の温度
で焼戻し処理を施した後、空冷以上の冷却速度で冷却す
ることを特徴とする高強度かつ耐食性、耐応力腐食割れ
性の優れたマルテンサイト系ステンレス鋼の製造方法。(6) The martensitic stainless steel according to claim 1 or 2 or 3 or 4 or 5 is heated at 920°C to 11°C.
High strength and A method for manufacturing martensitic stainless steel with excellent corrosion resistance and stress corrosion cracking resistance.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1068715A JP2602319B2 (en) | 1989-03-20 | 1989-03-20 | High-strength, high-temperature, high-chloride-ion-concentration, wet carbon dioxide gas-corrosion-resistant, martensitic stainless steel excellent in stress corrosion cracking resistance and method for producing the same |
| US07/480,599 US5049210A (en) | 1989-02-18 | 1990-02-15 | Oil Country Tubular Goods or a line pipe formed of a high-strength martensitic stainless steel |
| EP90103026A EP0384317A1 (en) | 1989-02-18 | 1990-02-16 | Martensitic stainless steel and method of heat treatment of the steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1068715A JP2602319B2 (en) | 1989-03-20 | 1989-03-20 | High-strength, high-temperature, high-chloride-ion-concentration, wet carbon dioxide gas-corrosion-resistant, martensitic stainless steel excellent in stress corrosion cracking resistance and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02247360A true JPH02247360A (en) | 1990-10-03 |
| JP2602319B2 JP2602319B2 (en) | 1997-04-23 |
Family
ID=13381766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1068715A Expired - Fee Related JP2602319B2 (en) | 1989-02-18 | 1989-03-20 | High-strength, high-temperature, high-chloride-ion-concentration, wet carbon dioxide gas-corrosion-resistant, martensitic stainless steel excellent in stress corrosion cracking resistance and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2602319B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0499154A (en) * | 1990-08-03 | 1992-03-31 | Nippon Steel Corp | High cr steel for high strength line pipe excellent in weldability |
| JPH08246107A (en) * | 1995-03-10 | 1996-09-24 | Nippon Steel Corp | Martensitic stainless steel excellent in carbon dioxide corrosion resistance and sulfide stress corrosion cracking resistance |
| US6090230A (en) * | 1996-06-05 | 2000-07-18 | Sumitomo Metal Industries, Ltd. | Method of cooling a steel pipe |
| US8157930B2 (en) | 2001-10-18 | 2012-04-17 | Sumitomo Metal Industries, Ltd. | Martensitic stainless steel |
| WO2016170761A1 (en) * | 2015-04-21 | 2016-10-27 | Ｊｆｅスチール株式会社 | Martensitic stainless steel |
| EP3444371A4 (en) * | 2016-04-12 | 2019-04-10 | JFE Steel Corporation | Martensitic stainless steel sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5113463A (en) * | 1974-07-24 | 1976-02-02 | Sharp Kk | Shitsukikokantaino seizohoho |
| JPS59173245A (en) * | 1983-03-24 | 1984-10-01 | Sumitomo Metal Ind Ltd | Steel for oil well pipe excellent in corrosion resistance |
| JPS62103319A (en) * | 1982-02-19 | 1987-05-13 | Kawasaki Steel Corp | Production of stainless steel products having high strength and excellent resistance to corrosion, stress corrosion cracking and sulfide cracking |
-
1989
- 1989-03-20 JP JP1068715A patent/JP2602319B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5113463A (en) * | 1974-07-24 | 1976-02-02 | Sharp Kk | Shitsukikokantaino seizohoho |
| JPS62103319A (en) * | 1982-02-19 | 1987-05-13 | Kawasaki Steel Corp | Production of stainless steel products having high strength and excellent resistance to corrosion, stress corrosion cracking and sulfide cracking |
| JPS59173245A (en) * | 1983-03-24 | 1984-10-01 | Sumitomo Metal Ind Ltd | Steel for oil well pipe excellent in corrosion resistance |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0499154A (en) * | 1990-08-03 | 1992-03-31 | Nippon Steel Corp | High cr steel for high strength line pipe excellent in weldability |
| JPH08246107A (en) * | 1995-03-10 | 1996-09-24 | Nippon Steel Corp | Martensitic stainless steel excellent in carbon dioxide corrosion resistance and sulfide stress corrosion cracking resistance |
| US6090230A (en) * | 1996-06-05 | 2000-07-18 | Sumitomo Metal Industries, Ltd. | Method of cooling a steel pipe |
| US8157930B2 (en) | 2001-10-18 | 2012-04-17 | Sumitomo Metal Industries, Ltd. | Martensitic stainless steel |
| WO2016170761A1 (en) * | 2015-04-21 | 2016-10-27 | Ｊｆｅスチール株式会社 | Martensitic stainless steel |
| CN107532259A (en) * | 2015-04-21 | 2018-01-02 | 杰富意钢铁株式会社 | Martensitic stain less steel |
| US10655195B2 (en) | 2015-04-21 | 2020-05-19 | Jfe Steel Corporation | Martensitic stainless steel |
| EP3444371A4 (en) * | 2016-04-12 | 2019-04-10 | JFE Steel Corporation | Martensitic stainless steel sheet |
| US10988825B2 (en) | 2016-04-12 | 2021-04-27 | Jfe Steel Corporation | Martensitic stainless steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2602319B2 (en) | 1997-04-23 |
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