JPS60200914A - Manufacture of steel superior in hydrogen corrosion cracking resistance - Google Patents
Manufacture of steel superior in hydrogen corrosion cracking resistanceInfo
- Publication number
- JPS60200914A JPS60200914A JP5644984A JP5644984A JPS60200914A JP S60200914 A JPS60200914 A JP S60200914A JP 5644984 A JP5644984 A JP 5644984A JP 5644984 A JP5644984 A JP 5644984A JP S60200914 A JPS60200914 A JP S60200914A
- Authority
- JP
- Japan
- Prior art keywords
- steel
- hydrogen
- hydrogen corrosion
- cracking resistance
- strength
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は耐水素侵食割れ性にすぐれた鋼の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing steel with excellent hydrogen corrosion cracking resistance.
背景技術
一般に室温近傍の温度域では鋼への水素の固溶量は水素
圧が数百気圧でも微／Ｊ％であり、鋼の脆化をきたすこ
とは稀であるが、石油Ｍ製などの２００〜６００Ｃの温
度域で、水素を多量に含むガス体などの環境で使用され
る圧力容器などに使用する鋼には水床侵食と呼ばれる内
部損傷を生ずることがある。この損傷は鋼中に拡散侵入
した水素原子が鋼中の炭化物と反応して生成するメタン
ガスが鋼中に容易に拡散しないために炭化物の析出位置
でメタンガスによる圧力を生じ、この位置で空調を生ず
ることが知られている。この対策としては、従来よりＯ
ｒやＭ。Background Art Generally, in the temperature range near room temperature, the amount of solid solution of hydrogen in steel is only a small amount per J% even if the hydrogen pressure is several hundred atmospheres, and it is rare that steel becomes embrittled. In the temperature range of 200 to 600 C, internal damage called water bed erosion may occur in steel used in pressure vessels and the like used in environments such as gas containing a large amount of hydrogen. This damage occurs when the hydrogen atoms that have diffused into the steel react with the carbides in the steel, producing methane gas that does not easily diffuse into the steel. This creates pressure from the methane gas at the location where the carbides are deposited, causing air conditioning at this location. It is known. As a countermeasure for this, conventional
r and M.
などの合金元素を添加して銅の強度を上げるとともに水
素に対して、より安定な炭化物を形成させる方法が開発
されているが、未だこのような水素侵食による損傷を十
分に免かれることができないのが現状でおる。A method has been developed to increase the strength of copper by adding alloying elements such as , and to form carbides that are more stable against hydrogen, but it is still not possible to sufficiently avoid damage caused by hydrogen attack. This is the current situation.
発明の概要
本発明はこのような現状に鑑み、石油精製装置などの水
素侵食が問題となる装置に使用される鋼として必要な強
度を維持しつ又耐水嵩侵食割れ性において従来の＃をは
るかに凌ぐ鋼の製造方法を提供するもので、重量％でＣ
： ０，０１〜ＯｊＯ％、Ｓｉ ： ０．０１〜１．０
％、Ｍｎ ：０，０１〜２．０％、Ｍｏ ： ｆ］、ｌ
〜２．Ｑ％を含み、さらに必要に応じてＯｒ ： ５
．５％以下、Ａｊ？、Ｔｉ、Ｎｂ、Ｖの１種又は２種以
上＝０．２％以下を添加し、残部は実質的にＦｅ より
成る鋼をＡＣ３変態点の±７０Ｃの温度範囲に加熱した
後、冷却過程の６０ＤＣ以上の温度で圧下率１０％以上
の加工を行ない、続いてＩ Ｃ／ ｓｅｃ以下の冷却速
度で４００Ｃまで冷却し共析変態を行なわせることを特
徴とする耐水素侵食割れ性にすぐれた鋼の製造方法全要
旨とするものである。Summary of the Invention In view of the current situation, the present invention has been developed to maintain the strength necessary for steel used in equipment where hydrogen corrosion is a problem, such as oil refineries, and to improve water bulk erosion and cracking resistance far superior to conventional steel. This method provides a method for manufacturing steel that surpasses C in weight percent.
: 0.01~OjO%, Si: 0.01~1.0
%, Mn: 0.01-2.0%, Mo: f], l
~2. Including Q%, and if necessary, Or: 5
．． Less than 5%, Aj? , Ti, Nb, and V (one or more types = 0.2% or less), and the remainder is essentially Fe. After heating the steel to a temperature range of ±70C of the AC3 transformation point, the cooling process is performed. Steel with excellent hydrogen erosion cracking resistance characterized by processing at a reduction rate of 10% or more at a temperature of 60DC or higher, and then cooling to 400C at a cooling rate of IC/sec or lower to cause eutectoid transformation. This is a complete summary of the manufacturing method.
詳細な説明
一般にこの釉のＭＯ鋼、Ｏｒ−Ｍｏ鋼は焼入れ焼もどし
ＪＰ規準焼もどしの熱処理ヲ経て使用されるが、この場
合鋼の組織は低温変態生成物であるマルテンサイトやベ
イナイトが焼戻され、主に結晶粒界に炭化物が連結して
析出した状態にある。このような組織では水素侵食によ
り結晶粒シ目
界に沿って連結した９訳が形成され、鋼の著しい劣化を
招く。一方、熱処理によって共析変態とが研究の結果見
い出された。この結果に基き／＜ ５イ１４−微細に分
散析出させる加工熱処理法を行なったところ耐水素侵食
性にすぐれた鋼を製造し得ることが明らかになり、本発
明法に成功するに到ったものである。即ちオーステナイ
ト化温度であるＡＣ３変態点の近傍（±７０ｃ）に加熱
することにより初期オーステナイト結晶粒の粗大化警防
ぐとともにオーステナイトとフェライトの２相混合域に
おいて加工を加えることにより続いて生ずるオーステナ
イト相の共析変態にか又わる結晶粒を微細となしかつ分
散させることができる。このような加工熱処理を経た組
織は微細なフェライトとパーライトの混合組織であり、
而も、パーライトが分散している剥
ため水素侵食による９論の連結が抑制され、鋼の劣化を
軽減させるものである。Detailed Description Generally, this glazed MO steel and Or-Mo steel are used after undergoing heat treatment of quenching, tempering, and JP standard tempering. The carbides are mainly connected and precipitated at grain boundaries. In such a structure, hydrogen erosion causes formation of crystals connected along the grain boundaries, leading to significant deterioration of the steel. On the other hand, research has revealed that heat treatment causes eutectoid transformation. Based on this result, it became clear that steel with excellent hydrogen corrosion resistance could be produced by carrying out a processing heat treatment method that causes finely dispersed precipitation, and the method of the present invention was successful. It is something. That is, by heating to a temperature close to the AC3 transformation point (±70c), which is the austenitizing temperature, coarsening of the initial austenite crystal grains is prevented, and by processing in the two-phase mixing region of austenite and ferrite, the subsequent austenite phase is prevented. Crystal grains related to eutectoid transformation can be made fine and dispersed. The structure that has undergone such processing heat treatment is a mixed structure of fine ferrite and pearlite.
Moreover, the connection of theory 9 due to hydrogen erosion due to the dispersion of pearlite is suppressed, thereby reducing the deterioration of the steel.
一般に共析変態によって生ずるフェライト、パーライト
の混合組織を有する鋼では、マルテンサイトやペイナイ
トヲ焼戻しだ組織に較べて強度が低くなるが、本発明の
加工熱処理では結晶粒の微細化ＶＣよってこの強度低下
全抑制している。従ってＭｎ、Ｏｒ、Ｍｏ などの合金
元素の少ない鋼では２相混合域での圧下率を太きくしな
ければならないので、本発明のような合金成分を有する
鋼では所定の強度と耐水素侵食性の見地から１０％以上
の圧下率が必要である。圧下率は上限を特に限定しない
が、圧延設備の能力や圧延スケジュールなどによりきめ
られる。同様にオーステナイト化温度が高くなると初期
のオーステナイト結晶粒を粗大化して、これに続く加工
によっても微細な結晶粒を得ることが困難なため初期の
加熱温度の上限奮オーステナイト変態点ＡＣ３より上の
７０Ｃに制限するが、一方この加熱温度が低すぎると炭
素のオーステナイトへの充分な固溶が得られなくなり、
２相温度域加工後の炭化物析出が期待できなくなるので
、加熱温度の下限１Ａｃ３変態点以下の７０ｃとする。In general, steel with a mixed structure of ferrite and pearlite produced by eutectoid transformation has lower strength than a structure in which martensite or paynite is tempered, but in the heat treatment of the present invention, this strength reduction is completely eliminated by the grain refinement VC. It's suppressed. Therefore, in steels with few alloying elements such as Mn, Or, Mo, etc., the reduction ratio in the two-phase mixing region must be increased, so in steels with alloying elements such as those of the present invention, it is necessary to achieve the specified strength and hydrogen corrosion resistance. From this point of view, a reduction ratio of 10% or more is required. The upper limit of the rolling reduction rate is not particularly limited, but is determined depending on the capacity of the rolling equipment, rolling schedule, etc. Similarly, when the austenitizing temperature becomes high, the initial austenite crystal grains become coarse, and it is difficult to obtain fine crystal grains by subsequent processing. However, if this heating temperature is too low, sufficient solid solution of carbon into austenite will not be obtained.
Since carbide precipitation cannot be expected after two-phase temperature range processing, the lower limit of the heating temperature is set to 70c, which is below the 1Ac3 transformation point.
又２相温度域での加工後、Ｉ Ｃ／ Ｓｅｃ以下の冷却
速度で４００ｉ、’Ｊで冷却させるのは、炭化物の析出
をこの温度域まで抑え微細な共析変態によるパーライト
【化成させるためである。冷却速度は特に下限を限定し
ないが、あまり速度を遅くすると生産性が低下する。ま
た４００Ｃ以下にまでこの冷却速度で冷却させるとマル
テンサイトやベイナイトなどの低温変態生成物が形成さ
れるため、この冷却速度で冷却する温度の下限を４００
Ｃとした。In addition, after processing in the two-phase temperature range, the reason for cooling at 400 i, J at a cooling rate of less than I C/Sec is to suppress the precipitation of carbides to this temperature range and to form pearlite through fine eutectoid transformation. be. There is no particular lower limit to the cooling rate, but if the cooling rate is too slow, productivity will decrease. In addition, if the temperature is cooled to 400C or less at this cooling rate, low-temperature transformation products such as martensite and bainite will be formed, so the lower limit of the temperature for cooling at this cooling rate should be set to 400C or lower.
It was set as C.
本発明はこのように鋼の組織を加工熱処理によって微細
化することによって強度の向上と微細分散したパーライ
ト組織によって耐水素侵食性の改善全図ったものである
。In this way, the present invention aims to improve the strength of the steel by making the structure of the steel finer through processing and heat treatment, and to improve the hydrogen corrosion resistance due to the finely dispersed pearlite structure.
次に本発明における鋼の成分範囲限定の理由について説
明する。Next, the reason for limiting the range of steel components in the present invention will be explained.
Ｃｏｏは安価な強化元素として鋼の強度を保つためには
０．・０１％以上が必要である。しかし０．６０％を超
えると靭性、溶接性を劣化さぜる。Coo is an inexpensive reinforcing element that is required to maintain the strength of steel.・More than 0.01% is required. However, if it exceeds 0.60%, toughness and weldability deteriorate.
Ｓｉ： Ｓｉは脱酸のためには０．０１％以上が必要で
あるが、１％を超えると靭性、溶接性全劣化させる。Si: 0.01% or more of Si is required for deoxidation, but if it exceeds 1%, toughness and weldability are completely degraded.
Ｍｎ”、 ＭｎはＳの固定及び鋼の強化に必要な元素で
あり、この目的には０．０１％以上を必要とするが、２
％を超えると靭性、溶接性全劣化させる。Mn", Mn is an element necessary for fixing S and strengthening steel, and for this purpose requires 0.01% or more, but 2.
%, the toughness and weldability will deteriorate completely.
Ｍｏ ： Ｍｏは耐クリープ特性に必要な元素であり、
この目的には０．１％以上が必要である。しかし２％を
超えると加工熱処理後の冷却過程でマルテンザイト組織
となって微細なパーライトを分散させることができない
ため本発明の目的を辻成することができない。Mo: Mo is an element necessary for creep resistance,
For this purpose, 0.1% or more is required. However, if it exceeds 2%, a martenzite structure forms during the cooling process after processing and heat treatment, making it impossible to disperse fine pearlite, making it impossible to achieve the object of the present invention.
Ｏｒ ： Ｏｒは耐クリープ特性に必要であるが６．５
％を超えると加工熱処理後の冷却過程でマルテンザイト
組織となってＭＯ同様、微細なパーライトを分散させる
ことができなくなる。Or: Or is necessary for creep resistance, but is 6.5
If it exceeds %, a martenzite structure will be formed in the cooling process after processing heat treatment, and like MO, fine pearlite cannot be dispersed.
ｈｅ ： ｈｅは脱酸に必要な元素であるか、０，２％
以上を超えると溶接性を劣化させる。he: He is an element necessary for deoxidation, or 0.2%
Exceeding the above results in deterioration of weldability.
Ｔｉ、Ｎｂ、Ｖ ：これらの元素は炭化物の安定に有効
であるが、総量で０．２％を超えるとパーライトの分散
形態をそこない、微細なパーライトを分散させることが
できなくなる。Ti, Nb, V: These elements are effective in stabilizing carbides, but if the total amount exceeds 0.2%, the dispersion form of pearlite will be impaired, making it impossible to disperse fine pearlite.
以下、本発明を実施例を示して説明する。Hereinafter, the present invention will be explained by showing examples.
実施例
下記第１表に示す４種の鋼を溶製し、２０訪厚の銅板に
熱間圧延し、これに第１表に併記した熱処理を与えた後
試験片に加工し、オートクレーブ中にて応力を加えずに
設置し温度と水素圧との条件全（／Ｊ ５００ Ｃ１２
００峙／ｃｒｒｒ’ （Ｂ〕４００ｃ、２００ｋｇ／ｄ
、（Ｃ）５００Ｃ，２００ｋｙ ／ ｃｍ’としてＩ
Ｏ，０００時間保持した。次いで、この試験片をオート
クレーブより取り出し、実験温度と同じ温度で引張試験
全行ない、オートクレーブ中で水素侵食試験全行なった
ものと同−鋼で水素侵食試験を行なわない試験片との引
張伸びを比較することにより水素侵食による鋼の劣化を
評価した。即ち、水素侵食感受性因子全水素侵食試験後
の引張伸び／水素侵食試験前の引張伸びと定義して、そ
の因子が０．７以下のものを×、０．７〜０．９を△、
０．９以上のものを○として、その結果を同じ第１表に
併記する。Examples Four types of steel shown in Table 1 below were melted and hot-rolled into a copper plate with a thickness of 20 mm.After being subjected to the heat treatment listed in Table 1, it was processed into a test piece and placed in an autoclave. Installed without applying stress, and under all conditions of temperature and hydrogen pressure (/J 500 C12
00/crrr' (B) 400c, 200kg/d
, (C) 500C, 200ky/cm' as I
It was held for 0,000 hours. Next, this test piece was taken out of the autoclave and subjected to a full tensile test at the same temperature as the experimental temperature, and the tensile elongation was compared between a test piece that underwent all hydrogen attack tests in the autoclave and a test piece made of the same steel but not subjected to a hydrogen attack test. The deterioration of steel due to hydrogen attack was evaluated by this method. That is, the hydrogen attack susceptibility factor is defined as the tensile elongation after the total hydrogen attack test/the tensile elongation before the hydrogen attack test, and the factor is 0.7 or less as ×, 0.7 to 0.9 as △,
Those of 0.9 or more are marked as ○, and the results are also listed in the same Table 1.
上記第１表に示した実験結果はＭ、鋼、Ｏｒ−ＭＯ鋼の
いずれも従来の熱処理に比較し、本発明による加工熱処
理法が耐水素侵食割れ性にすぐれたものであることを示
している。The experimental results shown in Table 1 above show that the processing heat treatment method of the present invention has excellent hydrogen corrosion cracking resistance compared to conventional heat treatment for M, steel, and Or-MO steel. There is.
Claims (1)
０％、Ｍｎ １１．０１〜２−０％、ＭＯＯｊ〜２．０
％を含有し、さらに必要に応じＣｒ ５．５％以下、Ａ
Ｊ。 Ｔｉ、Ｎｂ、Ｖの１種又は２ね以上Ｊ２％以下を含有し
、残部は実質的にＦｅ より成る鋼をＡＯ３変態点の±
７０Ｃ（Ｄ温度範囲に加熱した後、冷却過程の６０００
以上の温度で圧下率で１０％以上の加工を行ない、続い
てＩ ｉ：ｌ’ ／ Ｓｅｃ以下の冷却速度で４０００
まで冷却して共析変態を行なわせることを特徴とする耐
水素侵食割れ性にすぐれた鋼の製造方法。[Claims] 10 with CO, O+~0.30%, Si 0101~1.
0%, Mn 11.01~2-0%, MOOj~2.0
%, and if necessary Cr 5.5% or less, A
J. A steel containing one or more of Ti, Nb, and V and J2% or less, with the remainder substantially consisting of Fe, is heated to
After heating to 70C (D temperature range, 6000C in the cooling process)
Processing is carried out at a reduction rate of 10% or more at a temperature above, and then a cooling rate of 4000
A method for producing steel with excellent hydrogen erosion cracking resistance, which is characterized by cooling to a temperature of 100°C to cause eutectoid transformation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5644984A JPS60200914A (en) | 1984-03-24 | 1984-03-24 | Manufacture of steel superior in hydrogen corrosion cracking resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5644984A JPS60200914A (en) | 1984-03-24 | 1984-03-24 | Manufacture of steel superior in hydrogen corrosion cracking resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60200914A true JPS60200914A (en) | 1985-10-11 |
Family
ID=13027403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5644984A Pending JPS60200914A (en) | 1984-03-24 | 1984-03-24 | Manufacture of steel superior in hydrogen corrosion cracking resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60200914A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115852242A (en) * | 2021-09-24 | 2023-03-28 | 宝山钢铁股份有限公司 | High-temperature high-pressure hydrogen corrosion resistant thick steel plate and manufacturing method thereof |
-
1984
- 1984-03-24 JP JP5644984A patent/JPS60200914A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115852242A (en) * | 2021-09-24 | 2023-03-28 | 宝山钢铁股份有限公司 | High-temperature high-pressure hydrogen corrosion resistant thick steel plate and manufacturing method thereof |
| CN115852242B (en) * | 2021-09-24 | 2024-03-08 | 宝山钢铁股份有限公司 | High-temperature high-pressure hydrogen corrosion-resistant thick steel plate and manufacturing method thereof |
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