JP2017014556A - Martensitic stainless steel excellent in precipitation hardening performance - Google Patents
Martensitic stainless steel excellent in precipitation hardening performance Download PDFInfo
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- 238000004881 precipitation hardening Methods 0.000 title claims abstract description 13
- 229910001105 martensitic stainless steel Inorganic materials 0.000 title claims description 11
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 36
- 238000005260 corrosion Methods 0.000 abstract description 36
- 229910000831 Steel Inorganic materials 0.000 abstract description 27
- 239000010959 steel Substances 0.000 abstract description 27
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910000734 martensite Inorganic materials 0.000 abstract 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 230000032683 aging Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000005242 forging Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
Description
本願の発明は、自動車の主要装置であるエンジンの動力を伝えるために変速機と差動歯車とをつなぐ回転軸であるプロペラシャフトや自動車の懸架装置との関係でエンジンの動力を左右の車輪に伝達するためのドライブシャフトなど、あるいは圧延用のロールや鍛造用のロールなどの、高硬度、高耐食および高靱性が求められる析出硬化型であるマルテンサイト系ステンレス鋼に関する。 The invention of this application uses the propeller shaft, which is the rotating shaft that connects the transmission and the differential gear to transmit the power of the engine, which is the main device of the automobile, and the engine power to the left and right wheels in relation to the suspension system of the automobile. The present invention relates to a martensitic stainless steel that is a precipitation hardening type that requires high hardness, high corrosion resistance, and high toughness, such as a drive shaft for transmission, a roll for rolling, and a roll for forging.
ＪＩＳに規定するＳＵＳ６３０およびＳＵＳ６３１のステンレス鋼に代表される析出硬化系ステンレス鋼は、時効熱処理によって良好な耐食性と高硬度でかつ高靱性を有する材料である。しかし、これらの析出硬化系ステンレス鋼には、スクラップを再利用する鉄鋼材料の利点を阻害するトランプエレメントの１つであるＣｕを析出硬化元素として利用しているものが多く、Ｃｕを利用しない場合であっても、硬さや靱性に悪影響を及ぼすδフェライトやγの量を制御し、さらに耐食性を維持するために、高価なＮｉやＭｏを多量に添加したり、あるいは複雑な加工熱処理を行ったりしている。このために、コストアップが避けられない状況である。そこで、トランプエレメントや高価な元素などを多量に添加することなく、また複雑な加工熱処理に頼ることなく、安価で、かつ、高い硬度、高い靱性、優れた耐食性が発揮できる析出硬化系ステンレス鋼が求められている。 Precipitation hardening type stainless steel represented by JIS SUS630 and SUS631 stainless steel defined in JIS is a material having good corrosion resistance, high hardness and high toughness by aging heat treatment. However, many of these precipitation hardening stainless steels use Cu as a precipitation hardening element, which is one of the trump elements that hinder the advantages of steel materials that reuse scrap, and when Cu is not used. Even so, in order to control the amount of δ ferrite and γ that adversely affect hardness and toughness, and to maintain corrosion resistance, a large amount of expensive Ni and Mo are added, or complex thermomechanical heat treatment is performed. doing. For this reason, an increase in cost is inevitable. Therefore, precipitation hardened stainless steel that is inexpensive and can exhibit high hardness, high toughness, and excellent corrosion resistance without adding a large amount of playing elements, expensive elements, etc., and without relying on complicated processing heat treatment. It has been demanded.
ところで、従来の自動車の足回りの部品などに使用される鋼材として、焼入れ焼戻しなどの熱処理を必要とせず、熱間鍛造後、自然空冷のままで、優れた強度および靱性の得られる鋼材が提案されている（例えば、特許文献１参照。）。しかし、この鋼材は、Ｃｒを０．８〜２．０％含有しており、耐食性の鋼材ではない。 By the way, as a steel material used for parts of a conventional automobile undercarriage, etc., a steel material that does not require a heat treatment such as quenching and tempering and can be obtained with excellent strength and toughness while being naturally air cooled after hot forging. (For example, refer to Patent Document 1). However, this steel material contains 0.8 to 2.0% of Cr and is not a corrosion-resistant steel material.
本発明と技術分野および用途が同じで、鋼種も析出硬化型マルテンサイト系ステンレス鋼で同じであるが、析出硬化元素としてＣｕを必須元素とし、さらに被削性に特化するために、Ｓも積極的に添加している鋼が提案されている（例えば、特許文献２参照。）。しかしながら、一般にＣｕはトランプエレメントとして含有されるが、特許文献２のＣｕの含有量では多すぎて、トランプエレメントとしての鋼の再利用が阻害される。一方、Ｓは多く含有されると、延性、靱性、熱間加工性が劣化するので、積極的に添加することは一般には行われていない。したがって、この特許文献２のものは、高硬度、高耐食性および高靱性を得る目的で積極的に添加するものであって、本願発明のものとは相違するものである。 The technical field and application are the same as in the present invention, and the steel type is the same in precipitation hardening martensitic stainless steel, but Cu is an essential element as a precipitation hardening element, and in order to specialize in machinability, S is also used. Steel that is actively added has been proposed (see, for example, Patent Document 2). However, in general, Cu is contained as a playing element, but the Cu content of Patent Document 2 is too large, and the reuse of steel as a playing element is hindered. On the other hand, when a large amount of S is contained, ductility, toughness, and hot workability deteriorate, so that it is generally not actively added. Therefore, the thing of this patent document 2 is positively added in order to obtain high hardness, high corrosion resistance, and high toughness, and is different from the thing of this invention.
さらに、ＣｕおよびＳを積極的に添加して、高強度を有しつつ被削性に優れ、さらに良好な冷間加工性を有する鋼が提案されている（例えば、特許文献３参照。）。しかしながら、このものは、特許文献２と同様に、一般にＣｕはトランプエレメントとして含有されるが、特許文献３のＣｕの含有量では多すぎて、トランプエレメントとしての鋼の再利用が阻害される。 Furthermore, steel which has been added with Cu and S positively and has high strength and excellent machinability and further good cold workability has been proposed (for example, see Patent Document 3). However, as in Patent Document 2, this generally contains Cu as a playing element, but the Cu content of Patent Document 3 is too large, and the reuse of steel as a playing element is hindered.
また、ＣｕやＴｉ等の析出硬化元素を添加することなく、成分および調質圧延（圧延率１〜１０％）にて材料中のδフェライトおよび残留γ量を制御し、高硬度および高靱性が得られる鋼板の発明が提案されている（例えば、特許文献４参照。）。しかし、このものは目的の特性を得るためには、厳密に工程設計された調質圧延が必須であり、成分（添加元素）と熱処理にて高硬度および高靱性を得る本願の発明とは相違する。 Moreover, without adding precipitation hardening elements such as Cu and Ti, the amount of δ ferrite and residual γ in the material is controlled by ingredients and temper rolling (rolling ratio 1 to 10%), and high hardness and high toughness are achieved. Invention of the steel plate obtained is proposed (for example, refer patent document 4). However, in order to obtain the desired properties, temper rolling with strict process design is indispensable, which is different from the invention of the present application in which high hardness and high toughness are obtained by components (additive elements) and heat treatment. To do.
また、高耐食、高靱性および高硬度が得られる析出硬化型ステンレス鋼の発明が提案されている。（例えば、特許文献５参照。）。しかし、この提案のものは、Ｃｕ、高価なＣｏおよびＭｏを必須元素としており、再利用性およびコスト面で不利と見られる。 Further, an invention of a precipitation hardening type stainless steel capable of obtaining high corrosion resistance, high toughness and high hardness has been proposed. (For example, refer to Patent Document 5). However, this proposal uses Cu, expensive Co and Mo as essential elements, and is considered disadvantageous in terms of reusability and cost.
そこで、本願発明が解決しようとする課題は、鉄鋼材料の利点である再利用性を阻害するようなトランプエレメントを使用することなく、比較的安価で、高硬度、高靱性であり、かつ優れた耐食性を備えた材料の鋼を提供することである。 Therefore, the problem to be solved by the present invention is that it is relatively inexpensive, high hardness, high toughness, and excellent without using a trump element that hinders reusability, which is an advantage of steel materials. It is to provide a steel material with corrosion resistance.
課題を解決するための本願の手段は、第１の手段では、質量％で、Ｃ：０．０１〜０．１０％、Ｓｉ：０．３０〜２．００％、Ｍｎ：０．０１〜１．００％、Ｐ：０．０４０％以下、Ｓ：０．０３０％以下、Ｎｉ：３．０〜８．０％、Ｃｒ：１２．０〜２０．０％、Ｍｏ：０．２０〜０．８０％、Ｃｕ：０．５０％以下、Ｔｉ：０．３０〜２．５０％、Ｎｂ：０．０１〜２．００％、Ｎ：０．０５００％以下、残部Ｆｅおよび不可避不純物からなり、式１：［Ｃｒ］＋［Ｍｏ］＋［Ｎｂ］＋［Ｔｉ］＋［Ｓｉ］＋［Ｎｉ］−２６（［Ｃ］＋［Ｎ］）−１０．３≧１０．０、式２：［Ｃｒ］＋１．５［Ｓｉ］＋［Ｍｏ］＋０．５［Ｎｂ］＋２［Ｔｉ］−０．５［Ｎｉ］−６．７（［Ｃ］＋［Ｎ］）≦２０．０を満足することを特徴とする析出硬化能に優れたマルテンサイト系ステンレス鋼である。ただし、上記の式１および式２の［元素記号］は、質量％で示す成分元素の量を％で示す際の数値を表す。 The means of the present application for solving the problem is, in the first means, in mass%, C: 0.01 to 0.10%, Si: 0.30 to 2.00%, Mn: 0.01 to 1 0.000%, P: 0.040% or less, S: 0.030% or less, Ni: 3.0-8.0%, Cr: 12.0-20.0%, Mo: 0.20-0. 80%, Cu: 0.50% or less, Ti: 0.30 to 2.50%, Nb: 0.01 to 2.00%, N: 0.0500% or less, balance Fe and inevitable impurities, 1: [Cr] + [Mo] + [Nb] + [Ti] + [Si] + [Ni] −26 ([C] + [N]) − 10.3 ≧ 10.0, Formula 2: [Cr ] +1.5 [Si] + [Mo] +0.5 [Nb] +2 [Ti] −0.5 [Ni] −6.7 ([C] + [N]) ≦ 20.0 Characterized precipitation hardness An excellent martensitic stainless steel capacity. However, the [element symbol] in the above formulas 1 and 2 represents a numerical value when the amount of the component element represented by mass% is represented by%.
本願の発明は、鉄鋼材料の利点である再利用性を阻害するようなトランプエレメントを使用することなく、比較的に安価で、時効硬さが４５ＨＲＣ以上の高硬度で、シャルピー衝撃値が４５Ｊ／ｃｍ2以上の高靱性であり、かつ孔食試験における腐食度が２０ｇ／ｃｍ2／ｈ以下である耐食性に優れた材料のマルテンサイト系ステンレス鋼を得ることが複雑な加工熱処理に頼ることなくできる。 The invention of the present application is relatively inexpensive, has a high age hardness of 45 HRC or higher, and has a Charpy impact value of 45 J / min without using a trump element that hinders reusability, which is an advantage of steel materials. It is possible to obtain a martensitic stainless steel having a high toughness of cm 2 or more and a corrosion resistance in a pitting corrosion test of 20 g / cm 2 / h or less and having excellent corrosion resistance without resorting to complicated thermomechanical processing. .
本発明を実施するための形態を記載するに先立って、本願発明における化学成分の限定理由並びに式１および式２の限定理由を以下に説明する。なお、％は質量％である。 Prior to describing the embodiment for carrying out the present invention, the reasons for limiting chemical components and the reasons for limiting Formula 1 and Formula 2 in the present invention will be described below. In addition,% is the mass%.
Ｃ：０．０１〜０．１０％
Ｃは、γ相の安定化元素であって、過剰なδフェライトの生成を抑制し、良好な靱性を確保する元素である。このためには、Ｃは０．０１％以上含有されることが必要である。しかし、Ｃが０．１０％より多いと炭窒化物を生成して耐食性を劣化する。そこで、Ｃは０．０１〜０．１０％とする。
C: 0.01 to 0.10%
C is a γ-phase stabilizing element that suppresses the formation of excess δ ferrite and ensures good toughness. For this purpose, C must be contained in an amount of 0.01% or more. However, if C is more than 0.10%, carbonitrides are produced and the corrosion resistance is degraded. Therefore, C is set to 0.01 to 0.10%.
Ｓｉ：０．３０〜２．００％
Ｓｉは、製鋼段階での脱酸剤であり、析出硬化粒子を生成する元素である。このためには、Ｓｉは０．３０％以上含有される。しかし、Ｓｉが２．００％より多いと、鋼材の延性を阻害し、δフェライト生成による靱性の低下および鋼材の製造性を低下する。そこで、Ｓｉは０．３０〜２．００％とし、好ましくは０．５０〜１．８０％とする。
Si: 0.30 to 2.00%
Si is a deoxidizer in the steelmaking stage, and is an element that generates precipitation hardened particles. For this purpose, Si is contained in an amount of 0.30% or more. However, if Si is more than 2.00%, the ductility of the steel material is hindered, the toughness is reduced due to the formation of δ ferrite, and the productivity of the steel material is lowered. Therefore, Si is 0.30 to 2.00%, preferably 0.50 to 1.80%.
Ｍｎ：０．０１〜１．００％
Ｍｎは、製鋼段階での脱酸剤として必要な元素である。このためには、Ｍｎは０．０１％以上含有されることが必要である。しかし、Ｍｎが１．００％より多くても脱酸剤としての効果は飽和し、さらに硫化物の生成を促進して耐食性を落下する。そこで、Ｍｎは０．０１〜１．００％とし、好ましくは０．１０〜０．８０％とする。
Mn: 0.01 to 1.00%
Mn is an element necessary as a deoxidizer in the steelmaking stage. For this purpose, Mn needs to be contained in an amount of 0.01% or more. However, even if Mn is more than 1.00%, the effect as a deoxidizer is saturated, and further, the formation of sulfides is promoted and the corrosion resistance is lowered. Therefore, Mn is 0.01 to 1.00%, preferably 0.10 to 0.80%.
Ｐ：０．０４０％以下
Ｐは、不純物として含有される元素である。しかし、Ｐは０．０４０％より多いと、得られた鋼材の延性、靱性あるいは熱間加工性を劣化する。そこで、Ｐは０．０４０％以下とし、好ましくは０．０２０％以下とする。
P: 0.040% or less P is an element contained as an impurity. However, when P is more than 0.040%, the ductility, toughness or hot workability of the obtained steel material deteriorates. Therefore, P is set to 0.040% or less, preferably 0.020% or less.
Ｓ：０．０３０％以下
Ｓ、不純物として含有される元素である。しかし、Ｓは０．０３０％より多いと、得られた鋼材の延性、靱性あるいは熱間加工性を劣化する。そこで、Ｓは０．０３０％以下とし、好ましくは０．０２０％以下とする。
S: 0.030% or less S is an element contained as an impurity. However, when S is more than 0.030%, the ductility, toughness or hot workability of the obtained steel material is deteriorated. Therefore, S is set to 0.030% or less, preferably 0.020% or less.
Ｎｉ：３．０〜８．０％
Ｎｉは、γ相の安定化元素であって、過剰なδフェライトの生成を抑制し、良好な靱性を確保し、さらに焼入性の向上による均質な微細組織を形成する元素である。このためには、Ｎｉは３．０％以上含有されることが必要である。しかし、Ｎｉは８．０％より多く含有されても上記した効果は飽和し、さらに高価な元素であるので高コストとなる。そこで、Ｎｉは３．０〜８．０％とし、好ましくは４．５〜６．５％とする。
Ni: 3.0-8.0%
Ni is an element that stabilizes the γ phase and suppresses the formation of excessive δ ferrite, ensures good toughness, and forms a homogeneous microstructure by improving hardenability. For this purpose, Ni needs to be contained in an amount of 3.0% or more. However, even if Ni is contained in an amount of more than 8.0%, the above-described effects are saturated and the cost is high because it is an expensive element. Therefore, Ni is set to 3.0 to 8.0%, preferably 4.5 to 6.5%.
Ｃｒ：１２．０〜２０．０％
Ｃｒは、耐食性を向上させる元素である。このためには、Ｃｒは１２．０％以上含有されることが必要である。しかし、Ｃｒは２０．０％より多く含有されても、耐食性向上の効果は飽和し、δフェライト生成による靱性の劣化および脆化相を形成する。そこで、Ｃｒは１２．０〜２０．０％とし、好ましくは１４．０〜１８．０％とする。
Cr: 12.0 to 20.0%
Cr is an element that improves the corrosion resistance. For this purpose, Cr needs to be contained at 12.0% or more. However, even if Cr is contained in an amount of more than 20.0%, the effect of improving the corrosion resistance is saturated, and the toughness is deteriorated due to the formation of δ ferrite and an embrittled phase is formed. Therefore, Cr is 12.0 to 20.0%, preferably 14.0 to 18.0%.
Ｍｏ：０．２０〜０．８０％
Ｍｏは、耐食性を向上させる元素である。このためには、Ｍｏは０．２０％以上含有されることが必要である。しかし、Ｍｏは高価な元素であるので、０．８０％より多く含有されると高コストとなる。そこで、Ｍｏは０．２０〜０．８０％とする。
Mo: 0.20 to 0.80%
Mo is an element that improves the corrosion resistance. For this purpose, Mo needs to be contained by 0.20% or more. However, since Mo is an expensive element, if it is contained more than 0.80%, the cost becomes high. Therefore, Mo is 0.20 to 0.80%.
Ｃｕ：０．５０％以下
Ｃｕは、不純物として含有される元素である。ところで、Ｃｕは循環性元素すなわちトランプエレメントであり、多く含有されると鋼の再利用を阻害する元素である。そこで、Ｃｕは０．５０％以下とし、好ましくは０．２０％以下とする。
Cu: 0.50% or less Cu is an element contained as an impurity. By the way, Cu is a circulating element, that is, a trump element, and if contained in a large amount, Cu is an element that inhibits the reuse of steel. Therefore, Cu is 0.50% or less, preferably 0.20% or less.
Ｔｉ：０．３０〜２．５０％
Ｔｉは、析出硬化粒子を生成して得られた鋼を強化する元素である。このために、Ｔｉは０．７０％以上含有されることが必要である。しかし、Ｔｉは２．５０％より多く含有されると粗大炭窒化物を生成して耐食性を劣化すると共に、高コストとなる。そこで、Ｔｉは０．３０〜２．５０％とし、好ましくは０．７０〜２．３０％とする。
Ti: 0.30 to 2.50%
Ti is an element that strengthens steel obtained by generating precipitation hardening particles. For this reason, it is necessary to contain Ti 0.70% or more. However, if Ti is contained in an amount of more than 2.50%, coarse carbonitrides are generated to deteriorate the corrosion resistance and increase the cost. Therefore, Ti is 0.30 to 2.50%, preferably 0.70 to 2.30%.
Ｎｂ：０．０１〜２．００％
Ｎｂは、析出硬化粒子を生成して得られた鋼を強化する元素である。このために、Ｎｂは０．０１％以上含有されることが必要である。しかし、Ｎｂは２．００％より多く含有されると粗大なＮｂ炭化物が生成されて耐食性を劣化すると共に、高コストとなる。そこで、Ｎｂは０．０１〜２．００％とする。
Nb: 0.01 to 2.00%
Nb is an element that strengthens steel obtained by generating precipitation hardening particles. For this reason, Nb needs to contain 0.01% or more. However, if Nb is contained in an amount of more than 2.00%, coarse Nb carbides are generated to deteriorate the corrosion resistance and increase the cost. Therefore, Nb is set to 0.01 to 2.00%.
Ｎ：０．０５００％以下
Ｎは、耐食性および結晶粒粗大化の防止に有効な元素である。このために、Ｎは０．０５００％以下とする必要がある。Ｎが０．０５００％より多いと粗大炭窒化物を生成して耐食性を劣化する。そこで、Ｎは０．０５００％以下とする。
N: 0.0500% or less N is an element effective for preventing corrosion and coarsening of crystal grains. For this reason, N needs to be 0.0500% or less. When N is more than 0.0500%, coarse carbonitride is produced and the corrosion resistance is deteriorated. Therefore, N is set to 0.0500% or less.
式１：［Ｃｒ］＋［Ｍｏ］＋［Ｎｂ］＋［Ｔｉ］＋［Ｓｉ］＋［Ｎｉ］−２６（［Ｃ］＋［Ｎ］）−１０．３≧１０．０
式１は、マルテンサイトステンレス鋼の時効硬さおよび耐食性を確保するために必要な条件を示す式である。すなわち、この式１において、括弧中に元素記号を記載して示している［元素記号］は、本願のマルテンサイトステンレス鋼の各発明例または各比較例の供試材に含有される各成分元素の量を％で示す際の数値である。この式１の値が１０．０以上であれば、その式１で示すマルテンサイトステンレス鋼は、その鋼の時効硬さが４５ＨＲＣ以上であり、さらに孔食試験の腐食度が２０ｇ／ｍ2／ｈ未満で、耐食性が確保できる。そこで、式１の値は１０．０以上とする。
Formula 1: [Cr] + [Mo] + [Nb] + [Ti] + [Si] + [Ni] −26 ([C] + [N]) − 10.3 ≧ 10.0
Formula 1 is a formula which shows conditions required in order to ensure the aging hardness and corrosion resistance of martensitic stainless steel. That is, in the formula 1, [element symbol] indicated in parentheses by describing the element symbol is each component element contained in the sample material of each invention example or each comparative example of the martensitic stainless steel of the present application. It is a numerical value when the amount of is shown in%. If the value of the formula 1 is 10.0 or more, the martensitic stainless steel represented by the formula 1 has an aging hardness of 45 HRC or more, and further has a corrosion degree of 20 g / m 2 / pitting corrosion test. Less than h, corrosion resistance can be ensured. Therefore, the value of Equation 1 is set to 10.0 or more.
式２：［Ｃｒ］＋１．５［Ｓｉ］＋［Ｍｏ］＋０．５［Ｎｂ］＋２［Ｔｉ］−０．５［Ｎｉ］−６．７（［Ｃ］＋［Ｎ］）≦２０．０
式２は、時効硬さおよび耐食性を確保しつつ、δフェライト増量による衝撃特性の劣化を回避するために必要な条件を示す式である。式２において、［元素記号］は、本願のマルテンサイトステンレス鋼の各発明例または各比較例の供試材に含有される各成分元素の量を％で示す際の数値である。この式２の値が２０．０以下であれば、その式２で示すマルテンサイトステンレス鋼は、その鋼の時効硬さおよび耐食性を確保しつつ、δフェライト増量による衝撃特性の劣化を回避できる、すなわち、シャルピー衝撃値の値を４５Ｊ／ｃｍ2以上にすることができる。そこで、式２の値は２０．０以下とする。
Formula 2: [Cr] +1.5 [Si] + [Mo] +0.5 [Nb] +2 [Ti] −0.5 [Ni] −6.7 ([C] + [N]) ≦ 20.0
Expression 2 is an expression showing conditions necessary for avoiding deterioration of impact characteristics due to an increase in δ ferrite while ensuring aging hardness and corrosion resistance. In Formula 2, [element symbol] is a numerical value when the amount of each component element contained in the sample material of each invention example or each comparative example of the martensitic stainless steel of the present application is expressed in%. If the value of Formula 2 is 20.0 or less, the martensitic stainless steel represented by Formula 2 can avoid deterioration of impact characteristics due to an increase in δ ferrite while securing the aging hardness and corrosion resistance of the steel. That is, the Charpy impact value can be 45 J / cm 2 or more. Therefore, the value of Expression 2 is set to 20.0 or less.
次いで、本願発明の実施の形態について、表１に基づいて、以下に説明する。先ず、本願発明の実施例およびその比較例については、表１に示す発明例のＮｏ．１〜１３と、こ比較例のＮｏ．１４〜３３における、各Ｎｏ．の化学成分からなる供試材の鋼を、１００ｋｇ真空誘導加熱炉（ＶＩＭ）で溶解して鋼塊とした。これらの鋼塊を、１１５０℃に加熱して径２０ｍｍの丸棒材あるいは一辺１５ｍｍの角材に、それぞれ鍛伸した。その後、これらの棒材あるいは角材からなる鋼を９００℃〜１２００℃に１０分以上保持した後に水冷する固溶化熱処理を行った。その後、さらに、これらの鋼を−９０℃〜−２０℃に１０分以上に保持してサブゼロ処理し、さらに、時効熱処理として、３００℃〜８００℃に３０分以上保持した後、空冷して各試験片とした。 Next, embodiments of the present invention will be described below based on Table 1. First, with respect to the examples of the present invention and comparative examples thereof, No. 1-13 and No. of this comparative example. 14-33, each No. The steel of the test material consisting of the following chemical components was melted in a 100 kg vacuum induction heating furnace (VIM) to form a steel ingot. These ingots were heated to 1150 ° C. and forged into round bars with a diameter of 20 mm or squares with a side of 15 mm. Thereafter, the steel made of these rods or squares was held at 900 ° C. to 1200 ° C. for 10 minutes or more, and then subjected to a solution heat treatment that was water-cooled. Thereafter, these steels were further maintained at −90 ° C. to −20 ° C. for 10 minutes or more and subjected to subzero treatment. Further, as an aging heat treatment, the steel was maintained at 300 ° C. to 800 ° C. for 30 minutes or more, and then air-cooled. A test piece was obtained.
表１において、Ｆｅの項目における残部には不可避不純物も含む。さらに、式１および式２の項目の数値は、各Ｎｏ．における各式１および各式２の算出値である。 In Table 1, the remainder in the item of Fe includes inevitable impurities. Further, the numerical values of the items of the formula 1 and the formula 2 are respectively No. Are the calculated values of Equation 1 and Equation 2.
上記で作成した径２０ｍｍの丸棒材の時効熱処理後の試験片について、それらの鍛伸方向に垂直な断面の端部と中心部の間の箇所のロックウェル硬さを測定し、下記の表２に時効硬さを示し評価した。事項硬さの測定値が４５ＨＲＣ以上を評価の項目に○と記し、４５ＨＲＣ未満を評価の項目に×と記した。 About the test piece after aging heat treatment of the round bar material of diameter 20mm created above, the Rockwell hardness of the location between the edge part and center part of a cross section perpendicular | vertical to those forging directions was measured, and the following table | surface The aging hardness was shown in 2 and evaluated. When the measured hardness value was 45 HRC or more, the evaluation item was marked with “◯”, and when it was less than 45 HRC, the evaluation item was marked with “X”.
上記で作成した一辺１５ｍｍの角材を使用して、時効熱処理後に鍛伸方向に平行に一辺１０ｍｍの角状で長さ５５ｍｍの試験片を切り出し、これから２ｍｍＵノッチ試験片を作製し、これを常温にてシャルピー衝撃試験に供してシャルピー衝撃値を測定し、下記の表２にシャルピー衝撃値を示し評価した。シャルピー衝撃値の測定値が４５Ｊ／ｃｍ2以上を評価の項目に○と記し、４５Ｊ／ｃｍ2未満を評価の項目に×と記した。 Using the square material with a side of 15 mm created above, after aging heat treatment, cut out a test piece with a side of 10 mm and a length of 55 mm parallel to the forging direction, from which a 2 mm U-notch test piece was prepared. The Charpy impact value was measured using a Charpy impact test, and the Charpy impact value was shown in Table 2 below for evaluation. A measured value of Charpy impact value of 45 J / cm 2 or more was marked as “◯” as an evaluation item, and less than 45 J / cm 2 was marked as “X” as an evaluation item.
上記で作成した径２０ｍｍの丸棒材の時効熱処理後の試験片を、径１２ｍｍで長さ２１ｍｍの丸棒状の腐食試験片へ加工した。これらの丸棒状の腐食試験片を、６％塩化第二鉄の２５℃の孔食試験液に２４時間浸漬する孔食試験を実施し、その腐食度を測定し、下記の表２に孔食試験の腐食度を示し評価した。孔食試験の腐食度が２０ｇ／ｍ2／ｈ未満のものを○と記し、２０ｇ／ｍ2／ｈ以上ないし３０ｇ／ｍ2／ｈ未満のものを△と記し、３０ｇ／ｍ2／ｈ以上のものを×と記した。 The test piece after the aging heat treatment of the round bar material having a diameter of 20 mm prepared above was processed into a round bar-shaped corrosion test piece having a diameter of 12 mm and a length of 21 mm. A pitting corrosion test was conducted by immersing these round bar-shaped corrosion test pieces in a pitting corrosion test solution of 6% ferric chloride at 25 ° C. for 24 hours, and the degree of corrosion was measured. The corrosion degree of the test was shown and evaluated. A pitting corrosion test with a degree of corrosion of less than 20 g / m 2 / h is marked with ◯, and a value of 20 g / m 2 / h or more to less than 30 g / m 2 / h is marked with △, and 30 g / m 2 / h or more. Was marked with x.
表２において、比較例のＮｏ．１８は、表１に示すように、Ｎｉの含有量が８．６％であって、本願の請求項に規定するＮｉの含有量の３．０〜８．０％より多いので、高コストである。さらに、比較例のＮｏ．２４、Ｎｏ．２５、Ｎｏ．２８、Ｎｏ．２９は、時効硬さの測定値が４５ＨＲＣ未満であるため、シャルピー衝撃試験および孔食試験を実施していないので、それらのシャルピー衝撃値の項目および孔食試験の項目には、−を表記している。さらに比較例のＮｏ．３３は、表１に示すようにＣｕを２．１７％含有して本願の請求項で規定する０．０５％以下を大幅に超えているので、本発明の対象外のものである。 In Table 2, No. of the comparative example. No. 18, as shown in Table 1, the Ni content is 8.6%, which is more than 3.0 to 8.0% of the Ni content defined in the claims of the present application. is there. Furthermore, No. of the comparative example. 24, no. 25, no. 28, no. In No. 29, the measured value of aging hardness is less than 45 HRC, so the Charpy impact test and the pitting corrosion test are not performed. Therefore, the Charpy impact value item and the pitting corrosion test item indicate −. ing. Furthermore, No. of the comparative example. As shown in Table 1, since No. 33 contains 2.17% of Cu and greatly exceeds 0.05% or less specified in the claims of the present application, it is out of the scope of the present invention.
Claims (1)
ただし、上記の式１および式２の［元素記号］は、質量％で示す成分元素の量を％で示す際の数値を表す。 In mass%, C: 0.01 to 0.10%, Si: 0.30 to 2.00%, Mn: 0.01 to 1.00%, P: 0.040% or less, S: 0.030 %: Ni: 3.0-8.0%, Cr: 12.0-20.0%, Mo: 0.20-0.80%, Cu: 0.50% or less, Ti: 0.30 2.50%, Nb: 0.01 to 2.00%, N: 0.0500% or less, balance Fe and inevitable impurities, formula 1: [Cr] + [Mo] + [Nb] + [Ti] + [Si] + [Ni] −26 ([C] + [N]) − 10.3 ≧ 10.0, Formula 2: [Cr] +1.5 [Si] + [Mo] +0.5 [Nb] +2 [Ti] -0.5 [Ni] -6.7 ([C] + [N]) ≦ 20.0 Martensitic stainless steel excellent in precipitation hardening ability,
However, the [element symbol] in the above formulas 1 and 2 represents a numerical value when the amount of the component element represented by mass% is represented by%.
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| WO2021171698A1 (en) * | 2020-02-27 | 2021-09-02 | 日本冶金工業株式会社 | Precipitation-hardening martensitic stainless steel |
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| JP2003073783A (en) * | 2001-09-03 | 2003-03-12 | Nisshin Steel Co Ltd | Precipitation-hardening type martensitic stainless steel sheet for flapper valve, and manufacturing method therefor |
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| JP2003073783A (en) * | 2001-09-03 | 2003-03-12 | Nisshin Steel Co Ltd | Precipitation-hardening type martensitic stainless steel sheet for flapper valve, and manufacturing method therefor |
| US20030102057A1 (en) * | 2001-10-23 | 2003-06-05 | Short John William | High-strength high-toughness precipitation-hardened steel |
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| WO2021171698A1 (en) * | 2020-02-27 | 2021-09-02 | 日本冶金工業株式会社 | Precipitation-hardening martensitic stainless steel |
| JP2021134395A (en) * | 2020-02-27 | 2021-09-13 | 日本冶金工業株式会社 | Precipitation hardening martensitic stainless steel |
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