JPH0152464B2 - - Google Patents
Info
- Publication number
- JPH0152464B2 JPH0152464B2 JP11646084A JP11646084A JPH0152464B2 JP H0152464 B2 JPH0152464 B2 JP H0152464B2 JP 11646084 A JP11646084 A JP 11646084A JP 11646084 A JP11646084 A JP 11646084A JP H0152464 B2 JPH0152464 B2 JP H0152464B2
- Authority
- JP
- Japan
- Prior art keywords
- less
- amount
- martensitic stainless
- stainless steel
- 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.)
- Expired
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- 229910001208 Crucible steel Inorganic materials 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 229910001105 martensitic stainless steel Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000009864 tensile test Methods 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 238000005496 tempering Methods 0.000 description 9
- 229910000734 martensite Inorganic materials 0.000 description 6
- 229910001566 austenite Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Structures Of Non-Positive Displacement Pumps (AREA)
- Rolling Contact Bearings (AREA)
Description
〔発明の利用分野〕
本発明は、高耐食性マルテンサイト系ステンレ
ス鋳鋼に係り、特に原子炉等の高温高圧水中にお
いて使用されるインペラ、デイフユーザ、ケーシ
ングなどの材料として好適な高耐食性マルテンサ
イト系ステンレス鋳鋼に関するものである。
〔発明の背景〕
従来、水中において使用されるインペラ、デイ
フユーザ、ケーシングなどは耐食性、強度、靭性
の観点から、13％Cr系マルテンサイト系ステン
レス鋳鋼が主に使用されている。特に、原子炉等
の高温水中において使用される場合には、高温強
度、補修溶接の難易性および応力除去焼なまし特
性等からNiを含む13％Cr系マルテンサイト系ス
テンレス鋳鋼が多用される傾向にある。
しかしながら、上述したNiを含む13％Cr系マ
ルテンサイト系ステンレス鋳鋼は原子炉環境を模
擬した高温高圧純水中で低ひずみ速度引張試験
（以下、SSRT試験と称す）を実施すると、応力
腐食割れ（以下、SCCと略記する）を起し、実用
上問題を有していた。
〔発明の目的〕
本発明の目的は、高温高圧水中の耐SCC性が良
好で、しかも高強度、高靫性で溶接の容易な13％
Crマルテンサイト系ステンレス鋳鋼を提供する
にある。
〔発明の概要〕
本発明に係る高耐食性マルテンサイト系ステン
レス鋳鋼は、重量比にてＣ：0.02〜0.07％、Si：
0.1〜0.25％、Mn：0.1〜0.4％、Cr：11〜15％、
Ni：３〜６％およびMo：2.6％以下を含有し、
特にSi＋１／２Mn量が0.4％以下であり、残部がFe
および不可避不純物からなることを特徴としてい
る。一般に、13％Crマルテンサイト系ステンレ
ス鋳鋼は、溶解−製練の際に脱酸、脱硫する目的
でSiおよびMnが付加され、通常Si0.3〜0.6％およ
びMn0.5〜0.8％程度が含有されている。
本発明は高耐食性で、高強度、高靭性でかつ溶
接性の容易な13％Crマルテンサイト系ステンレ
ス鋳鋼を得るため、SiおよびMnの含有量を0.25
％以下および0.40％以下におさえ、SCC感受性を
示さないように改善すると共に、288℃の原子炉
環境模擬試験液において、従来材料（伸び10％）
に比べて約50％高い伸び15％に改良したものであ
る。
次に、本発明に係るNiを含むマルテンサイト
系ステンレス鋳鋼の化学成分を上記のように限定
した理由は次の通りである。
Ｃ：0.02〜0.07％
ＣはFe−Cr合金のオーステナイト領域を拡大
し、焼入性を高めると共に、強さに付与する元素
であるが、0.02％以下ではその効果が小さい一
方、0.07％を越えると、Crと結合して炭化物を生
成し、耐食性を著しく害するばかりでなく、溶接
性が悪くなるので、Ｃは0.02〜0.07％の範囲に限
定した。特に強度面から最も好ましい範囲として
は0.04〜0.06％の範囲である。
Si：0.4％以下
Siは脱酸剤として付加し、基地を強化するが、
SCC感受性に悪い影響を与える主要な元素であ
り、そのため上限を0.4％とした。また、Siは溶
鋼の湯流れに大きく影響するため、精密な型に鋳
込むためには、下限値は0.1％以上とすることが
好ましい。
Mn：0.80％以下
Mnは製練の際、脱酸および脱硫剤として必要
な元素であり、かつ基地を強化するが、Siと同様
にSCC感受性に悪い影響を及ぼす主な元素である
ため、Mn付加量の上限を0.80％とした。また、
Mnの下限値は脱硫効果を考慮して硫黄の含有値
（0.01％）に対して約10倍の0.1％以上は必要であ
る。ただし、SiおよびMnはSCC感受性を小さく
する観点から、Si＋１／２Mn量が0.4％以下に調整
する必要がある。
Cr：11〜15％
Crは鋼の焼入性を増し、強度を上げるのに重
要な元素である。また、腐食環境の下でステンレ
ス鋼の表面を不働態化する作用を有する元素であ
つて、ステンレス鋼の耐食性を向上させるのに不
可欠の元素である。その含有量は11％以下ではそ
の効果が小さい一方、15％を越えるとデルタフエ
ライトが析出し、脆くなるのでCrの量は11〜15
％とした。
Ni：３〜６％
NiはＣと同様にオーステナイト生成元素であ
つて、焼入性を増加すると共に、強度を上げ、さ
らに残留オーステナイトを生じて靭性を増すと同
時に、溶接性を向上させる元素である。Ni量が
３％以下ではこのような効果が小さい。また、６
％を越えると残留オーステナイト量（以下、rR量
という）が増えて強度が低下するので、Ni量は
３〜６％範囲に限定した。
Mo：2.6％以下
Moは強度および耐食性を増すのに必要な元素
であるが、Mo量の増加と共に靭性が徐々に低下
し、2.6％を越えると急速に靭性が低下するので、
Mo量の上限は2.6％とした。
一般に、含Ni13％Crマルテンサイト系ステン
レス鋼は、Ni量および焼入、焼もどし温度によ
つて残留オーステナイト量（rR量）が異つてい
る。例えば３％Ni量を含む13％Cr鋼では、630℃
焼もどし処理でrR量は約10％であり、Ni量が６
％になると、600℃の焼もどしではrR量は40％と
高くなる。
rR量はNi量によつて変化し、Ni量を一定とし
rR量が最大となる焼もどし温度（靭性が最大とな
る温度）の前後ではrR量が急激に変化する。
この焼もどし温度は13％Cr系鋼の組織図にお
けるAc1〜Ac3変態区間、すなわちα−γ二相領
域の間である。そして焼もどし後の金属組織は主
に焼もどしマルテンサイトであつて、一部Ni量
によつて残留オーステナイト相が生成する。
この焼もどし後の冷却過程では、微量の焼入れ
マルテンサイトが生成するが、組織上では判別は
困難である。
このように、Ac1変態点以上で焼もどすことに
よつて、高温焼もどしマルテンサイトの生成を利
用して高強度、高靫性化を図つている。しかし、
鋳鋼品となると、靭性が低下するという問題があ
る。そこで、靭性の低下の少ないもので、かつ耐
SCC性に優れたマルテンサイト系ステンレス鋼と
しては主要な化学成分をそれほど変えることな
く、特にSiおよびMn量を調整させることによつ
て、高温水中で耐食性、強度、溶接性、および靭
性に優れたものを開発することができた。
以下、本発明の実施例を詳細に説明する。
＜実施例 １＞
第１表に示す化学組成の13％Cr系鋼（本発明
鋼と比較鋼）を19種溶製して造塊した後、1000℃
×5hの拡散処理を施し、焼入（950℃×2h→Ａ，
Ｃ）および焼もどし（620℃×5h→Ａ，Ｃ）を実
施した。
[Field of Application of the Invention] The present invention relates to highly corrosion-resistant martensitic stainless steel cast steel, and in particular, highly corrosion-resistant martensitic stainless steel cast steel suitable as a material for impellers, diffusers, casings, etc. used in high-temperature, high-pressure water in nuclear reactors and the like. It is related to. [Background of the Invention] Conventionally, 13% Cr martensitic stainless cast steel has been mainly used for impellers, diffusers, casings, etc. used underwater, from the viewpoints of corrosion resistance, strength, and toughness. In particular, when used in high-temperature water such as in nuclear reactors, 13% Cr-based martensitic stainless steel cast steel containing Ni tends to be frequently used due to its high-temperature strength, difficulty in repair welding, and stress relief annealing properties. It is in. However, when the above-mentioned 13% Cr martensitic stainless steel cast steel containing Ni is subjected to a low strain rate tensile test (hereinafter referred to as SSRT test) in high-temperature, high-pressure pure water that simulates a nuclear reactor environment, it shows stress corrosion cracking (SSRT test). (hereinafter abbreviated as SCC), which was a practical problem. [Objective of the Invention] The object of the present invention is to provide a 13% carbon fiber which has good SCC resistance in high-temperature, high-pressure water, and which has high strength, high adhesion, and is easy to weld.
We provide Cr martensitic stainless steel cast steel. [Summary of the Invention] The highly corrosion-resistant martensitic stainless steel cast steel according to the present invention has a weight ratio of C: 0.02 to 0.07% and Si:
0.1~0.25%, Mn: 0.1~0.4%, Cr: 11~15%,
Contains Ni: 3 to 6% and Mo: 2.6% or less,
In particular, it is characterized in that the amount of Si+1/2Mn is 0.4% or less, with the remainder consisting of Fe and unavoidable impurities. Generally, 13% Cr martensitic stainless steel cast steel has Si and Mn added for the purpose of deoxidizing and desulfurizing during melting and smelting, and usually contains about 0.3 to 0.6% Si and 0.5 to 0.8% Mn. has been done. In order to obtain a 13% Cr martensitic stainless steel cast steel with high corrosion resistance, high strength, high toughness, and easy weldability, the content of Si and Mn is reduced to 0.25.
% or less and 0.40% or less so as not to exhibit SCC susceptibility, and in the reactor environment simulating test liquid at 288℃, compared to conventional material (10% elongation)
The elongation has been improved to 15%, which is about 50% higher than that of the original. Next, the reason why the chemical components of the Ni-containing martensitic stainless cast steel according to the present invention are limited as described above is as follows. C: 0.02 to 0.07% C is an element that expands the austenite region of Fe-Cr alloys, improves hardenability, and imparts strength. Below 0.02%, the effect is small, while above 0.07%. Since C combines with Cr to form carbides, which not only significantly impairs corrosion resistance but also deteriorates weldability, C is limited to a range of 0.02 to 0.07%. In particular, from the viewpoint of strength, the most preferable range is 0.04 to 0.06%. Si: 0.4% or less Si is added as a deoxidizer and strengthens the base, but
It is a major element that has a negative effect on SCC susceptibility, so the upper limit was set at 0.4%. Furthermore, since Si greatly affects the flow of molten steel, the lower limit is preferably 0.1% or more in order to cast it into a precise mold. Mn: 0.80% or less Mn is a necessary element as a deoxidizing and desulfurizing agent during smelting and strengthens the base, but like Si, it is the main element that has a negative effect on SCC susceptibility. The upper limit of the amount added was set at 0.80%. Also,
The lower limit of Mn needs to be 0.1% or more, about 10 times the sulfur content (0.01%), taking into account the desulfurization effect. However, from the viewpoint of reducing the SCC sensitivity of Si and Mn, it is necessary to adjust the amount of Si+1/2Mn to 0.4% or less. Cr: 11-15% Cr is an important element for increasing the hardenability and strength of steel. Further, it is an element that has the effect of passivating the surface of stainless steel in a corrosive environment, and is an essential element for improving the corrosion resistance of stainless steel. If the content is less than 11%, the effect will be small, but if it exceeds 15%, delta ferrite will precipitate and become brittle, so the amount of Cr should be 11 to 15%.
%. Ni: 3-6% Like C, Ni is an austenite-forming element that increases hardenability, increases strength, produces residual austenite, increases toughness, and improves weldability. be. This effect is small when the Ni content is 3% or less. Also, 6
%, the amount of retained austenite (hereinafter referred to as r R amount) increases and the strength decreases, so the amount of Ni was limited to a range of 3 to 6%. Mo: 2.6% or less Mo is an element necessary to increase strength and corrosion resistance, but as the amount of Mo increases, toughness gradually decreases, and when it exceeds 2.6%, toughness decreases rapidly.
The upper limit of the amount of Mo was set at 2.6%. Generally, the amount of retained austenite ( R amount) of Ni-containing 13% Cr martensitic stainless steel varies depending on the amount of Ni and the quenching and tempering temperatures. For example, for 13% Cr steel containing 3% Ni, 630℃
In the tempering process, the r R amount is approximately 10%, and the Ni amount is 6
%, in tempering at 600°C, the r R amount becomes as high as 40%. r The amount of R changes depending on the amount of Ni, assuming the amount of Ni is constant.
The r R amount changes rapidly before and after the tempering temperature where the r R amount is maximum (the temperature where the toughness is maximum). This tempering temperature is between the Ac 1 to Ac 3 transformation zone in the microstructure diagram of the 13% Cr steel, that is, the α-γ two-phase region. The metal structure after tempering is mainly tempered martensite, and a retained austenite phase is partially formed depending on the amount of Ni. In the cooling process after tempering, a small amount of quenched martensite is generated, but it is difficult to distinguish it from the structure. In this way, by tempering at a temperature above the Ac 1 transformation point, high strength and high tenacity are achieved by utilizing the formation of high temperature tempered martensite. but,
When it comes to cast steel products, there is a problem of reduced toughness. Therefore, we decided to use a material with less decrease in toughness and durability.
As a martensitic stainless steel with excellent SCC properties, it has excellent corrosion resistance, strength, weldability, and toughness in high-temperature water by adjusting the amount of Si and Mn without changing the main chemical components. I was able to develop things. Examples of the present invention will be described in detail below. <Example 1> 19 types of 13% Cr steel (invention steel and comparison steel) having the chemical composition shown in Table 1 were melted and made into ingots, and then heated at 1000°C.
Diffusion treatment for x5h, quenching (950℃ x 2h→A,
C) and tempering (620°C x 5h → A, C) were performed.
以上のように本発明によれば、高温高圧水中に
おいてもSCCを防止することができ、かつ腐食損
傷から起る腐食疲労等を防止することができる高
耐食性マルテンサイト系ステンレス鋳鋼を提供す
ることができるという効果を有する。
As described above, according to the present invention, it is possible to provide a highly corrosion-resistant martensitic stainless cast steel that can prevent SCC even in high-temperature, high-pressure water and can prevent corrosion fatigue caused by corrosion damage. It has the effect of being able to.
第１図は13％Crマルテンサイト系ステンレス
鋳鋼の高温水中のSCC感受性の有無とSiおよび
Mn付加量との関係を示す線図、第２図は本発明
鋼および比較鋼の伸び率とSCC感受性の有無を示
す線図、第３図はSi量を種々変えてMn量と伸び
率との関係を示す線図、第４図はSi量と伸び率と
の関係を示す線図、第５図は13％Crマルテンサ
イト系ステンレス鋳鋼の（Si＋１／２Mn）量と伸び
率との関係を示す線図、第６図はABWRに用い
るインターナルポンプの概要断面図である。
１……インペラ、２……デイフユーザ、３……
スタンドボルト、５……ポンプシヤフト、６……
モータ。
Figure 1 shows the presence or absence of SCC susceptibility of 13%Cr martensitic stainless steel cast steel in high-temperature water, Si and
Figure 2 is a diagram showing the relationship between the amount of Mn added and the elongation rate of the invention steel and comparative steel, and the presence or absence of SCC susceptibility. Figure 4 is a diagram showing the relationship between Si content and elongation rate. Figure 5 is a diagram showing the relationship between (Si+1/2Mn) content and elongation rate of 13%Cr martensitic stainless steel cast steel. The diagram shown in FIG. 6 is a schematic sectional view of an internal pump used in ABWR. 1... impeller, 2... differential user, 3...
Stand bolt, 5... Pump shaft, 6...
motor.
Claims (1)
下、Mn：0.8％以下、Cr：11〜15％、Ni：３〜
６％およびMo：2.6％以下を含有し、Si＋１／２Mn 量が0.4％以下であり、残部Feおよび不可避的不
純物からなることを特徴とする高温高圧水中の高
耐食性マルテンサイト系ステンレス鋳鋼。 ２ 特許請求の範囲第１項において、前記高耐食
性マルテンサイト系ステンレス鋼は、288℃の原
子炉環境模擬試験液において低ひずみ速度引張試
験でSCC破面率が０％を示し、かつ伸びが14％以
上を有することを特徴とする高温高圧水中の高耐
食性マルテンサイト系ステンレス鋳鋼。[Claims] 1. C: 0.02 to 0.07%, Si: 0.4% or less, Mn: 0.8% or less, Cr: 11 to 15%, Ni: 3 to 3% by weight.
6% and Mo: 2.6% or less, Si+1/2Mn content is 0.4% or less, and the balance is Fe and inevitable impurities. 2 In claim 1, the highly corrosion-resistant martensitic stainless steel exhibits an SCC fracture ratio of 0% in a low strain rate tensile test in a 288°C nuclear reactor environment simulating test liquid, and an elongation of 14 % or more of martensitic stainless steel cast steel with high corrosion resistance in high temperature and high pressure water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11646084A JPS60262944A (en) | 1984-06-08 | 1984-06-08 | Highly corrosion resistant martensitic stainless steel cast steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11646084A JPS60262944A (en) | 1984-06-08 | 1984-06-08 | Highly corrosion resistant martensitic stainless steel cast steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262944A JPS60262944A (en) | 1985-12-26 |
| JPH0152464B2 true JPH0152464B2 (en) | 1989-11-08 |
Family
ID=14687660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11646084A Granted JPS60262944A (en) | 1984-06-08 | 1984-06-08 | Highly corrosion resistant martensitic stainless steel cast steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262944A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01152243A (en) * | 1987-12-08 | 1989-06-14 | Kubota Ltd | Martensitic stainless steel having high corrosion fatigue strength and excellent corrosion resistance |
| CN109811246A (en) * | 2019-03-14 | 2019-05-28 | 南京玖铸新材料研究院有限公司 | High-toughness heat-resistant cast stainless steel and its manufacturing method |
-
1984
- 1984-06-08 JP JP11646084A patent/JPS60262944A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60262944A (en) | 1985-12-26 |
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