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JP4785302B2 - High strength austenitic stainless steel for metal gaskets - Google Patents
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JP4785302B2 - High strength austenitic stainless steel for metal gaskets - Google Patents

High strength austenitic stainless steel for metal gaskets Download PDF

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Publication number
JP4785302B2
JP4785302B2 JP2001273552A JP2001273552A JP4785302B2 JP 4785302 B2 JP4785302 B2 JP 4785302B2 JP 2001273552 A JP2001273552 A JP 2001273552A JP 2001273552 A JP2001273552 A JP 2001273552A JP 4785302 B2 JP4785302 B2 JP 4785302B2
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mass
stainless steel
austenitic stainless
dislocations
gaskets
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JP2003082441A (en
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宏紀 冨村
直人 平松
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Nippon Steel Nisshin Co Ltd
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Nisshin Steel Co Ltd
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Description

【0001】
【産業上の利用分野】
本発明は、内燃機関のエンジンや排気ガス配管等の高温雰囲気に曝されても、優れた耐ヘタリ性を維持するメタルガスケットとして使用されるオーステナイト系ステンレス鋼に関する。
【0002】
【従来技術及び問題点】
昇温が予定されている雰囲気に曝されるエンジン等には、従来からアスベスト製のガスケットが使用されきたが、エンジンの高性能化やノンアスベストの法規制化に対応してメタルガスケットが使用されるようになってきた。
ガスケットは、接合面の気密性を維持するための諸特性を備えていることが要求される。たとえば、排気系のエキゾストマニホルドガスケットやマフラー部分のガスケットでは、エンジン特有の高温・高圧及び高振動下で、しかも温度変化,圧力変化や排気系での温度上昇に対応できる疲労特性やシール性を維持するため、被加工部分の形状凍結性(耐ヘタリ性)に優れていることが要求される。そこで、オーステナイト系の中でも耐熱性や高温強度を重視してSUS310S等の高Ni−高Cr鋼がメタルガスケット材料に使用されている。
【0003】
しかし、SUS310SはNiを20質量%程度含有するオーステナイト系ステンレス鋼であり、おのずと材料コストが高くなる。また、SUS310Sほどの高合金では、熱間圧延や冷間圧延時に変形抵抗が大きく、製造性に難点がある。しかも、メタルガスケットの製品厚さに対応したゲージコントロールを実現するために工程に加わる制約も多くなる。
【0004】
【課題を解決するための手段】
本発明は、このような問題を解消すべく案出されたものであり、Ni量の低減により材料コストの上昇を抑制すると共に、オーステナイト自体の硬さ及び高温保持中の歪み時効を積極的に利用して高温強度を改善し、耐ヘタリ性に有効な合金設計を採用することにより、500〜800℃の高温雰囲気においても優れた耐ヘタリ性を呈し、高温用メタルガスケットに適したオーステナイト系ステンレス鋼を提供することを目的とする。
【0005】
本発明のメタルガスケット用オーステナイト系ステンレス鋼は、その目的を達成するため、C:0.02〜0.20質量%,Si:0.8〜3.0質量%,Mn:2.5質量%以下,P:0.060質量%以下,S:0.020質量%以下,Ni:7.0〜15.0質量%,Cr:13.0〜25.0質量%,Nb:0.80質量%以下,N:0.05〜0.25質量%を含み、残部Fe及び不可避的不純物の組成をもち、C+2N:0.20質量%以上でHVR=C+2N+0.12Si+1.4Nbと定義されるHVR値が0.45以上に調整されていることを特徴とする。
【0007】
【実施の形態】
本発明者等は、Ni含有量を15質量%以下に抑えたオーステナイト系ステンレス鋼の範疇で、過酷な使用環境に耐え得る、具体的には高温雰囲気に曝されても硬度低下が少なく、良好な耐ヘタリ性を維持する高温用ガスケットに適したオーステナイト系ステンレス鋼板を合金設計の面から種々調査検討した。
高温メタルガスケットは、加熱・冷却が頻繁に繰り返される500℃以上の高温雰囲気で使用される。このような過酷な雰囲気を考慮すると、ビード加工した個所を変形させたとき、弾性変形内で当初のビード形状に復元しようとする力、すなわちスプリング力が重要なファクターになる。なかでも、振動の激しい部位に使用される高温用メタルガスケットでは、大きな復元力を呈することが必要とされる。
【0008】
復元力の増大には、冷間圧延等により歪を導入し、多くの転位を組織に導入することが有効である。導入された転位は転位相互の干渉によって所定の変形が外部から加えられた際に大きな抵抗となって働き、結果としてスプリング力を向上させる。しかし、高温用メタルガスケットのように500℃以上の高温雰囲気に長時間曝される用途では、スプリング性に有効な転位がミクロ組織的に移動し、転位密度が低下する傾向にある(回復過程)。
本発明にあっては、転位の移動を抑制することにより転位回復を遅らせ、優れたスプリング性を維持することを狙っている。転位の移動抑制は、(1)加熱前の初期状態で転位を相互干渉させることによって動きやすい可動転位の割合を少なくすること、(2)高温雰囲気における転位の移動(ミクロ的に原子の運動)を抑制すること、(3)転位が移動する場合にあっても転位の移動を阻止する障害物を作り込んでおくことによって達成される。
【0009】
前掲(1)〜(3)の機能を付与するため、本発明ではC,N,Si,Nb量を規制している。侵入型原子として固溶するC,Nは、マトリックスを固溶強化すると共に転位の導入過程を複雑化し、可動転位の割合を減少させる。また、転位近傍に集積しやすく、転位の移動抑制にも有効である。更に、炭窒化物として析出した場合には、転位の移動を阻止するピニング効果が発現する。Siは高温雰囲気における転位の移動抑制に有効である。原子半径の大きなNbは,それ自体の拡散が遅くなるドラッグ効果によって高温雰囲気における転位の移動抑制に働き、析出物を生成した場合にはピニング効果を発現させる。
転位の移動抑制に有効なC,N,Si,Nbの影響を総合的に調査し、それぞれの寄与度を解析した結果、C+N≧0.20質量%でHVR=C+2N+0.12Si+1.4Nbと定義されるHVR値を0.45以上に調整するとき、要求特性に応じた転位の移動抑制効果が得られ、優れたスプリング性を呈するメタルガスケットが得られることを解明した。
【0010】
以下、本発明が対象とするオーステナイト系ステンレス鋼に含まれる合金成分,含有量等を説明する。
C:0.02〜0.20質量%
高温強度の向上に有効な合金成分であり、固溶強化や析出硬化によってステンレス鋼を高強度化する。このような作用は、0.02質量%以上のC含有で顕著になる。しかし、0.20質量%を超える過剰量のCが含まれると、高温保持中に巨大な粒界炭化物が析出しやすくなり、材料を脆化させる。
【0011】
Si:0.8〜3.0質量%
フェライト形成元素であり、オーステナイト相中で大きな固溶強化能を呈し、高温保持中に歪み時効によって時効硬化を促進させる。このような効果は、0.8質量%以上のSi含有量で顕著になる。しかし、3.0質量%を超える過剰量のSiを添加すると、高温割れが誘発され、製造上で種々のトラブルを引き起こす。
Mn:2.5質量%以下
オーステナイト形成元素であり、高価なNiの代替成分として使用され、Niの必要量を低減できる。また、Sを固定することによって熱間加工性を改善することにも有効である。しかし、2.5質量%を超える過剰量のMn添加は、σ相等の金属間化合物を析出させる原因となり、高温強度や機械的性質を低下させる。
【0012】
P:0.060質量%以下
固溶強化能の大きな合金成分であるが、靭性に悪影響を及ぼすことを考慮し、通常許容されている0.060質量%にP含有量の上限を設定した。
S:0.020質量%以下
熱間圧延段階で耳割れ発生の原因となる硫化物を生成させる有害元素であることから、S含有量は低いほど好ましい。しかし、B添加によってS含有量の許容範囲も拡大するので、0.020質量%をS含有量の上限に設定した。
【0013】
Ni:7.0〜15.0質量%
安定なオーステナイト組織を確保するために必須の合金成分であり、Niの最適含有量は鋼材に含まれるCr,Si,Mo等のフェライト形成元素量に依存する。しかし、7.0質量%未満のNi含有量ではオーステナイト相の安定化が困難になる。他方、15.0質量%を越えるNi含有量では、鋼材コストが上昇して経済的に不利となる。
Cr:13.0〜25.0質量%
耐食性・耐酸化性に必要な合金成分であり、過酷な高温腐食雰囲気に曝されるメタルガスケット用途を考慮すると少なくとも13.0質量%のCr量が必要である。しかし、25.0質量%を超える過剰量のCrが含まれると、δフェライトが形成され、安定したオーステナイト相が維持できなくなる。
【0014】
Nb:0.80質量%以下
メタルガスケットが曝される高温雰囲気下で析出物を形成し、或いはオーステナイトマトリックスに固溶することにより、硬度を上昇させ、耐ヘタリ性を改善する。しかし、0.80質量%を超える過剰量のNb含有は、高温強度向上に起因して熱間加工性を低下させる。
N:0.05〜0.25質量%
オーステナイト系ステンレス鋼の高温強度を上昇させると共に、マルテンサイト相の硬化に有効な合金成分であり、0.05質量%以上でNの添加効果が顕著になる。しかし、0.25質量%を超える過剰量のNが含まれると、鋳造時にブローホールが発生しやすくなる。
【0019】
【実施例】
表1に示す組成のステンレス鋼を真空溶解炉で溶製し、鍛造,熱延,焼鈍,冷延工程を経て板厚0.5〜0.2mmのステンレス鋼帯を製造した。
【0020】
【表1】

Figure 0004785302
【0021】
各ステンレス鋼帯から150mm×150の正方形試験片を切り出し、試験片の中央に内径75mmの円形開口を形成し、開口周辺に幅2.5mm,高さ0.25mm,突起部2Rのビードをプレス成形することによりメタルガスケット(図1)を作製した。次いで、ビード部を含んで200mm角に切り出し、ビード部がフラットになるように治具で押え、700℃に48時間保持した後、室温まで徐冷した。
徐冷後の試験片について、室温での素材硬度及び残存ビード高さを測定した。
なお、残存ビード高さの測定には焦点顕微鏡を使用し、3点の平均値として算出した。
【0022】
表2の測定結果にみられるように、鋼種No.1〜7(本発明例)では700℃×48時間加熱後に室温での残存ビード高さが0.210mm以上であり、メタルガスケットに要求される耐ヘタリ性を備えていた。
他方、比較鋼No.8〜13(比較例)では、何れも残存ビード高さが0.200mm未満であり、メタルガスケットとしての性能上に問題があった。残存ビード高さが低い理由には、次のような原因が考えられる。比較鋼No.8はSi量が不足し、比較鋼No.11,12はHVR値,C+2Nが低すぎるため、耐ヘタリ性が十分でない。比較鋼No.9は、過剰量のCを含んでいることから加熱保持中に炭化物が過剰析出してビード部に割れが発生した。比較鋼No.10は、過剰なCr含有のためδフェライト生成に起因する割れが発生した。比較鋼No.13は、Ni量が不足するためオーステナイト単相組織を維持できず、マルテンサイトの生成によって高温保持中で著しく軟化し、ヘタリ量が多くなった。
【0023】
この対比から明らかなように、Ni量を低減したオーステナイト系ステンレス鋼であっても、HVR値、C+2Nの適正管理により、形状凍結性に優れ、長期間にわたって気密性を維持するメタルガスケットが得られることが確認された。
【0024】
【表2】
Figure 0004785302
【0025】
【発明の効果】
以上に説明したように、本発明のオーステナイト系ステンレス鋼は、Ni量を低減した成分系においてC+2Nが0.20質量%以上でHVR値が0.45以上となる成分設計を採用することにより、メタルガスケットに要求される500〜800℃の高温環境での耐ヘタリ性に優れている。また、このオーステナイト系ステンレス鋼をエギゾストマニホルド,インテックマニホルド等の低温用メタルガスケットとして自動車用エンジンに組み込むと、周辺機器の寿命やエンジン自体の性能が向上する。また、エンジン用ガスケットの他に、自動車排ガス部品,自動車排気管の振動遮断用継手に使用されるボールジョイント部に組み込まれる弾性ガスケットにも使用できる。
【図面の簡単な説明】
【図1】 圧縮疲労試験,ヘタリ試験に用いたビード付き試験片[0001]
[Industrial application fields]
The present invention relates to an austenitic stainless steel that is used as a metal gasket that maintains excellent sag resistance even when exposed to a high temperature atmosphere such as an engine of an internal combustion engine or an exhaust gas pipe.
[0002]
[Prior art and problems]
Asbestos gaskets have been used for engines that are exposed to the atmosphere where the temperature is expected to rise, but metal gaskets have been used in response to higher engine performance and non-asbestos legislation. It has come to be.
The gasket is required to have various characteristics for maintaining the airtightness of the joint surface. For example, exhaust system exhaust manifold gaskets and muffler gaskets have fatigue characteristics and sealability that can respond to temperature changes, pressure changes, and exhaust system temperature increases under engine-specific high temperatures, high pressures, and high vibrations. In order to maintain it, it is required that the processed part has excellent shape freezing property (sag resistance). Therefore, high Ni-high Cr steel such as SUS310S is used as a metal gasket material with an emphasis on heat resistance and high temperature strength among austenitic materials.
[0003]
However, SUS310S is an austenitic stainless steel containing about 20% by mass of Ni, which naturally increases the material cost. Further, a high alloy such as SUS310S has a large deformation resistance during hot rolling or cold rolling, and has a difficulty in manufacturability. In addition, there are many restrictions on the process in order to realize gauge control corresponding to the product thickness of the metal gasket.
[0004]
[Means for Solving the Problems]
The present invention has been devised to solve such a problem, and while suppressing the increase in material cost by reducing the amount of Ni, the hardness of austenite itself and strain aging during high temperature holding are positively suppressed. Utilizing an alloy design that improves high-temperature strength and is effective in setting resistance, austenitic stainless steel that exhibits excellent settling resistance even in a high-temperature atmosphere of 500 to 800 ° C. and is suitable for high-temperature metal gaskets The purpose is to provide steel.
[0005]
The austenitic stainless steel for metal gasket according to the present invention has the following objectives: C: 0.02 to 0.20% by mass, Si: 0.8 to 3.0% by mass, Mn: 2.5% by mass Hereinafter, P: 0.060 mass% or less, S: 0.020 mass% or less, Ni: 7.0 to 15.0 mass%, Cr: 13.0 to 25.0 mass%, Nb: 0.80 mass HVR value defined as HVR = C + 2N + 0.12Si + 1.4Nb with a composition of the balance Fe and inevitable impurities , C + 2N: 0.20% by mass or more, including N: 0.05 to 0.25% by mass Is adjusted to 0.45 or more.
[0007]
Embodiment
The present inventors are a category of austenitic stainless steel in which the Ni content is suppressed to 15% by mass or less, and can withstand harsh use environments. Specifically, even when exposed to a high temperature atmosphere, there is little decrease in hardness and good Various austenitic stainless steel sheets suitable for high-temperature gaskets that maintain excellent sag resistance were investigated from the aspect of alloy design.
The high temperature metal gasket is used in a high temperature atmosphere of 500 ° C. or higher where heating and cooling are frequently repeated. In consideration of such a harsh atmosphere, the force that restores the original bead shape within the elastic deformation, that is, the spring force, becomes an important factor when the beaded portion is deformed. In particular, a high temperature metal gasket used in a site where vibration is intense is required to exhibit a large restoring force.
[0008]
In order to increase the restoring force, it is effective to introduce strain by cold rolling or the like and introduce many dislocations into the structure. The introduced dislocations act as a large resistance when a predetermined deformation is applied from the outside due to mutual interference between the dislocations, and as a result, the spring force is improved. However, in applications that are exposed to a high temperature atmosphere of 500 ° C or higher for a long time, such as high-temperature metal gaskets, dislocations effective for spring properties tend to move microscopically and the dislocation density tends to decrease (recovery process). .
The present invention aims to delay dislocation recovery by suppressing the movement of dislocations and maintain excellent spring properties. Control of dislocation movement is as follows: (1) The ratio of mobile dislocations that can move easily is reduced by causing the dislocations to interfere with each other in the initial state before heating, and (2) Dislocation movement in a high-temperature atmosphere (microscopic atomic motion). (3) Even if the dislocation moves, it is achieved by building an obstacle that prevents the dislocation from moving.
[0009]
In order to provide the functions (1) to (3) described above, the present invention regulates the amounts of C, N, Si, and Nb. C and N dissolved as interstitial atoms strengthen the solid solution, complicate the process of introducing dislocations, and reduce the ratio of movable dislocations. In addition, it is easy to accumulate in the vicinity of dislocations and is effective in suppressing the movement of dislocations. Further, when precipitated as carbonitrides, a pinning effect for preventing the movement of dislocations appears. Si is effective in suppressing the movement of dislocations in a high temperature atmosphere. Nb having a large atomic radius acts to suppress the movement of dislocations in a high-temperature atmosphere by a drag effect that slows the diffusion of itself, and causes a pinning effect when precipitates are generated.
As a result of comprehensively investigating the influence of C, N, Si, and Nb effective in controlling dislocation migration and analyzing the respective contributions, it is defined as HVR = C + 2N + 0.12Si + 1.4Nb when C + N ≧ 0.20 mass%. It has been clarified that when the HVR value is adjusted to 0.45 or more, a dislocation movement suppressing effect corresponding to the required characteristics can be obtained, and a metal gasket exhibiting excellent spring properties can be obtained.
[0010]
Hereinafter, alloy components, contents, and the like included in the austenitic stainless steel targeted by the present invention will be described.
C: 0.02 to 0.20% by mass
It is an alloy component that is effective for improving high-temperature strength, and strengthens stainless steel by solid solution strengthening and precipitation hardening. Such an effect becomes remarkable when the C content is 0.02% by mass or more. However, when an excessive amount of C exceeding 0.20% by mass is included, huge grain boundary carbides are likely to precipitate during holding at a high temperature, and the material becomes brittle.
[0011]
Si: 0.8-3.0 mass%
It is a ferrite forming element, exhibits a large solid solution strengthening ability in the austenite phase, and promotes age hardening by strain aging while maintaining a high temperature. Such an effect becomes remarkable when the Si content is 0.8 mass% or more. However, when an excessive amount of Si exceeding 3.0% by mass is added, hot cracking is induced, causing various troubles in production.
Mn: 2.5% by mass or less An austenite forming element, used as an alternative component of expensive Ni, and can reduce the necessary amount of Ni. It is also effective to improve hot workability by fixing S. However, addition of an excessive amount of Mn exceeding 2.5% by mass causes precipitation of intermetallic compounds such as the σ phase, and decreases high-temperature strength and mechanical properties.
[0012]
P: 0.060% by mass or less P is an alloy component having a large solid solution strengthening ability, but considering the adverse effect on toughness, the upper limit of P content is set to 0.060% by mass which is normally allowed.
S: not more than 0.020 mass% Since it is a harmful element that generates sulfides that cause ear cracking in the hot rolling stage, the lower the S content, the better. However, since the allowable range of the S content is expanded by addition of B, 0.020% by mass is set as the upper limit of the S content.
[0013]
Ni: 7.0 to 15.0 mass%
It is an essential alloy component for ensuring a stable austenite structure, and the optimum content of Ni depends on the amount of ferrite-forming elements such as Cr, Si, and Mo contained in the steel material. However, when the Ni content is less than 7.0% by mass, it becomes difficult to stabilize the austenite phase. On the other hand, if the Ni content exceeds 15.0% by mass, the steel material cost increases, which is economically disadvantageous.
Cr: 13.0 to 25.0 mass%
It is an alloy component necessary for corrosion resistance and oxidation resistance, and considering the use of a metal gasket exposed to a severe high temperature corrosion atmosphere, an amount of Cr of at least 13.0% by mass is necessary. However, if an excessive amount of Cr exceeding 25.0% by mass is contained, δ ferrite is formed and a stable austenite phase cannot be maintained.
[0014]
Nb: 0.80% by mass or less By forming a precipitate in a high temperature atmosphere to which the metal gasket is exposed, or by dissolving in austenite matrix, the hardness is increased and the settling resistance is improved. However, the excessive Nb content exceeding 0.80% by mass reduces the hot workability due to the improvement of the high temperature strength.
N: 0.05-0.25 mass%
It is an alloy component that increases the high-temperature strength of austenitic stainless steel and is effective for hardening the martensite phase. The effect of N addition becomes noticeable at 0.05% by mass or more. However, if an excessive amount of N exceeding 0.25% by mass is included, blow holes are likely to occur during casting.
[0019]
【Example】
Stainless steel having the composition shown in Table 1 was melted in a vacuum melting furnace, and a stainless steel strip having a thickness of 0.5 to 0.2 mm was manufactured through forging, hot rolling, annealing, and cold rolling processes.
[0020]
[Table 1]
Figure 0004785302
[0021]
A 150 mm x 150 square test piece is cut out from each stainless steel strip, a circular opening with an inner diameter of 75 mm is formed in the center of the test piece, and a bead with a width of 2.5 mm, a height of 0.25 mm, and a protrusion 2R is pressed around the opening. A metal gasket (FIG. 1) was produced by molding. Subsequently, it was cut out into 200 mm square including the bead portion, pressed with a jig so that the bead portion was flat, held at 700 ° C. for 48 hours, and then gradually cooled to room temperature.
About the test piece after slow cooling, the raw material hardness and residual bead height in room temperature were measured.
In addition, the focus bead microscope was used for the measurement of residual bead height, and it computed as an average value of 3 points | pieces.
[0022]
As seen in the measurement results in Table 2, steel types Nos. 1 to 7 (examples of the present invention) had a residual bead height of 0.210 mm or more at room temperature after heating at 700 ° C. for 48 hours, which is required for metal gaskets. It had anti-slip resistance.
On the other hand, in comparative steel Nos. 8 to 13 (comparative examples), the residual bead height was less than 0.200 mm, and there was a problem in performance as a metal gasket. The reason why the remaining bead height is low can be considered as follows. The comparative steel No. 8 has insufficient Si amount, and the comparative steel Nos. 11 and 12 have an HVR value and C + 2N that are too low, so that the settling resistance is not sufficient. Since Comparative Steel No. 9 contained an excessive amount of C, carbides excessively precipitated during heating and holding, and cracks occurred in the bead portion. In comparative steel No. 10, cracks due to the formation of δ ferrite occurred due to excessive Cr content. Comparative Steel No. 13 could not maintain the austenite single phase structure due to insufficient Ni amount, and was softened significantly during the holding at a high temperature due to the formation of martensite, and the amount of settling was increased.
[0023]
As is clear from this comparison, even with austenitic stainless steel with a reduced amount of Ni, a metal gasket that has excellent shape freezing properties and maintains hermeticity over a long period of time can be obtained by appropriate management of the HVR value and C + 2N. It was confirmed.
[0024]
[Table 2]
Figure 0004785302
[0025]
【The invention's effect】
As described above, the austenitic stainless steel of the present invention adopts a component design in which C + 2N is 0.20% by mass or more and the HVR value is 0.45 or more in the component system in which the amount of Ni is reduced. Excellent sag resistance in a high temperature environment of 500 to 800 ° C. required for metal gaskets. In addition, when this austenitic stainless steel is incorporated in an automobile engine as a low-temperature metal gasket such as an exhaust manifold or intech manifold, the life of peripheral devices and the performance of the engine itself are improved. In addition to engine gaskets, the present invention can also be used for elastic gaskets incorporated in ball joint parts used in automobile exhaust parts and vibration isolation joints for automobile exhaust pipes.
[Brief description of the drawings]
[Fig.1] Specimens with beads used for compression fatigue test and settling test

Claims (1)

C:0.02〜0.20質量%,Si:0.8〜3.0質量%,Mn:2.5質量%以下,P:0.060質量%以下,S:0.020質量%以下,Ni:7.0〜15.0質量%,Cr:13.0〜25.0質量%,Nb:0.80質量%以下,N:0.05〜0.25質量%を含み、残部Feおよび不可避的不純物の組成をもち、C+2N:0.20質量%以上でHVR=C+2N+0.12Si+1.4Nbと定義されるHVR値が0.45以上に調整されていることを特徴とするメタルガスケット用オーステナイト系ステンレス鋼。C: 0.02-0.20 mass%, Si: 0.8-3.0 mass%, Mn: 2.5 mass% or less, P: 0.060 mass% or less, S: 0.020 mass% or less , Ni: 7.0 to 15.0 mass%, Cr: 13.0 to 25.0 mass%, Nb: 0.80 mass% or less, N: 0.05 to 0.25 mass%, and the balance Fe And an austenite for metal gaskets having a composition of inevitable impurities and having an HVR value defined as HVR = C + 2N + 0.12Si + 1.4Nb at C + 2N: 0.20% by mass or more, adjusted to 0.45 or more. Stainless steel.
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