JP2017171990A - Martensitic stainless steel sheet and metal gasket manufacturing method - Google Patents
Martensitic stainless steel sheet and metal gasket manufacturing method Download PDFInfo
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Abstract
Description
本発明は、メタルガスケットに好適なマルテンサイト系ステンレス鋼板およびその製造法、並びにそれを用いたメタルガスケットの製造法に関する。 The present invention relates to a martensitic stainless steel plate suitable for a metal gasket, a method for producing the same, and a method for producing a metal gasket using the same.
自動車、オートバイ等におけるエンジンのシリンダヘッドガスケットやエキゾーストマニホールドガスケットは、エンジン特有の高温、高圧、高振動下での繰り返しの圧力変動に曝される。なかでも自動車エンジンのシリンダガスケットでは圧縮時に高圧が加わるので、シール性を維持するためには双方の接触相手材と高い接触圧力（面圧）で接している必要がある。エンジンや排ガス経路に使用されるメタルガスケットには、十分な接触圧力を確保するために、一定高さのビード（連続する***部）が形成されるのが一般的である。ビードは通常、プレスによるビード成形によって形成される。この種のメタルガスケットには、高強度および高耐食性が要求される。 Engine cylinder head gaskets and exhaust manifold gaskets in automobiles, motorcycles, and the like are exposed to repeated pressure fluctuations under the high temperature, high pressure, and high vibration specific to the engine. In particular, since a cylinder gasket of an automobile engine is subjected to a high pressure during compression, it needs to be in contact with both contact counterparts with a high contact pressure (surface pressure) in order to maintain the sealing performance. A metal gasket used for an engine or an exhaust gas path is generally formed with a bead (continuous raised portion) having a certain height in order to ensure a sufficient contact pressure. The bead is usually formed by bead molding by a press. This type of metal gasket is required to have high strength and high corrosion resistance.
従来、自動車エンジンやその排ガス経路に適用するガスケットには加工硬化型の準安定オーステナイト系ステンレス鋼（ＳＵＳ３０１系など）が多用されている。この種の鋼は冷間圧延で加工誘起マルテンサイトを生成させることによって高強度化を図るものである。ただし、強度レベルを引き上げるためには冷間圧延率を高める必要がある。冷間圧延率の増大は、靭性、耐疲労特性および加工性を低下させる要因となる。 Conventionally, work-hardening type metastable austenitic stainless steel (SUS301 series or the like) is frequently used for gaskets applied to automobile engines and exhaust gas paths thereof. This type of steel is intended to increase strength by generating work-induced martensite by cold rolling. However, it is necessary to increase the cold rolling rate in order to raise the strength level. An increase in the cold rolling rate is a factor that decreases toughness, fatigue resistance, and workability.
また、工業用の配管などには、塗装を施したメタルガスケットが使用される場合がある。この種のメタルガスケットには、塗膜密着性も要求される。 In addition, a painted metal gasket may be used for industrial piping or the like. This type of metal gasket also requires coating film adhesion.
一方、冷間圧延率の増大に頼らずに高強度化を図る素材としてマルテンサイト系ステンレス鋼がある。特許文献１には、マルテンサイト系ステンレス鋼をガスケットに適用することが記載されている。特許文献２には、介在物組成を適正化することによってマルテンサイト系ステンレス鋼を用いたガスケットの疲労特性を改善する技術が記載されている。 On the other hand, there is martensitic stainless steel as a material for increasing the strength without depending on the increase in the cold rolling rate. Patent Document 1 describes that martensitic stainless steel is applied to a gasket. Patent Document 2 describes a technique for improving the fatigue characteristics of a gasket using martensitic stainless steel by optimizing the inclusion composition.
マルテンサイト系ステンレス鋼は高価なＮｉを多量に含有する準安定オーステナイト系ステンレス鋼よりも原料コストが安価である。また、高い冷間圧延率を付与して加工硬化させる必要もないので、加工硬化に伴う靭性低下や集合組織による異方性の問題も生じにくい。特許文献２の技術に従えば、疲労特性も改善する。しかしながら、マルテンサイト系ステンレス鋼板は高強度を得るための熱処理において冷却速度の影響を強く受けるため、鋼板全体について材質を均一化することは容易でない。発明者らの調査によれば、厳しい評価基準で見た場合、焼戻し軟化や鋭敏化による固溶Ｃ、Ｎの減少に起因すると考えられる、強度低下、機械的性質の変化、および耐食性の低下が問題となりうることがわかった。これらの特性はメタルガスケットの性能に影響を及ぼす。 Martensitic stainless steel has a lower raw material cost than metastable austenitic stainless steel containing a large amount of expensive Ni. Further, since there is no need to impart a high cold rolling rate and work hardening, problems of toughness reduction due to work hardening and anisotropy due to texture are unlikely to occur. According to the technique of Patent Document 2, fatigue characteristics are also improved. However, since the martensitic stainless steel plate is strongly influenced by the cooling rate in the heat treatment for obtaining high strength, it is not easy to make the material uniform for the entire steel plate. According to the inventors' investigation, when viewed under strict evaluation criteria, there is a decrease in strength, a change in mechanical properties, and a decrease in corrosion resistance, which are thought to be due to a decrease in solid solution C and N due to temper softening and sensitization. I found it could be a problem. These characteristics affect the performance of the metal gasket.
メタルガスケットにおいて、ビードの硬さ（強度）分布を均一化することは、安定した面圧の維持に寄与するため、リーク特性等の改善につながる。また、メタルガスケット製品間での特性のバラツキを低減することも安定な品質を確保するうえで重要である。これらの要求に対応するためには、素材である鋼板において、その鋼帯の幅方向および長手方向での素材特性を均一化することが極めて有利となる。しかし、従来の開示技術では、広幅の鋼帯を連続生産する際に、幅方向および長手方向での素材特性を十分に均一化することが難しかった。 In the metal gasket, making the hardness (strength) distribution of the beads uniform contributes to the maintenance of a stable surface pressure, which leads to improvement of leak characteristics and the like. In addition, reducing the variation in characteristics among metal gasket products is also important for ensuring stable quality. In order to meet these requirements, it is extremely advantageous to make the material properties uniform in the width direction and the longitudinal direction of the steel strip in the steel plate as the material. However, in the conventional disclosed technique, it has been difficult to sufficiently uniform the material characteristics in the width direction and the longitudinal direction when continuously producing a wide steel strip.
本発明は、マルテンサイト系ステンレス鋼板において、焼戻し軟化や鋭敏化による強度、耐食性の低下を低減させることを目的とする。また、塗膜密着性の改善を図る。 An object of this invention is to reduce the fall of the intensity | strength by a temper softening and sensitization, and corrosion resistance in a martensitic stainless steel plate. In addition, the coating film adhesion is improved.
マルテンサイト相の強度は、成分と熱処理条件の影響を強く受ける。
〔成分の影響〕
侵入型元素であるＣ、Ｎの量が多いほど高強度が得られる。しかし、過剰のＣ、Ｎの含有は靭性低下を招く要因となるので、それらの含有量には制約がある。また、鋼中に存在するＣ、Ｎのうち強度に寄与するのは、マルテンサイト相中に固溶しているＣ、Ｎである。炭窒化物の過度の生成は鋼中のＣ、Ｎを過剰に消費し、強度低下を招く。
〔熱処理の影響〕
マルテンサイト系ステンレス鋼では、Ａｃ1点以上に加熱したのち冷却することによってオーステナイト相をマルテンサイト相へ変態させ、高強度を得ている（焼入れ）。この焼入れによる強化の程度は、加熱温度および冷却速度に影響される。焼入れ性が悪い（すなわち冷却速度が遅くなると硬質なマルテンサイトが生成しにくい）鋼では、鋼帯を生産する際に操業条件のわずかな変動が特性のバラツキにつながりやすい。
これらのことが鋼帯内における材質の均一化を難しくする要因となっている。
The strength of the martensite phase is strongly influenced by the components and heat treatment conditions.
[Influence of ingredients]
The higher the amount of interstitial elements C and N, the higher the strength. However, since excessive C and N contents cause a decrease in toughness, their contents are limited. Further, among C and N present in the steel, it is C and N dissolved in the martensite phase that contribute to the strength. Excessive formation of carbonitrides consumes C and N in steel excessively and causes strength reduction.
[Effect of heat treatment]
In martensitic stainless steel, the austenite phase is transformed into a martensite phase by cooling after heating to Ac 1 point or higher, and high strength is obtained (quenching). The degree of strengthening by quenching is affected by the heating temperature and the cooling rate. In steels with poor hardenability (that is, hard martensite is less likely to be produced when the cooling rate is slow), slight fluctuations in operating conditions tend to lead to variations in properties when producing steel strips.
These are factors that make it difficult to make the material uniform in the steel strip.
ステンレス鋼中にはＣｒ、Ｆｅなど、ＣやＮと結びつきやすい金属元素が多量に存在する。これらの金属元素が炭化物を形成する場合と窒化物を形成する場合とを比べると、炭化物を形成する場合の方が冷却速度の影響を大きく受けることがわかった。すなわち冷却速度が同じであれば、炭化物生成反応は、窒化物生成反応よりも迅速に進行する。そのため、鋼帯内で冷却速度が比較的遅い箇所では、固溶Ｃが炭化物形成に消費されやすく、固溶Ｃによる強化への寄与が低減する。これが鋼帯内での特性のバラツキを生じさせる要因となっている。一方、窒化物生成反応は炭化物生成反応ほど迅速に進行しないので、冷却速度が比較的遅い箇所でも固溶Ｎの存在量は維持されやすく、固溶Ｎによる強化への寄与は失われにくい。そこで本発明では、マルテンサイト相の強化への寄与をできるだけＮに負担させるという思想により、成分設計を行って、素材特性の均一性が高い鋼板を実現している。その成分設計においてはＣ／Ｎ含有量比を制限し、かつＣｒ、Ｍｎ、Ｃｕ等の合金元素含有量を適正化してＮの固溶限を十分に確保することが重要である。 In stainless steel, there are a large amount of metal elements such as Cr and Fe, which are easily combined with C and N. Comparing the case where these metal elements form carbide and the case where nitride is formed, it has been found that the case where carbide is formed is greatly affected by the cooling rate. That is, if the cooling rate is the same, the carbide forming reaction proceeds more rapidly than the nitride forming reaction. Therefore, at a location where the cooling rate is relatively slow in the steel strip, the solid solution C is easily consumed for carbide formation, and the contribution to strengthening by the solid solution C is reduced. This is a factor causing variations in characteristics within the steel strip. On the other hand, since the nitride formation reaction does not proceed as rapidly as the carbide formation reaction, the abundance of solid solution N is easily maintained even at locations where the cooling rate is relatively slow, and the contribution to strengthening by solid solution N is unlikely to be lost. Therefore, in the present invention, a component design is performed based on the idea of making N contribute as much as possible to the strengthening of the martensite phase, thereby realizing a steel sheet with high uniformity of material characteristics. In the component design, it is important to limit the C / N content ratio and to optimize the content of alloy elements such as Cr, Mn, Cu, etc. to ensure a sufficient solid solubility limit of N.
すなわち本発明では、質量％で、Ｃ：０.１００〜０.１８０％、Ｓｉ：０.２０〜１.５０％、Ｍｎ：０.１０〜２.００％、Ｎｉ：０.０１〜１.００％、Ｃｒ：１１.００〜１８.００％、Ｃｕ：０.２０〜１.６０％、Ｍｏ：０〜０.５０％、Ｎ：０.０３０〜０.１００％、Ｖ：０〜０.５０％、Ｎｂ：０〜０.５０％、Ｔｉ：０〜０.５０％、Ｂ：０〜０.０２０％、残部Ｆｅおよび不可避的不純物からなり、ＣとＮの合計含有量が０.１３０質量％以上、Ｃ／Ｎ含有量比（質量％比）が５.０以下、かつ下記（１）式により定まるγmax値が８０.０以上である化学組成を有するマルテンサイト系ステンレス鋼板が提供される。
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には質量％で表される当該元素の含有量が代入される。
That is, in the present invention, by mass%, C: 0.10 to 0.180%, Si: 0.20 to 1.50%, Mn: 0.10 to 2.00%, Ni: 0.01 to 1. 00%, Cr: 11.00 to 18.00%, Cu: 0.20 to 1.60%, Mo: 0 to 0.50%, N: 0.030 to 0.100%, V: 0 to 0 .50%, Nb: 0 to 0.50%, Ti: 0 to 0.50%, B: 0 to 0.020%, remaining Fe and inevitable impurities, and the total content of C and N is 0.5. Provided is a martensitic stainless steel sheet having a chemical composition of 130% by mass or more, a C / N content ratio (mass% ratio) of 5.0 or less, and a γmax value determined by the following formula (1) of 80.0 or more. Is done.
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the content of the element represented by mass% is substituted for the element symbol in the formula (1).
上記鋼成分元素のうちＭｏ、Ｖ、Ｎｂ、Ｔｉ、Ｂは任意添加元素である。この鋼板の板面（圧延面）の硬さは例えば４００〜５７０ＨＶである。その板厚は例えば０.０５〜０.５ｍｍとすることができ、０.１〜０.３ｍｍに管理することもできる。この鋼板は、ビード頭頂部を接触相手材に押し当てて使用するメタルガスケットに好適である。「ビード頭頂部」は接触相手材と接触するビード凸部の頂上部を意味する。 Of the steel component elements, Mo, V, Nb, Ti, and B are arbitrarily added elements. The hardness of the plate surface (rolled surface) of this steel plate is, for example, 400 to 570 HV. The plate thickness can be set to 0.05 to 0.5 mm, for example, and can be controlled to 0.1 to 0.3 mm. This steel plate is suitable for a metal gasket that is used by pressing the top of the bead against a contact partner material. "Bead head top" means the top of the bead convex portion in contact with the contact partner material.
上記鋼板において、特に塗膜密着性の良好なものとして、開口径１.０μｍ以上のピットを１０個／０.０１ｍｍ2以上の個数密度で表面に有し、圧延直角方向の表面粗さＲａが０.５００μｍ以下である鋼板が提供される。 The steel sheet has particularly good coating film adhesion, and has pits with an opening diameter of 1.0 μm or more on the surface with a number density of 10 pieces / 0.01 mm 2 or more, and a surface roughness Ra in the direction perpendicular to the rolling direction. A steel sheet having a thickness of 0.5 μm or less is provided.
上記ピットは、仕上焼鈍後の酸洗処理で析出粒子が脱落することにより形成されたものである。前記析出粒子は主としてＭ23Ｃ6（ＭはＣｒなどの遷移金属元素）型の炭化物粒子である。炭窒化物が形成されることもあるが、本明細書では炭窒化物を含めて炭化物と呼んでいる。表面粗さＲａはＪＩＳ Ｂ０６０１：２０１３に規定の算術平均粗さＲａである。圧延直角方向とは、圧延方向に対して直角の方向を意味する。ピットの開口径は、鋼板表面を板厚方向に見たＳＥＭ（走査型電子顕微鏡）画像において、当該ピットの輪郭で囲まれる開口部の最も長い部分の径（長径）を意味する。 The pits are formed by the precipitation particles falling off during the pickling treatment after finish annealing. The precipitated particles are mainly M 23 C 6 (M is a transition metal element such as Cr) type carbide particles. Although carbonitride may be formed, in this specification, carbonitride including carbonitride is called. The surface roughness Ra is an arithmetic average roughness Ra defined in JIS B0601: 2013. The rolling perpendicular direction means a direction perpendicular to the rolling direction. The opening diameter of a pit means the diameter (major diameter) of the longest part of the opening surrounded by the outline of the pit in an SEM (scanning electron microscope) image in which the steel plate surface is viewed in the plate thickness direction.
上記鋼板の製造法として、前記の化学組成を有する中間製品鋼板を、８００〜１１００℃の範囲にある、オーステナイト単相温度域またはオーステナイト相＋２０体積％以下のフェライト相となる２相温度域に加熱した後、冷却して、前記オーステナイト相をマルテンサイト相に変態させる工程（仕上焼鈍工程）を有する製造法が提供される。前記の冷却は、８００℃から２００℃までの平均冷却速度が１〜１５０℃／ｓｅｃとなる条件とすることがより好ましい。 As a manufacturing method of the steel sheet, the intermediate product steel sheet having the above chemical composition is heated to a two-phase temperature range in which the austenite single-phase temperature range or the austenite phase + 20 vol% or less ferrite phase is in the range of 800 to 1100 ° C. After that, a manufacturing method is provided which includes cooling and transforming the austenite phase into a martensite phase (finish annealing step). More preferably, the cooling is performed under the condition that the average cooling rate from 800 ° C. to 200 ° C. is 1 to 150 ° C./sec.
特に塗膜密着性の良好な鋼板を得る手法として、上記の仕上焼鈍工程における加熱を酸化性雰囲気で行い、さらに、仕上焼鈍工程後の鋼板を酸洗処理することにより表面の酸化スケールを除去するとともに、表面に存在する炭化物粒子を脱落させて表面にピットを形成する工程（酸洗工程）を有する鋼板の製造法が提供される。 In particular, as a technique for obtaining a steel sheet having good coating film adhesion, heating in the finish annealing step is performed in an oxidizing atmosphere, and further, the surface oxidized scale is removed by pickling the steel plate after the finish annealing step. In addition, there is provided a method for producing a steel sheet having a step (pickling step) in which carbide particles present on the surface are dropped to form pits on the surface.
本発明によれば、Ｃより冷却速度の影響を受けにくいＮを十分に活用してマルテンサイト相を強化することにより、焼入れ安定性の向上による材質の均一化、並びに耐焼戻し軟化性および耐鋭敏化性の向上による材質変化の低減が可能となった。その結果、この鋼板を素材とするメタルガスケットの使用時においては、ビード頭頂部に負荷される接触面圧がより均一に維持され、耐リーク性に優れたメタルガスケットが実現される。 According to the present invention, by making full use of N, which is less susceptible to the cooling rate than C, and strengthening the martensite phase, it is possible to make the material uniform by improving the quenching stability, as well as tempering softening resistance and sharpness resistance. It has become possible to reduce material changes due to improved chemical properties. As a result, when a metal gasket made of this steel plate is used, the contact surface pressure applied to the top of the bead is more uniformly maintained, and a metal gasket excellent in leak resistance is realized.
〔化学組成〕
本発明の対象となる鋼の化学組成について説明する。以下、鋼組成における「％」は特に断らない限り「質量％」を意味する。
Ｃは、オーステナイト生成元素であり、フェライト相およびマルテンサイト相の強化に有効な元素である。Ｃ含有量が少なすぎると上記の強化作用が十分に発揮されず、また、Ａｃ1点以上の温度でのオーステナイト生成量を適正範囲にコントロールする成分調整（γmaxの適正化）が難しくなり、所定のマルテンサイト量を確保するうえで不利となる。種々検討の結果、Ｃ含有量は０.１００％以上とする必要がある。ただし、過剰のＣ含有はオーステナイト生成温度域からの冷却過程でＣｒ系炭化物の粒界析出を招きやすく、耐食性低下の要因となる。また、鋼帯内強度バラツキに及ぼす冷却速度変動の影響が大きくなる。Ｃ含有量は０.１８０％以下の範囲で調整する。
[Chemical composition]
The chemical composition of the steel that is the subject of the present invention will be described. Hereinafter, “%” in the steel composition means “% by mass” unless otherwise specified.
C is an austenite forming element and is an element effective for strengthening the ferrite phase and the martensite phase. If the C content is too small, the above-described strengthening effect cannot be fully exhibited, and it is difficult to adjust the component (optimization of γmax) for controlling the austenite generation amount at a temperature of Ac 1 point or higher to an appropriate range. This is disadvantageous in securing the amount of martensite. As a result of various studies, the C content needs to be 0.100% or more. However, excessive C content tends to cause grain boundary precipitation of Cr-based carbides in the cooling process from the austenite generation temperature range, and causes a decrease in corrosion resistance. In addition, the influence of the cooling rate fluctuation on the strength variation in the steel strip increases. The C content is adjusted in the range of 0.180% or less.
Ｎは、オーステナイト生成元素であり、Ｃと同様にフェライト相およびマルテンサイト相の強化に有効である。上述のようにＮは、Ｃと比べ、仕上焼鈍時の冷却速度が比較的緩やかになった場合でもマトリックス中に固溶した状態でとどまりやすい。そのため、鋼帯中の強度バラツキを抑制する上で、本発明ではＮによる焼入れ強化作用を活用する。この場合、Ｎ含有量は０.０３０％以上を必要とする。過剰のＮ含有は焼鈍後の冷却過程で窒化物を形成させ、耐食性や耐疲労特性の低下要因となる。Ｎ含有量は０.１００％以下に制限される。 N is an austenite-forming element and is effective for strengthening the ferrite phase and the martensite phase in the same manner as C. As described above, N is likely to remain in a solid solution state in the matrix even when the cooling rate during finish annealing is relatively slow as compared to C. Therefore, in order to suppress the strength variation in the steel strip, the present invention utilizes the quenching strengthening action by N. In this case, the N content needs to be 0.030% or more. Excessive N content causes nitrides to form during the cooling process after annealing, which causes a decrease in corrosion resistance and fatigue resistance. N content is limited to 0.100% or less.
メタルガスケットに要求される強度を安定して確保するためには、ＣとＮの合計含有量を０.１３％以上確保する必要がある。その上で、冷却速度による強度バラツキに影響を及ぼしやすいＣの含有量上限を上述のように厳しく制限し、かつ、Ｎの含有量を十分に確保する。種々検討の結果、質量％におけるＣ／Ｎ含有量比を５.０以下とすることが、焼入れ安定性の向上に極めて有効であることがわかった。Ｃ／Ｎ含有量比を４.０以下とすることがより効果的である。 In order to stably secure the strength required for the metal gasket, it is necessary to secure a total content of C and N of 0.13% or more. In addition, the upper limit of the C content that easily affects the variation in strength due to the cooling rate is strictly limited as described above, and the N content is sufficiently secured. As a result of various studies, it was found that setting the C / N content ratio in mass% to 5.0 or less is extremely effective for improving the quenching stability. It is more effective to set the C / N content ratio to 4.0 or less.
Ｓｉは、製鋼時に脱酸剤として添加される。Ｓｉ含有量が０.２０％以上となるようにＳｉを添加する必要がある。ただし、Ｓｉはフェライト相およびマルテンサイト相に固溶し、特にマルテンサイト相を硬質化する作用が大きい。適度な硬質化はガスケットの高強度化に有効であるが、過度の硬質化は加工性や靭性の低下要因となる。また、過剰なＳｉ含有は高温割れを誘発する。Ｓｉ含有量は１.５０％以下の範囲に制限される。 Si is added as a deoxidizer during steelmaking. It is necessary to add Si so that the Si content is 0.20% or more. However, Si dissolves in the ferrite phase and the martensite phase, and has a particularly large effect of hardening the martensite phase. Moderate hardening is effective for increasing the strength of the gasket, but excessive hardening is a factor that reduces workability and toughness. Further, excessive Si content induces hot cracking. The Si content is limited to a range of 1.50% or less.
Ｍｎは、オーステナイト生成元素であり、高温でのオーステナイト相域を拡大する。マルテンサイト量の増大にはＭｎ含有量を高めることが有効である。また、Ｎの固溶限を確保するためにも有効である。Ｍｎ含有量は０.１０％以上とする。ただし、Ｍｎ含有量が多くなると高温で生成したオーステナイト相が安定となり、常温までの冷却過程でマルテンサイト変態しきれなかったオーステナイト相が残存するようになる。種々検討の結果、Ｍｎ含有量は２.００％以下の範囲とする。１.００％未満に管理してもよい。 Mn is an austenite generating element and expands the austenite phase region at high temperatures. Increasing the Mn content is effective for increasing the martensite content. It is also effective for securing the solid solubility limit of N. The Mn content is 0.10% or more. However, when the Mn content increases, the austenite phase generated at a high temperature becomes stable, and the austenite phase that cannot be fully martensitic transformed during the cooling process to room temperature remains. As a result of various studies, the Mn content is set to a range of 2.00% or less. You may manage to less than 1.00%.
Ｎｉは、オーステナイト生成元素であり、マルテンサイト量を十分に確保する上で有である。Ｎｉ含有量は０.０１％以上とすることが効果的である。ただし、Ｎｉ含有が過大になると残留オーステナイト相が存在しやすくなり、強度向上に不利となる。Ｎｉ含有量は１.００％以下に制限され、０.６５％以下とすることがより好ましい。 Ni is an austenite-forming element and is effective in securing a sufficient amount of martensite. It is effective that the Ni content is 0.01% or more. However, if the Ni content is excessive, a residual austenite phase tends to exist, which is disadvantageous for improving the strength. The Ni content is limited to 1.00% or less, and more preferably 0.65% or less.
Ｃｒは、ステンレス鋼として必要な耐食性を付与するうえで必須の元素である。また、Ｎの固溶限を確保するためにも有効である。ただしマルテンサイト生成量を十分に確保するためにはＣｒ含有量の増大に応じてＣ、Ｎ、Ｎｉ、Ｍｎ等のオーステナイト形成元素の含有量を増大させる必要が生じ、鋼材コストの上昇を招く。靭性低下の要因になもる。本発明ではＣｒ含有量が１１.００〜１８.００％である鋼を対象とする。 Cr is an essential element for imparting the necessary corrosion resistance as stainless steel. It is also effective for securing the solid solubility limit of N. However, in order to secure a sufficient amount of martensite, it is necessary to increase the content of austenite forming elements such as C, N, Ni and Mn as the Cr content increases, resulting in an increase in steel material costs. It becomes a factor of toughness fall. In the present invention, steel with a Cr content of 11.00 to 18.00% is targeted.
Ｃｕは、オーステナイト生成元素であり、マルテンサイト量を十分に確保する上で有効である。また、Ｎの固溶限を確保するためにも有効である。Ｃｕ含有量は０.２０％以上とすることが効果的である。ただし、Ｃｕ含有量が過大になると残留オーステナイト相が存在しやすくなり、強度向上や熱間加工性確保に不利となる。Ｃｕ含有量は１.６０％以下とする。 Cu is an austenite generating element and is effective in securing a sufficient amount of martensite. It is also effective for securing the solid solubility limit of N. It is effective that the Cu content is 0.20% or more. However, if the Cu content is excessive, a residual austenite phase is likely to be present, which is disadvantageous for improving the strength and ensuring hot workability. The Cu content is 1.60% or less.
Ｍｏは、耐食性の向上に有効であり、必要に応じて添加することができる。その場合、０.１０％以上の添加量とすることがより効果的である。過剰のＭｏ添加はコスト増となる。Ｍｏを添加する場合は０.５０％以下の範囲で行う。 Mo is effective in improving the corrosion resistance, and can be added as necessary. In that case, it is more effective to set the addition amount to 0.10% or more. Excessive Mo addition increases costs. When adding Mo, it is performed within a range of 0.50% or less.
Ｖ、Ｎｂ、Ｔｉ、Ｂは、製造性、強度、耐疲労特性などを改善するうえで有効な元素である。必要に応じてこれらの１種以上を添加することができる。Ｖは０.５０％以下、Ｎｂは０.５０％以下、Ｔｉは０.５０％以下、Ｂは０.０２０％以下の含有量範囲とする。より効果的な含有量範囲は、Ｖ：０.０１〜０.５０％、Ｎｂ：０.０１〜０.５０％、Ｔｉ：０.０１〜０.５０％、Ｂ：０.０００５〜０.０２０％である。 V, Nb, Ti, and B are effective elements for improving manufacturability, strength, fatigue resistance, and the like. One or more of these may be added as necessary. V is 0.50% or less, Nb is 0.50% or less, Ti is 0.50% or less, and B is 0.020% or less. More effective content ranges are: V: 0.01 to 0.50%, Nb: 0.01 to 0.50%, Ti: 0.01 to 0.50%, B: 0.0005 to 0.5. 020%.
下記（１）式により定まるγmax値が８０.０以上となるように各元素含有量を調整する。
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には当該元素の質量％の値が代入される。
上記γmaxは、Ａｃ1点以上の温度域に昇温したときに生成する最大オーステナイト量（体積％）を表す指標である。各元素の含有量が上述の範囲にある鋼では、高温でのオーステナイト相は常温への冷却過程でほぼ全部がマルテンサイト相に変態すると見てよい。従って、本発明で対象とする冷延焼鈍材の鋼素地（マトリックス）は、マルテンサイト量がほぼγmaxに等しい量（体積％）であり、残部がフェライト相である。γmaxが１００を超える場合は鋼素地がほぼ１００％マルテンサイト組織となる。
The content of each element is adjusted so that the γmax value determined by the following equation (1) is 80.0 or more.
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the value of mass% of the element is substituted for the element symbol in the formula (1).
The γmax is an index representing the maximum amount of austenite (volume%) generated when the temperature is raised to a temperature range of Ac 1 point or higher. In the steel in which the content of each element is in the above-described range, it can be seen that almost all of the austenite phase at a high temperature is transformed into a martensite phase in the course of cooling to room temperature. Therefore, the steel base (matrix) of the cold-rolled annealed material that is the subject of the present invention is an amount (volume%) in which the martensite amount is substantially equal to γmax, and the balance is the ferrite phase. When γmax exceeds 100, the steel substrate has an almost 100% martensite structure.
鋼素地に占めるフェライト相の割合が多くなりすぎると、メタルガスケットに適した高強度を安定して実現することが難しくなる。またフェライト相とマルテンサイト相の強度差により相界面からの割れが生じやすくなり、加工性および耐疲労特性の異方性が大きくなる。種々検討の結果、本発明ではγmaxが８０.０以上となる鋼組成を採用する。 If the proportion of the ferrite phase in the steel substrate is too large, it will be difficult to stably realize high strength suitable for a metal gasket. In addition, the strength difference between the ferrite phase and the martensite phase tends to cause cracks from the phase interface, increasing the anisotropy of workability and fatigue resistance. As a result of various studies, the present invention employs a steel composition in which γmax is 80.0 or more.
〔製造方法〕
代表的な製造方法を以下に例示する。上述の化学組成に調整された鋼を通常のステンレス鋼の製鋼設備によって溶製し、鋳片を得る。鋳片に通常のマルテンサイト系ステンレス鋼板の製造と同様に熱間圧延を施し、熱延鋼板を得る。
〔Production method〕
A typical manufacturing method is illustrated below. The steel adjusted to the above-mentioned chemical composition is melted by normal stainless steel making equipment to obtain a slab. The slab is hot-rolled in the same manner as in the production of a normal martensitic stainless steel plate to obtain a hot-rolled steel plate.
熱延鋼板に焼鈍を施し、その後、冷間圧延を施して板厚を減じる。必要に応じて冷間圧延の途中で中間焼鈍を施す。最終的な製品板厚は例えば０.０５〜０.５ｍｍとすればよい。所定の最終製品板厚となった冷延鋼板に仕上焼鈍を施す。仕上焼鈍温度はＡｃ1点以上のオーステナイト生成温度域とする。具体的には、８００〜１１００℃の範囲にある、「オーステナイト単相温度域」または「オーステナイト相＋２０体積％以下のフェライト相となる２相温度域」に加熱することが好ましい。本発明で規定する鋼組成範囲であれば、通常９００〜１０５０℃の範囲の温度域でγmaxに対応した量のオーステナイト相を生成させることができる。仕上焼鈍温度での保持時間は０〜６０秒の範囲で設定すればよい。 The hot-rolled steel sheet is annealed, and then cold-rolled to reduce the sheet thickness. If necessary, intermediate annealing is performed during cold rolling. The final product plate thickness may be, for example, 0.05 to 0.5 mm. Finish annealing is performed on the cold-rolled steel sheet having a predetermined final product thickness. The finish annealing temperature is an austenite generation temperature range of Ac 1 point or higher. Specifically, it is preferable to heat to an “austenite single-phase temperature range” or “two-phase temperature range in which an austenite phase + 20 vol% or less ferrite phase” in the range of 800 to 1100 ° C. If it is the steel composition range prescribed | regulated by this invention, the austenite phase of the quantity corresponding to (gamma) max can be normally produced | generated in the temperature range of 900-1050 degreeC. The holding time at the finish annealing temperature may be set in the range of 0 to 60 seconds.
仕上焼鈍後、常温までの冷却過程でオーステナイト相はほぼ全量がマルテンサイト相に変態する。一般にマルテンサイト相は、Ｃ、Ｎが過飽和に固溶していること、および多量の転位を内在することによって硬質化する。マルテンサイト変態時の冷却速度が大きいほど硬質化の程度も大きくなり、高強度が得られる。しかし、急冷時に生成したマルテンサイト相は靭性に乏しく、焼戻し熱処理などの後処理を必要とする。発明者らの検討によれば、焼戻し等の後処理を行うことなく、靭性の良好なマルテンサイト組織を得るためには、「オーステナイト単相温度域」または「オーステナイト相＋２０体積％以下のフェライト相となる２相温度域」に加熱した後、比較的緩やかな（急冷ではない）冷却速度で冷却することが有効である。ただし、冷却速度が過剰に遅くなるとＣ、Ｎの固溶量が減少し、マルテンサイト相の強度低下を招く。また、オーステナイト生成元素であるＣ、Ｎの固溶量が減少すると、フェライト相の生成量が増大しやすくなり、それによる強度低下も加わる。種々検討の結果、８００℃から２００℃までの平均冷却速度が１〜１５０℃／ｓとなるように冷却速度を調整することが好ましい。この範囲の冷却速度は、空冷によって実現しやすいが、水冷を採用することも可能である。なお、上記の比較的緩やかな冷却速度での冷却は、マルテンサイト相への靭性付与に加えて、後述のピット形成源となる炭化物生成にも有効である。 After the finish annealing, almost all of the austenite phase is transformed into the martensite phase during the cooling process to room temperature. In general, the martensite phase is hardened by the solid solution of C and N in supersaturation and the presence of a large amount of dislocations. The greater the cooling rate during the martensitic transformation, the greater the degree of hardening and the higher the strength. However, the martensite phase produced during quenching has poor toughness and requires post-treatment such as tempering heat treatment. According to the study by the inventors, in order to obtain a martensitic structure with good toughness without performing post-treatment such as tempering, the “austenite single phase temperature range” or “the austenite phase + 20% by volume or less of ferrite phase” After heating to a “two-phase temperature range”, it is effective to cool at a relatively slow (not rapid) cooling rate. However, when the cooling rate is excessively slow, the solid solution amount of C and N decreases and the strength of the martensite phase is reduced. Further, when the amount of C and N, which are austenite-generating elements, decreases, the amount of ferrite phase generated easily increases, and the strength is thereby reduced. As a result of various studies, it is preferable to adjust the cooling rate so that the average cooling rate from 800 ° C. to 200 ° C. is 1 to 150 ° C./s. The cooling rate in this range is easily realized by air cooling, but water cooling can also be adopted. The cooling at the relatively slow cooling rate described above is effective not only for imparting toughness to the martensite phase, but also for the generation of carbides that will be the pit formation source described later.
塗膜密着性を改善するためには、（i）仕上焼鈍を大気中などの酸化性雰囲気で行い、（ii）８００℃から２００℃までの平均冷却速度を１〜１５０℃／ｓとし、（iii）その後の酸洗において脱スケールを行う、という焼鈍酸洗工程が極めて有効である。
酸化性雰囲気下での加熱により鋼板表面に酸化スケールが形成される。この状態の鋼板を、８００℃から２００℃までの平均冷却速度が１〜１５０℃／ｓである冷却速度で冷却すると、その冷却過程で炭化物が析出成長する時間的余裕が大きくなり、マトリックス（金属素地）中に球状の炭化物粒子が分散した組織状態が得られる。球状の炭化物粒子が分散した焼鈍鋼板に対して脱スケールを主目的とする酸洗を施すと、鋼板表面のスケール直下に存在する球状の炭化物粒子は、スケール除去に伴って鋼板表面から脱落しやすいことがわかった。酸洗により球状の炭化物粒子が脱落した部分には脱落痕として円形状のピットが形成される。その円形状のピットが塗膜に対するアンカー効果を発揮し、塗膜密着性が向上する。
In order to improve coating film adhesion, (i) finish annealing is performed in an oxidizing atmosphere such as in the air, and (ii) the average cooling rate from 800 ° C. to 200 ° C. is 1 to 150 ° C./s, iii) An annealing pickling process in which descaling is performed in the subsequent pickling is extremely effective.
An oxide scale is formed on the surface of the steel sheet by heating in an oxidizing atmosphere. When the steel plate in this state is cooled at a cooling rate of 1 to 150 ° C./s from 800 ° C. to 200 ° C., the time margin for precipitation of carbides during the cooling process increases, and the matrix (metal A textured state in which spherical carbide particles are dispersed in the substrate is obtained. When pickling for the purpose of descaling is applied to an annealed steel sheet in which spherical carbide particles are dispersed, the spherical carbide particles that exist directly under the scale on the steel sheet surface are likely to fall off the steel sheet surface as the scale is removed. I understood it. A circular pit is formed as a drop mark at a portion where the spherical carbide particles are dropped by pickling. The circular pits exert an anchor effect on the coating film, and the coating film adhesion is improved.
炭化物粒子の脱落痕を形成させるための酸洗は、脱スケールを目的とする酸洗と同様の過程とすればよい。例えば、（ａ）中性塩、硫酸、硝酸などを用いた電解、（ｂ）フッ酸と硝酸との混酸浴への浸漬、といった代表的な酸洗手法が挙げられる。上記（ａ）、（ｂ）のいずれか一方、または双方を採用することができる。酸洗条件を強めると、いわゆる過酸洗となり、マトリックス（金属素地）が溶解することに起因して表面粗さが大きくなる。塗膜密着性に関して言えば、一般的に表面粗さが大きい方が有利である。しかし、表面粗さが過大であると、ガスケット用材料に要求される特性（加工性、耐疲労特性、シール性）が低下する要因となる。そこで本発明では、平滑性の高い金属素地を有する表面内に、上述のピット（脱落痕）が分散している表面形態とすることにより、ガスケット材料に要求される特性と塗膜密着性の両立を図る。具体的には、仕上焼鈍後の酸洗処理で析出粒子が脱落することにより形成された開口径１.０μｍ以上のピットを１０個／０.０１ｍｍ2以上の個数密度で表面に有し、圧延直角方向の表面粗さＲａが０.５００μｍ以下である表面形態とすることが望ましい。圧延直角方向Ｒａが０.２００〜０.５００μｍであることがより好ましい。
酸洗処理で析出粒子が脱落することにより形成された開口径１.０μｍ以上のピットの個数密度は以下のようにして測定することができる。
The pickling for forming the falling marks of the carbide particles may be performed in the same manner as the pickling for descaling. For example, typical pickling techniques such as (a) electrolysis using a neutral salt, sulfuric acid, nitric acid, etc. and (b) immersion in a mixed acid bath of hydrofluoric acid and nitric acid can be mentioned. Either one or both of the above (a) and (b) can be employed. When the pickling conditions are increased, so-called peracid cleaning is performed, and the surface roughness increases due to dissolution of the matrix (metal substrate). In terms of coating film adhesion, it is generally advantageous that the surface roughness is large. However, if the surface roughness is excessive, the characteristics (workability, fatigue resistance, sealability) required for the gasket material are reduced. Therefore, in the present invention, by making the surface form in which the above-mentioned pits (drop-off marks) are dispersed in the surface having a metal substrate with high smoothness, both the characteristics required for the gasket material and the coating film adhesion can be achieved. Plan. Specifically, it has pits with an opening diameter of 1.0 μm or more formed on the surface at a number density of 10 / 0.01 mm 2 or more formed by dropping the precipitated particles in the pickling treatment after finish annealing, and rolling. It is desirable to have a surface form in which the surface roughness Ra in the perpendicular direction is 0.500 μm or less. The rolling perpendicular direction Ra is more preferably 0.200 to 0.500 μm.
The number density of pits having an opening diameter of 1.0 μm or more formed by dropping the precipitated particles by pickling treatment can be measured as follows.
〔ピット個数密度の測定方法〕
鋼板表面上に無作為に定めた１または２以上の観察視野において総面積０.１ｍｍ2以上の観察領域内に存在する開口径１.０μｍ以上の脱落痕の数をカウントし、そのカウント総数を観察領域の総面積で除して０.０１ｍｍ2あたりの個数に換算する。設定した観察領域の境界線上に存在するピットについては、観察領域側の開口部輪郭と境界線とに囲まれた形状のピットであるとして開口径１.０μｍ以上の脱落痕に該当するか否かを判定する。
[Measurement method of pit number density]
Count the number of omission marks with an opening diameter of 1.0 μm or more present in an observation area with a total area of 0.1 mm 2 or more in one or more observation fields randomly defined on the surface of the steel sheet. Divide by the total area of the observation area and convert to the number per 0.01 mm 2 . Whether or not a pit existing on the boundary line of the set observation area falls into a drop mark having an opening diameter of 1.0 μm or more because the pit is surrounded by the opening outline and the boundary line on the observation area side. Determine.
上述のように、ピットの開口径は、当該ピットの輪郭で囲まれる開口部の最も長い部分の径（長径）を意味するが、球状の炭化物粒子が脱落して形成されたピットの開口部は円形状を呈するという特徴がある。ピット開口部において、上記長径に対して直角方向に測定した開口部の最も長い部分の径を「短径」と呼び、長径／短径の比を当該ピット開口部のアスペクト比と呼ぶとき、球状の炭化物粒子が脱落して形成されたピットは、開口部のアスペクト比が概ね２.０以下の円形状の形態を呈する。
仕上焼鈍後の酸洗処理で炭化物粒子が脱落することにより形成された開口径１.０μｍ以上、かつ開口部のアスペクト比２.０以下のピットを１０個／０.０１ｍｍ2以上の個数密度で表面に有する鋼板が、本発明において、より好適な対象となる。
As described above, the opening diameter of the pit means the diameter (long diameter) of the longest portion of the opening surrounded by the outline of the pit, but the opening of the pit formed by dropping the spherical carbide particles is It is characterized by a circular shape. In the pit opening, the diameter of the longest part of the opening measured in a direction perpendicular to the long diameter is called “short diameter”, and the ratio of the long diameter / short diameter is called the aspect ratio of the pit opening. The pits formed by dropping off the carbide particles have a circular shape with an opening aspect ratio of approximately 2.0 or less.
With a number density of 10 / 0.01 mm 2 or more of pits having an opening diameter of 1.0 μm or more and an aspect ratio of 2.0 or less formed by the removal of carbide particles by pickling after finish annealing. The steel plate on the surface is a more suitable target in the present invention.
このようにして得られた冷延焼鈍鋼板は、焼戻し軟化や鋭敏化に起因していた強度低下が解消しており、メタルガスケットをはじめとする各種プレス加工用途に適している。また、表面に上述の析出粒子脱落痕が分散している冷延焼鈍鋼板は、塗膜密着性にも優れる。メタルガスケットを製造する過程ではビードプレス成形により一定高さのビードが形成される。得られたプレス加工品に対して、必要に応じて１００〜５００℃で時効処理を施すことができる。 The cold-rolled annealed steel sheet thus obtained is free from strength reduction caused by temper softening and sensitization, and is suitable for various press working applications including metal gaskets. Moreover, the cold-rolled annealed steel sheet in which the above-mentioned precipitate particle drop marks are dispersed on the surface is excellent in coating film adhesion. In the process of manufacturing the metal gasket, a bead having a certain height is formed by bead press molding. The obtained pressed product can be subjected to an aging treatment at 100 to 500 ° C. as necessary.
《実施例１》
表１に示す化学組成の鋼を溶製し、鋳片を得た。鋳片に熱間圧延を施して板厚３.０ｍｍの熱延鋼板を得た。各熱延鋼板に８００℃×２４時間、炉冷の熱処理を施したのち、冷間圧延により板厚を減じた。冷間圧延の途中で８００℃×均熱６０秒の中間焼鈍を１回または複数回入れて、最終板厚０.２ｍｍの冷延鋼板とした。各冷延鋼板から切り出した試料について、表２に示す温度で均熱６０秒の加熱を施したのち、８００℃から２００℃までの平均冷却速度を表２に示すように１５０℃／sまたは５℃／ｓコントロールして常温まで冷却し、各焼鈍温度につき冷却速度の異なる２種類の冷延焼鈍鋼板を得た。
Example 1
Steel having the chemical composition shown in Table 1 was melted to obtain a slab. The slab was hot-rolled to obtain a hot-rolled steel plate having a thickness of 3.0 mm. Each hot-rolled steel sheet was subjected to furnace-cooled heat treatment at 800 ° C. for 24 hours, and then the sheet thickness was reduced by cold rolling. During the cold rolling, intermediate annealing at 800 ° C. × soaking for 60 seconds was performed once or a plurality of times to obtain a cold rolled steel sheet having a final thickness of 0.2 mm. Samples cut from each cold-rolled steel sheet were heated for 60 seconds at a temperature shown in Table 2, and then the average cooling rate from 800 ° C. to 200 ° C. was 150 ° C./s or 5 as shown in Table 2. It was cooled to room temperature under the control of ° C./s to obtain two types of cold-rolled annealed steel sheets having different cooling rates for each annealing temperature.
上記の冷延焼鈍鋼板の板面（圧延面）について、ＪＩＳ Ｚ２２４４：２００９に従い試験力９.８Ｎ（硬さ記号ＨＶ１）にてビッカース硬さを測定した。そして、平均冷却速度５℃／ｓの硬さと平均冷却速度１５０℃／ｓの硬さの差を、硬さ変化量ΔＨとして求めた。このΔＨの絶対値が１０ＨＶ以下であれば、実操業で冷却速度が比較的遅くなった箇所でも所定の強度が維持され、鋼帯内の特性バラツキが非常に小さく抑えられる性質を有していると評価できる。従ってΔＨの絶対値が１０以下であるものを○（焼入れ安定性；顕著に改善）、それ以外を×（焼入れ安定性；改善不十分）と評価し、○評価を合格と判定した。結果を表２に示す。 About the plate | board surface (rolling surface) of said cold-rolled annealing steel plate, Vickers hardness was measured by test force 9.8N (hardness symbol HV1) according to JISZ2244: 2009. And the difference of the hardness of average cooling rate 5 degree-C / s and the hardness of average cooling rate 150 degree-C / s was calculated | required as hardness variation | change_quantity (DELTA) H. If the absolute value of ΔH is 10 HV or less, a predetermined strength is maintained even at a location where the cooling rate is relatively slow in actual operation, and the characteristic variation in the steel strip is extremely small. Can be evaluated. Therefore, a case where the absolute value of ΔH was 10 or less was evaluated as ◯ (quenching stability; remarkably improved), and other cases were evaluated as x (quenching stability; insufficient improvement), and a ◯ evaluation was determined as acceptable. The results are shown in Table 2.
発明対象鋼のものはいずれも焼入れ安定性が顕著に改善されていた。
これに対し、比較鋼である鋼Ｎｏ.１、Ｎｏ.２はＮ含有量が低く、ＣとＮの合計含有量が低く、かつＣ／Ｎ含有量比が高いので、焼き入れ安定性が悪かった。鋼Ｎｏ.３は、Ｃ含有量が高く、Ｎ含有量が低く、かつＣ／Ｎ含有量比が高いので、焼き入れ安定性が更に悪かった。
In all the steels of the invention, the quenching stability was remarkably improved.
In contrast, steels No. 1 and No. 2, which are comparative steels, have a low N content, a low total content of C and N, and a high C / N content ratio, so the quenching stability is poor. It was. Steel No. 3 had a higher C content, a lower N content, and a higher C / N content ratio, and therefore the quenching stability was even worse.
図１に、これらの例について、Ｃ／Ｎ含有量比と硬さ変化量ΔＨの関係を示す。Ｃ／Ｎ含有量比が５.０以下である場合に、ΔＨが−１０以上となり、仕上焼鈍での冷却速度が低下した際の焼入れ安定性が顕著に改善されることがわかる。 FIG. 1 shows the relationship between the C / N content ratio and the hardness change ΔH for these examples. It can be seen that when the C / N content ratio is 5.0 or less, ΔH is −10 or more, and the quenching stability is significantly improved when the cooling rate in the finish annealing is lowered.
《実施例２》
実施例１で作成した冷延鋼板（仕上焼鈍前のもの）から試料を切り出し、１０５０℃で均熱６０秒の加熱を施したのち、８００℃から２００℃までの平均冷却速度を表３に示すようにコントロールして、冷延焼鈍鋼板を得た。仕上焼鈍後の冷却は空冷とし、炉温あるいは空気吹き付け量の調整により冷却速度をコントロールした。試料表面に取り付けた熱電対により冷却時の温度変化を測定し、その冷却曲線に基づき８００℃から２００℃までの平均冷却速度を求めた。板温が常温付近まで下がったのち、３質量％フッ酸＋１２質量％硝酸、６０℃の酸洗液に試料を浸漬する方法で酸洗処理を施した。酸化スケールが除去できた時点で酸洗を終了し、通常の水洗を経て供試材（酸洗材）とした。各供試材について圧延方向および板厚方向に平行な断面（Ｌ断面）を鏡面研磨し、１０質量％シュウ酸水溶液中で６Ｖ、１５秒の電解エッチングを施して調製した観察面について光学顕微鏡で組織観察を行い、鋭敏化の有無を調べた。鋭敏化が認められなかったものを○（鋭敏化；なし）、認められたものを×（鋭敏化；あり）と評価し、○を合格と判定した。結果を表３に示す。
Example 2
Table 3 shows the average cooling rate from 800 ° C. to 200 ° C. after cutting out a sample from the cold-rolled steel sheet (before finish annealing) prepared in Example 1 and heating at 1050 ° C. for 60 seconds. Thus, a cold-rolled annealed steel sheet was obtained. Cooling after the finish annealing was air cooling, and the cooling rate was controlled by adjusting the furnace temperature or the air blowing amount. The temperature change at the time of cooling was measured with the thermocouple attached to the sample surface, and the average cooling rate from 800 ° C. to 200 ° C. was determined based on the cooling curve. After the plate temperature dropped to near room temperature, pickling treatment was performed by dipping the sample in a pickling solution of 3% by mass hydrofluoric acid + 12% by mass nitric acid and 60 ° C. When the oxide scale could be removed, the pickling was finished, and the sample material (pickling material) was obtained through normal water washing. Each specimen was mirror-polished on a cross section (L cross section) parallel to the rolling direction and the plate thickness direction, and subjected to electrolytic etching in a 10% by mass oxalic acid aqueous solution for 6 V for 15 seconds using an optical microscope. Tissue observation was performed to examine the presence or absence of sensitization. The case where no sensitization was observed was evaluated as ◯ (sensitization; none), and the case where sensitization was observed was evaluated as x (sensitization; present). The results are shown in Table 3.
発明対象鋼のものは冷却速度が遅い場合の耐鋭敏化性が改善されていた。これに対し、比較鋼のものは冷却速度が遅い場合に鋭敏化が生じた。本発明に従えば、仕上焼鈍の冷却速度が遅い場合も粒界へのＣｒ炭化物の析出が抑制され、粒界腐食が抑止されたと考えられる。 The steels of the invention had improved sensitization resistance when the cooling rate was slow. In contrast, the comparative steels were sensitized when the cooling rate was slow. According to the present invention, it is considered that the precipitation of Cr carbide at the grain boundaries is suppressed even when the cooling rate of the finish annealing is slow, and the intergranular corrosion is suppressed.
《実施例３》
表１のＮｏ.４の鋼を用いて、実施例１と同様に最終板厚０.２ｍｍの冷延鋼板を得た。この冷延鋼板に表４に示す条件で仕上焼鈍を施した。実施例２と同様の手法で、仕上焼鈍後の８００℃から２００℃までの平均冷却速度をコントロールし、冷延焼鈍鋼板を得た。得られた冷延焼鈍鋼板に３質量％フッ酸＋１２質量％硝酸、６０℃の酸洗液に浸漬する方法で酸洗処理を施した。酸化スケールが除去できた時点で酸洗を終了し、通常の水洗を経て供試材（酸洗材）とした。比較のために還元雰囲気で仕上焼鈍を施したままのＢＡ処理材も用意した。各供試材について鋼板表面の圧延直角方向の表面粗さＲａを触針式の表面粗さ計により測定した。酸洗材についてＳＥＭで鋼板表面を観察することにより、上掲の「ピット個数密度の測定方法」に従い、酸洗処理で析出粒子が脱落することにより形成された開口径１.０μｍ以上のピットの個数密度を求めた。その際、各供試材につき１２視野のＳＥＭ画像を調べた。
Example 3
A cold-rolled steel sheet having a final thickness of 0.2 mm was obtained in the same manner as in Example 1 using No. 4 steel in Table 1. The cold-rolled steel sheet was subjected to finish annealing under the conditions shown in Table 4. In the same manner as in Example 2, the average cooling rate from 800 ° C. to 200 ° C. after finish annealing was controlled to obtain a cold-rolled annealed steel plate. The obtained cold-rolled annealed steel sheet was pickled by a method of dipping in 3% by mass hydrofluoric acid + 12% by mass nitric acid and 60 ° C. pickling solution. When the oxide scale could be removed, the pickling was finished, and the sample material (pickling material) was obtained through normal water washing. For comparison, a BA-treated material that was subjected to finish annealing in a reducing atmosphere was also prepared. For each specimen, the surface roughness Ra in the direction perpendicular to the rolling direction of the steel sheet surface was measured with a stylus type surface roughness meter. By observing the steel plate surface with an SEM for the pickling material, in accordance with the above-mentioned “Method for measuring the number density of pits”, pits having an opening diameter of 1.0 μm or more formed by the precipitation particles dropping out by pickling treatment are used. The number density was determined. At that time, SEM images of 12 visual fields were examined for each specimen.
各供試材の鋼板表面にエポキシ系プライマーを塗布して２００℃で４０ｓｅｃ焼付け乾燥したのち、その上にポリエステル系塗料を塗布して２１５℃で５０ｓｅｃ焼付け乾燥し、塗装鋼板試料を得た。各塗装鋼板試料について、ＪＩＳ ３３２０：１９９９に規定される曲げ試験を施した。曲げ試験片は長手方向が圧延方向となるように採取し、曲げ軸が圧延直角方向、曲げの外側表面が塗装面となるように常温で１８０°曲げを行った。曲げ試験後の曲げ稜線における塗膜剥離の有無を観察し、塗膜剥離が認められなかったものを○評価（塗膜密着性；良好）、塗膜剥離が認められたものを×評価（塗膜密着性；不良）と判定した。結果を表４に示す。 An epoxy-based primer was applied to the surface of each steel plate and baked and dried at 200 ° C. for 40 seconds, and then a polyester-based paint was applied thereon and baked and dried at 215 ° C. for 50 seconds to obtain a coated steel plate sample. Each coated steel plate sample was subjected to a bending test specified in JIS 3320: 1999. The bending test piece was sampled so that the longitudinal direction was the rolling direction, and was bent 180 ° at room temperature so that the bending axis was the direction perpendicular to the rolling direction and the outer surface of the bending was the painted surface. Observe the presence or absence of coating film peeling at the bending ridge line after the bending test, evaluate ○ for coating film peeling (good adhesion); evaluate x for coating film peeling observed (coating Film adhesion; poor). The results are shown in Table 4.
仕上焼鈍の雰囲気を酸化性雰囲気（大気）とし、仕上焼鈍後の８００℃から２００℃までの平均冷却速度を１〜１５０℃／ｓｅｃとしたもの（Ｎｏ.４−２、４−３、４−４）は、酸洗処理で析出粒子が脱落することにより形成された開口径１.０μｍ以上のピットの個数密度が１０個／０.０１ｍｍ2以上であり、塗膜密着性が良好であった。圧延直角方向の表面粗さＲａは０.５００μｍ以下であり、シール性の高いガスケットを得ることができる。 The atmosphere of finish annealing is an oxidizing atmosphere (atmosphere), and the average cooling rate from 800 ° C. to 200 ° C. after finish annealing is 1 to 150 ° C./sec (No. 4-2, 4-3, 4- In 4), the number density of pits having an opening diameter of 1.0 μm or more formed by dropping the precipitated particles by pickling treatment was 10 / 0.01 mm 2 or more, and the coating film adhesion was good. . The surface roughness Ra in the direction perpendicular to rolling is 0.500 μm or less, and a gasket with high sealing properties can be obtained.
これに対し、Ｎｏ.４−１は仕上焼鈍後の冷却速度が大きかったのでマルテンサイト相が過度に硬質化し、曲げ試験で１８０°まで曲げる加工ができなかった。また、炭化物の析出成長が不十分であり、開口径１.０μｍ以上のピットの個数密度が少なかった。Ｎｏ.４−５は仕上焼鈍後の冷却速度を極端に遅くした例であり、硬さが低かった。また、酸洗では酸化スケールが除去された段階で過酸洗となり、圧延直角方向の表面粗さＲａが０.５００μｍを超えて大きくなった。Ｎｏ.４−６は仕上焼鈍を還元性雰囲気で行った例であり、酸洗を行っていないので表面の平滑性が高く、塗膜密着性に劣った。 On the other hand, in No. 4-1, since the cooling rate after the finish annealing was large, the martensite phase became excessively hard, and the bending test could not be performed up to 180 °. Further, precipitation growth of carbide was insufficient, and the number density of pits having an opening diameter of 1.0 μm or more was small. No. 4-5 was an example in which the cooling rate after finish annealing was extremely slow, and the hardness was low. Further, in pickling, peroxidation was performed at the stage where the oxide scale was removed, and the surface roughness Ra in the direction perpendicular to the rolling increased beyond 0.500 μm. No. 4-6 was an example in which finish annealing was performed in a reducing atmosphere, and since pickling was not performed, the surface smoothness was high and the coating film adhesion was inferior.
すなわち本発明では、質量％で、Ｃ：０.１００〜０.１８０％、Ｓｉ：０.２０〜１.５０％、Ｍｎ：０.１０〜２.００％、Ｎｉ：０.０１〜１.００％、Ｃｒ：１１.００〜１８.００％、Ｃｕ：０.１８〜１.６０％、Ｍｏ：０〜０.５０％、Ｎ：０.０３０〜０.１００％、Ｖ：０〜０.５０％、Ｎｂ：０〜０.５０％、Ｔｉ：０〜０.５０％、Ｂ：０〜０.０２０％、残部Ｆｅおよび不可避的不純物からなり、ＣとＮの合計含有量が０.１３０質量％以上、Ｃ／Ｎ含有量比（質量％比）が５.０以下、かつ下記（１）式により定まるγmax値が８０.０以上である化学組成を有するマルテンサイト系ステンレス鋼板が提供される。
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には質量％で表される当該元素の含有量が代入される。
That is, in the present invention, by mass%, C: 0.10 to 0.180%, Si: 0.20 to 1.50%, Mn: 0.10 to 2.00%, Ni: 0.01 to 1. 00%, Cr: 11.00 to 18.00%, Cu: 0.18 to 1.60%, Mo: 0 to 0.50%, N: 0.030 to 0.100%, V: 0 to 0 .50%, Nb: 0 to 0.50%, Ti: 0 to 0.50%, B: 0 to 0.020%, remaining Fe and inevitable impurities, and the total content of C and N is 0.5. Provided is a martensitic stainless steel sheet having a chemical composition of 130% by mass or more, a C / N content ratio (mass% ratio) of 5.0 or less, and a γmax value determined by the following formula (1) of 80.0 or more. Is done.
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the content of the element represented by mass% is substituted for the element symbol in the formula (1).
Ｃｕは、オーステナイト生成元素であり、マルテンサイト量を十分に確保する上で有効である。また、Ｎの固溶限を確保するためにも有効である。ただし、Ｃｕ含有量が過大になると残留オーステナイト相が存在しやすくなり、強度向上や熱間加工性確保に不利となる。Ｃｕ含有量は０.１８％以上１.６０％以下とする。 Cu is an austenite generating element and is effective in securing a sufficient amount of martensite. Further, it is also effective to ensure the solid solubility limit of N. However, it is retained austenite phase content of Cu becomes excessive is easily exist, which is disadvantageous for improving the strength and hot workability ensured. The Cu content is 0.18% or more and 1.60% or less.
Claims (10)
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には質量％で表される当該元素の含有量が代入される。 In mass%, C: 0.100 to 0.180%, Si: 0.20 to 1.50%, Mn: 0.10 to 2.00%, Ni: 0.01 to 1.00%, Cr: 11.0 to 18.00%, Cu: 0.20 to 1.60%, Mo: 0 to 0.50%, N: 0.030 to 0.100%, V: 0 to 0.50%, Nb : 0 to 0.50%, Ti: 0 to 0.50%, B: 0 to 0.020%, balance Fe and inevitable impurities, the total content of C and N is 0.130% or more, C A martensitic stainless steel sheet having a chemical composition having a / N content ratio of 5.0 or less and a γmax value determined by the following formula (1) of 80.0 or more.
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the content of the element represented by mass% is substituted for the element symbol in the formula (1).
を有するマルテンサイト系ステンレス鋼板の製造法。
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には質量％で表される当該元素の含有量が代入される。 In mass%, C: 0.100 to 0.180%, Si: 0.20 to 1.50%, Mn: 0.10 to 2.00%, Ni: 0.01 to 1.00%, Cr: 11.0 to 18.00%, Cu: 0.20 to 1.60%, Mo: 0 to 0.50%, N: 0.030 to 0.100%, V: 0 to 0.50%, Nb : 0 to 0.50%, Ti: 0 to 0.50%, B: 0 to 0.020%, balance Fe and inevitable impurities, the total content of C and N is 0.130% or more, C An austenite single-phase temperature of an intermediate product steel sheet having a chemical composition having a / N content ratio of 5.0 or less and a γmax value determined by the following formula (1) of 80.0 or more in a range of 800 to 1100 ° C. Or austenite phase + 20 volume% or less of the two-phase temperature range, which is a ferrite phase, and then cooled to cool the austenite phase to martensite. Step of transformation to (finish annealing process),
Method for producing martensitic stainless steel sheet having
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the content of the element represented by mass% is substituted for the element symbol in the formula (1).
を有するマルテンサイト系ステンレス鋼板の製造法。
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には質量％で表される当該元素の含有量が代入される。 In mass%, C: 0.100 to 0.180%, Si: 0.20 to 1.50%, Mn: 0.10 to 2.00%, Ni: 0.01 to 1.00%, Cr: 11.0 to 18.00%, Cu: 0.20 to 1.60%, Mo: 0 to 0.50%, N: 0.030 to 0.100%, V: 0 to 0.50%, Nb : 0 to 0.50%, Ti: 0 to 0.50%, B: 0 to 0.020%, balance Fe and inevitable impurities, the total content of C and N is 0.130% or more, C An austenite single-phase temperature of an intermediate product steel sheet having a chemical composition having a / N content ratio of 5.0 or less and a γmax value determined by the following formula (1) of 80.0 or more in a range of 800 to 1100 ° C. The average cooling rate from 800 ° C to 200 ° C is 1-1 to Step of cooling such that 0 ° C. / sec (final annealing step),
Method for producing martensitic stainless steel sheet having
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the content of the element represented by mass% is substituted for the element symbol in the formula (1).
仕上焼鈍工程後の鋼板を酸洗処理することにより表面の酸化スケールを除去するとともに、表面に存在する炭化物粒子を脱落させて表面にピットを形成する工程（酸洗工程）、
を有するマルテンサイト系ステンレス鋼板の製造法。
γmax＝４２０Ｃ−１１.５Ｓｉ＋７Ｍｎ＋２３Ｎｉ−１１.５Ｃｒ−１２Ｍｏ＋９Ｃｕ−４９（Ｔｉ＋Ｎｂ＋Ｖ）＋４７０Ｎ＋１８９ …（１）
ここで、（１）式の元素記号の箇所には質量％で表される当該元素の含有量が代入される。 In mass%, C: 0.100 to 0.180%, Si: 0.20 to 1.50%, Mn: 0.10 to 2.00%, Ni: 0.01 to 1.00%, Cr: 11.0 to 18.00%, Cu: 0.20 to 1.60%, Mo: 0 to 0.50%, N: 0.030 to 0.100%, V: 0 to 0.50%, Nb : 0 to 0.50%, Ti: 0 to 0.50%, B: 0 to 0.020%, balance Fe and inevitable impurities, the total content of C and N is 0.130% or more, C An intermediate product steel sheet having a chemical composition having a / N content ratio of 5.0 or less and a γmax value determined by the following formula (1) of 80.0 or more is in the range of 800 to 1100 ° C. in an oxidizing atmosphere. After heating to an austenite single phase temperature range or a two-phase temperature range that becomes an austenite phase + 20% by volume or less ferrite phase, the temperature ranges from 800 ° C. to 200 ° C. Step of precipitating carbide particles by cooling as average cooling rate is 1 to 150 ° C. / sec (final annealing step),
Removing the surface oxide scale by pickling the steel plate after the finish annealing step, dropping the carbide particles present on the surface to form pits on the surface (pickling step),
Method for producing martensitic stainless steel sheet having
γmax = 420C-11.5Si + 7Mn + 23Ni-11.5Cr-12Mo + 9Cu-49 (Ti + Nb + V) + 470N + 189 (1)
Here, the content of the element represented by mass% is substituted for the element symbol in the formula (1).
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