CN110088323A - Product and application thereof comprising two phase stainless steel - Google Patents

Product and application thereof comprising two phase stainless steel Download PDF

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Publication number
CN110088323A
CN110088323A CN201780079046.9A CN201780079046A CN110088323A CN 110088323 A CN110088323 A CN 110088323A CN 201780079046 A CN201780079046 A CN 201780079046A CN 110088323 A CN110088323 A CN 110088323A
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phase
product
stainless steel
weight
equal
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CN110088323B (en
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托马斯·福斯曼
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2204/00—End product comprising different layers, coatings or parts of cermet

Abstract

This disclosure relates to a kind of product comprising two phase stainless steel, particularly the product is suitable for flexible application.The two phase stainless steel has the consisting of in terms of weight %: C is less than or equal to 0.040；Si is less than or equal to 0.60；Mn 0.80~10.0；Cr 21.0~28.0；Ni 4.0~9.0；Mo 0.9~4.5；N 0.10~0.45；Cu is less than or equal to 0.50；V is less than or equal to 0.10；P is less than or equal to 0.010；S is less than or equal to 0.006；Surplus is Fe and inevitable impurity.Present disclosure also relates to a kind of methods of product of the manufacture comprising the two phase stainless steel.

Description

Product and application thereof comprising two phase stainless steel
Technical field
This disclosure relates to a kind of product comprising two phase stainless steel, particularly the product is suitable for flexible application or conduct Spring itself.Present disclosure also relates to a kind of methods for manufacturing the product.
Background technique
The flexible application of wire rod or ribbon form can be loaded statically or dynamically.For the steel grade of static elastic application Most important properties are high proof strength or yield strength, clearly defined elasticity modulus, highly corrosion resistant and high resistance to stress relaxation Property.Most important properties for the steel grade of dynamic elasticity application are high proof strength or yield strength, clearly defined springform Amount, highly corrosion resistant, high resistance to stress relaxation property and highly anti-fatigue breaking property.
JP 2,010 059541 discloses a kind of method, and wherein final step is intended to obtain the maximum elongation rate of stainless steel Annealing process, the stainless steel is low-alloy dual phase steel.The austenite phase of this grade is unstable, and is become in plasticity Martensite can be partly transformed into when shape.
The rustproof spring steel kind in austenite or martensite source usually has the excellent combination of most of above-mentioned properties.So And a major defect of austenite steel grade is elasticity modulus as load increases to bullet limit stress (Rp0.2) and it is almost linear Reduce, and as described above, the steel grade for flexible application there should be holding when increasing load to be in high level simultaneously And the elasticity modulus that will not reduce in a linear fashion.Martensite steel grade, which can be presented, linearly to be reduced as load increases Elasticity modulus.However, a major defect of martensite steel grade is that there are problems for the corrosion resistances of these steel.
Therefore, an aspect of this disclosure is to provide a kind of suitable flexible application and will solve or at least reduce above-mentioned lack The product of point.
Summary of the invention
Therefore, an aspect of this disclosure is to provide a kind of product by two-phase stainless steel making, wherein the two-phase is not Ladle become rusty containing the consisting of in terms of weight %:
C is less than or equal to 0.040；
Si is less than or equal to 0.60；
Mn 0.80~10.0；
Cr 21.0~28.0；
Ni 4.0~9.0；
Mo 0.9~4.5；
N 0.10~0.45；
Cu is less than or equal to 0.50；
V is less than or equal to 0.10；
P is less than or equal to 0.010；
S is less than or equal to 0.006；
Surplus is Fe and inevitable impurity；
And wherein the two phase stainless steel is by the austenite phase of 55~75 volume % and the ferrite of 25~45 volume % Phase composition；
And wherein the product has the alternating layer of ferritic phase and austenite phase, the plane of the alternating layer and product It is substantially parallel, and the alternating layer has the average layer thickness less than or equal to about 4.5 μm.As used herein, term " about " refer to and add deduct 5% using the numerical value of its number.In addition, in the disclosure, abbreviation " FCC " refers to austenite phase, and contracts It writes " BCC " and refers to ferritic phase.It is less than in addition, stating " substantially parallel " as used herein and being intended to refer to from the deviation of plane 10%.
In addition, the product comprising two phase stainless steel such as above or defined below is by σ phase and/or precipitation with low content Chromium nitride or chromium nitride without σ phase and/or precipitation.In addition, the product will compared with the behavior of pure austenitic stainless steel With relatively high elasticity modulus will be kept when increasing load.The σ phase of low content and/or the chromium nitride of precipitation are free of σ phase And/or the chromium nitride being precipitated refers to that existing amount does not answer the corrosion resistance or toughness of severe exacerbation two phase stainless steel.
Another aspect of the present disclosure provides a kind of method for manufacturing such as product above or defined below, the side Method the following steps are included:
Main body such as two phase stainless steel above or defined below is provided；
One or more hot procedures are to be transformed into workpiece for the main body, and the hot procedure is about It is executed at a temperature of 1050 DEG C to about 1300 DEG C；
One or more cold working processes, are changed into the product for the workpiece.
Wherein the final step of the method must be cold working process.
The final step of the method must be cold working process, because the process will farthest influence two-phase stainless The micro-structure of steel, to have significant impact to elasticity modulus.In addition, the method for the present invention will provide more after cold working for product High intensity, and be cold worked and will also ensure that the hardening that will deform in product.
Specific embodiment
This disclosure relates to a kind of product by two-phase stainless steel making, wherein the two phase stainless steel includes in terms of weight % Consisting of:
C is less than or equal to 0.040；
Si is less than or equal to 0.60；
Mn 0.80~10.0；
Cr 21.0~28.0；
Ni 4.0~9.0；
Mo 0.9~4.5；
N 0.10~0.45；
Cu is less than or equal to 0.50；
V is less than or equal to 0.10；
P is less than or equal to 0.010；
S is less than or equal to 0.006；
Surplus is Fe and inevitable impurity；
And wherein the two phase stainless steel is by the austenite phase of 55~75 volume % and the ferrite of 25~45 volume % Phase composition；
And wherein the product has the alternating layer of ferritic phase and austenite phase, the plane of the alternating layer and product It is substantially parallel, and the alternating layer has the average thickness less than or equal to about 4.5 μm.
As two phase stainless steel above or defined below will provide high corrosion resistance for product.In addition, ferritic phase and Austria The alternating layer of family name's body phase will provide clearly defined elasticity modulus for product, and the elasticity modulus will keep phase when increasing load To higher.Clearly defined elasticity modulus refers to that elasticity modulus will remain in high level in the load increase on material, and As load increases to bullet limit stress (Rp0.2) and hardly linear reduction.Therefore, the product is by suitable flexible application.
According to one embodiment, two phase stainless steel has the PRE greater than 28.PRE is defined herein as PRE=Cr+ The 3.3*Mo+16*N corresponding weight percent of respective alloy element (coefficient multiplied by).Therefore, such as two-phase above or defined below Stainless steel will provide the product with highly corrosion resistant, particularly high pitting corrosion resistance, this is because it is in ferritic phase and Ovshinsky Body mutually all has high PRE value, i.e. the PRE value of ferritic phase and austenite phase is greater than about 28.Therefore, selection Cr, Mo and N is respective Amount, so that the PRE in austenite phase and ferritic phase is respectively greater than about 28.
According to one embodiment, if two phase stainless steel above or defined below is by the austenite phase of 55~70 volume % It is formed with the ferritic phase of 30~45 volume %, such as by the iron of the austenite phase of 65~70 volume % and 30~35 volume % element Body phase composition.It means that in the two phase stainless steel of the disclosure and therefore in the product being made of the two phase stainless steel In there is no deformation induce martensite.This is possible, because if two phase stainless steel above or defined below is that height is closed Aurification, therefore the product will have through cold working generation cold deformation without its austenitic structure is transformed into martensite knot The ability of structure.
According to one embodiment, if product above or defined below is in the form of sheet material or band or wire rod.It is described Sheet material or band or wire rod can be used for manufacturing spring, therefore present disclosure also relates to a kind of springs.
According to one embodiment, at least one described hot procedure is hot rolling.The hot procedure is at 1050 DEG C It is executed at a temperature of to 1300 DEG C.In addition, according to one embodiment, at least one described hot procedure executes primary or more In primary, for example, in one embodiment, hot-working such as hot rolling can execute main body several times, such as 6 times or until Obtain the required hot-working compression of workpiece.Hot-working also will form the layer of austenite phase and ferritic phase, but the thickness of these layers Degree is greater than the thickness in final product.According to another embodiment, the workpiece can heat between thermal work steps.
According to one embodiment, at least one described cold working process is cold rolling.According to another embodiment, described At least one cold working is cold stretch.According to one embodiment, the cold working process executes primary or more than one.One In a embodiment, cold working process can be executed several times workpiece, such as 4 times or the institute until obtaining final product Need cold deformation.According to one embodiment, the cold deformation of final product, therefore refer to the deformation of product, it is at least 10%, such as At least 25%, such as at least 50%, such as at least 75%, such as 75% to 95%.According to one embodiment, it is obtained most Whole product under the conditions of its cold rolling with a thickness of 20 μm to 5mm.
According to one embodiment, the method includes a hot procedures, cold working process, a hot-working Process and a cold working process.According to another embodiment, the method includes a hot procedure, one to be cold worked Journey, a hot procedure, a cold working process and a cold working process.
According to one embodiment, such as method above or defined below includes heat treatment step, wherein the heat treatment It is the product annealing for making to obtain after cold working step.Annealing can be executed to reduce the intermetallic phase of any formation, such as σ Phase and chromium nitride either reduce the intensity of product or change the content of austenite or ferritic phase in product.Annealing temperature will Composition and thickness depending on product.In general, annealing temperature is higher than 1000 DEG C.According to another embodiment, product at least exists Annealing steps are subjected between penultimate cold working step and the last one cold working step.In addition, according to another implementation Mode, can be (such as, more using several annealing steps between each cold working step (such as more than one cold working step) In an annealing steps).According to one embodiment, the product anneals about 1 within the temperature range of 1050 DEG C to 1250 DEG C The time of second to 600 seconds.During product is heated to the temperature range, it is instead important to avoid that the product is exposed to 750 DEG C to 1000 DEG C of temperature long time, because this is the temperature range that wherein σ phase and/or chromium nitride most quickly form.Therefore, Temperature, which rises, can make through the time of the range below about 2 minutes.In addition, the final step of the process is cold working step Suddenly.
According to one embodiment, the method for the present invention further includes after cold working step or aging after the anneal step The step of product obtained.The step will provide the bullet limit stress of product it is additional increase and elasticity modulus behavior into One step improves.It, can be to the shaped operation processing of product, wherein being formed spring before through aging process.The aging Can 400 DEG C to 450 DEG C at a temperature of execute 0.25 hour to 4 hours.It, can since Aging Step executes at low temperature To be executed after final cold working step.
Hereinafter, the alloying element such as two phase stainless steel above or defined below is discussed.This tittle is with weight Amount % (wt%) provides:
Carbon, C are the representative element of stable austenite phase, and are to maintain the important element of mechanical strength.However, if There are a large amount of carbon, then can carbide precipitate, this will reduce corrosion resistance.Therefore, carbon content is limited to less than 0.040 weight Measure %.
Manganese, Mn have strain hardening effect, and the transformation from austenitic structure to martensitic structure is offset in deformation. In order to generate these effects, Mn must exist with the amount at least or equal to 0.80 weight %.In addition, Mn is until about 10 weight % Content under have austenite stabilizing effect.Higher than the level, ferritic stability will increase, and therefore, it is difficult to not obtain Such as other of Cr and Mo ferritic stabilizer is added in mostly ferritic situation.Therefore, the maximum level of Mn should not be greater than 10 weight %.According to one embodiment, the content of Mn is equal to or less than 6.0 weight %.According to another embodiment, etc. In or less than 5.0 weight %.According to one embodiment, the content of Mn is in the range of 2.0 weight % to 5.0 weight %.When In the presence of Mn is with amount as proposed above, by the strain hardening ability for increasing two phase stainless steel and also prevent austenite phase from becoming So unstable, i.e., it will prevent from being transformed into martensitic structure from austenitic structure in deformation.
Nitrogen, N has positive effect to the corrosion resistance of the two phase stainless steel defined hereinbefore or hereinafter, and works as to resistance to spot corrosion Amount PRE also has strong influence, and PRE is defined as Cr+3.3Mo+16N.In addition, solution strengthening and deformation of the N to two phase stainless steel Hardening has powerful contribution.N also has strong austenite stabilizing effect, and offsets in plastic deformation from austenitic structure To the transformation of martensitic structure.In order to contribute all these positive effects, the additive amount of N is 0.10 weight % or higher.However, Under too high level, N tends to form chromium nitride, due to the negative effect to ductility and corrosion resistance, it should avoid this Kind situation.Therefore, the content of N should be equal to or lower than 0.45 weight %.According to one embodiment, the content of N is 0.30 weight Measure % to 0.42 weight %.
Molybdenum, Mo has strong influence to the corrosion resistance of two phase stainless steel such as above or defined below, and it is serious It influences PRE and all there is powerful contribution to solution strengthening and strain hardening.Therefore, the additive amount of Mo is equal to or more than 0.90 Weight %.However, Mo also increases the stable temperature of undesirable σ phase and it is promoted to generate rate, therefore the content of Mo should wait In or less than 4.5 weight %.According to one embodiment, the content of Mo is 2.0 weight % to 4.0 weight %.
Chromium, Cr have the corrosion resistance of two phase stainless steel such as above or defined below, especially pitting corrosion resistance strong It influences.In addition, Cr improves yield strength when two phase stainless steel deforms and counteracts austenitic structure to martensitic structure Transformation.Cr also has ferrite stabilizing effect to two phase stainless steel.Therefore, the content of Cr should be equal to or more than 21.0 weight %. At a high level, the increase of Cr content will lead to the higher temperature and faster for undesirable stable σ phase and chromium nitride The σ phase of speed generates.Therefore, the content of Cr is equal to or less than 28.0 weight %.According to one embodiment, the content of Cr is 24.0 Weight % to 28.0 weight %, such as 26.0 weight % are to 28.0 weight %.
Copper, Cu have positive effect to corrosion resistance.Optionally, however Cu is added to such as pair above or defined below In phase stainless steel.In general, Cu is present in the waste product for producing steel, and allow to be retained in steel with the level of appropriateness.Cause This, the content of Cu can be equal to or less than 0.50 weight %.According to one embodiment, the content of Cu is equal to or less than 0.02 weight Measure %.
Nickel, Ni have positive effect for resisting general corrosion.Ni also has a strong austenite stabilizing effect, and The transformation from austenitic structure to martensitic structure is offset when two phase stainless steel deforms.Therefore, the content of Ni is equal to or more than 4.0 Weight %.Under the level higher than 9.0 weight %, Ni will lead to austenite level higher than 70%.Therefore, the content of Ni should be little In or equal to 9.0 weight %.According to one embodiment, the content of Ni is 7.0 weight % to 9.0 weight %.
Silicon, Si are almost always existed in two phase stainless steel, because it may have been used to deoxidation, or are being used for two-phase In the waste material of stainless steel, although target is that have amount as few as possible.Its with ferrite stabilizing effect, and at least partly by In the reason, the content of Si should be less than 0.60 weight %, such as in 0.40 weight % between 0.60 weight %.
Vanadium, the impurity element that V can be used as are present in two phase stainless steel, and because it is generally followed by waste material, It is difficult to control its content.Due to the precipitation of carbide, two phase stainless steel should preferably comprise amount as few as possible, and for this hair The content of bright two phase stainless steel, V should be equal to or less than 0.10 weight %, such as equal to or less than 0.01 weight %.
Phosphorus (P) can be impurity and be included in as in two phase stainless steel above or defined below；Content is less than 0.010 Weight %.
Sulphur (S) can be the impurity as contained in two phase stainless steel above or defined below.S may be under impaired low temperature Hot-workability.Therefore, the permission content of S is less than 0.006 weight %.
It is optionally possible to other a small amount of alloying elements are added to as in two phase stainless steel above or defined below, To improve such as machinability or hot-working property such as high-temperature ductility.The example (but non-limiting) of these elements is As, Ca, Co, Ti, Nb, W, Sn, Ta, Mg, B, Pb and Ce.One of these elements or a variety of amounts are most 0.5 weight %, Such as most 0.1 weight %.
According to one embodiment, product of the invention includes pair being made of all elements mentioned above or below Phase stainless steel.
When using term " most " or " being less than or equal to ", one skilled in the art will appreciate that unless specifically illustrating another One number, otherwise the lower limit of the range is 0 weight %.
If the surplus element of two phase stainless steel above or defined below is iron (Fe) and usually existing impurity.
The example of impurity is the element and compound that not specially adds but cannot avoid completely, because they usually make Exist in the raw material or other alloying element for example for manufacturing two phase stainless steel for impurity.
According to one embodiment, two phase stainless steel is made of alloying element and above range.
There is provided the step of two phase stainless steel main body above or defined below such as may include providing the two phase stainless steel Melt and the melt of casting, with obtain as two phase stainless steel above or defined below main body.The casting can wrap Include the continuous casting of melt.
As the method and step used as a result, as previously mentioned, it can be seen that ferrite and austenite in the product Alternating layer, the plane of the layer and the product is substantially parallel.The thickness of layer will affect the bullet limit stress of product.In order to obtain Enough to bullet limit stress, every layer of average FCC thickness and BCC thickness should be less than or be equal to about 4.5 μm.According to other embodiment party Formula, every layer with a thickness of 0.01 μm to about 4.5 μm, such as about 0.5 μm to about 4.5 μm, such as about 1.0 μm to about 4.5 μm, such as About 1.0 μm to about 4.2 μm, such as 2.0 μm to 4.2 μm.Under the conditions of final cold working (last whole cold working step it The thickness of product can be 20 μm to 5mm afterwards).Before cold working, two phase stainless steel such as above or defined below will be included Main body carry out hot-working, wherein according to one embodiment, the thickness of the main body is reduced to from about 100mm to 200mm 2mm to 15mm.
The thickness measure of BCC phase and FCC phase is respectively by taking the vertical cross-section of product (band, sheet material or wire rod), so Afterwards in acid (such as HNO3) in polish and etch and executed with obtaining the comparison between this two-phase.Then make under an optical microscope Measurement is executed with suitable magnifying power (100~1000 times), so as to each phase as it can be seen that so as to count enough phase boundaries To obtain reasonable statistics certainty (more than 30 phase boundaries).Appropriate cross-section location in wire rod for measurement is in its diameter 25% at.Band or sheet material should be measured in mid-depth at away from 25% width of edge.It is online to measure each BCC with FCC phase In the diametrical direction of material or along band or the thickness of the thickness direction of sheet material, and thus calculate separately average BCC and FCC thickness.
The disclosure is also illustrated by following non-limiting embodiment.
Embodiment
By the alloy melting with chemical composition as shown in table 1 and it is cast into 1kg ingot.It is melting and is casting it Afterwards, using 9 rolling passes by ingot obtained about 1250 DEG C at a temperature of be rolled into band.By sample during hot rolling It reheats 3 times, to keep the temperature at 1050 DEG C or more.The final thickness of band is 3.7mm to 4.0mm.
Then by hot-rolled band cold rolling, until obtaining about 75% cold compression.5 passages are used in cold-rolling mill.
Ferrite content is determined by using the measurement of magnetic scale.The measurement of magnetic scale is executed according to IEC60404-1.It is assumed that Magnetic phase content is equal to ferrite content, and assumes that rest part is austenite.Value is listed in Table 2 below.
In order to measure the thickness measure of BCC phase and FCC phase, at away from 25% width of edge at the vertical cross-section of band Then sampling polishes simultaneously etched sample (1M HNO3).Suitable magnifying power is used at optical microscopy (Nikon (Nikon)) (1000 times) execute measurement, i.e., each phase is visible and sees more than 30 phase boundaries.Through-thickness measures each BCC The thickness of phase and FCC phase, and calculate separately average BCC thickness and average FCC thickness.The value of acquisition is shown in Table 2.
By the intensity for measuring cold-strip according to SS EN ISO 6891-1 extension test in the rolling direction.From Each cold-strip sample water injection cuts to obtain two tensile samples.Collection is in table 3.It can from the table Out, all samples all have good tensile strength.
Chemical composition-all values of 1. sample of table are provided with weight % (wt%).
Sample Mn N Cr Ni Mo C Si V P S Cu
1 0.86 0.15 22.1 5.28 3.28 0.030 0.51 0.006 0.006 0.004 0.013
2 1.94 0.16 22.6 6.45 3.02 0.032 0.51 0.006 0.006 0.004 0.013
3 1.85 0.32 23.0 4.04 3.14 0.031 0.53 0.005 0.006 0.005 0.015
4 1.87 0.34 27.0 6.50 1.15 0.032 0.51 0.006 0.006 0.005 0.012
5 9.14 0.26 22.9 6.13 2.96 0.031 0.52 0.006 0.010 0.005 0.014
6 1.85 0.18 22.9 4.03 0.98 0.033 0.51 0.005 0.006 0.004 0.011
7 1.67 0.21 21.7 4.05 3.14 0.031 0.50 0.005 0.006 0.003 0.013
8 1.85 0.20 24.7 6.25 2.94 0.033 0.52 0.006 0.006 0.003 0.012
9 0.83 0.27 25.8 7.22 4.07 0.035 0.53 0.007 0.006 0.005 0.013
10 1.12 0.24 26.6 7.52 3.10 0.030 0.52 0.005 0.007 0.005 0.014
11 2.68 0.41 26.0 6.51 3.30 0.032 0.51 0.005 0.008 0.003 0.015
12 2.69 0.31 27.8 8.03 2.95 0.035 0.52 0.007 0.009 0.006 0.010
13 5.86 0.32 25.7 7.69 3.36 0.035 0.53 0.006 0.009 0.004 0.013
14 2.76 0.34 27.9 7.42 2.08 0.035 0.50 0.006 0.008 0.005 0.013
15 2.65 0.34 23.4 5.51 3.34 0.036 0.49 0.005 0.008 0.005 0.014
The phase thickness of 2. sample of table and the phase content of sample
3. extension test result of table
As can be seen that product obtained after cold rolling will there is the bullet higher than 1200MPa to limit stress Rp0.2。
As previously mentioned, using the pitting corrosion resistance of PRE formula (being defined as PRE=Cr+3.3Mo+16N) assessment experimental grade. Pass through inputIn total composition (come from table 1), can derive each under specific BCC content (from table 2) Equilibrium composition in phase, so as to calculate the PRE of every phase according to table 4.
Every kind of composition and pitting corrosion resistance in 4. two-phase of table
Therefore, from the above experiment as can be seen that the product of the disclosure will have high-yield strength and good ductility with And good corrosion resistance and high tensile, this is attributed to the variation of solution strengthening and strain hardening, phase thickness and content.
It can be seen from the results above that when average phase thickness is lower than 4.5 μm, in cold working two phase stainless steel of the invention The very fine micro-structure (as shown in table 5) of middle acquisition will have influence to engineering properties.

Claims (16)

1. a kind of product by two-phase stainless steel making, wherein the two phase stainless steel includes the consisting of in terms of weight %:
C is less than or equal to 0.040；
Si is less than or equal to 0.60；
Mn0.80~10.0；
Cr21.0~28.0；
Ni4.0~9.0；
Mo0.9~4.5；
N0.10~0.45；
Cu is less than or equal to 0.50；
V is less than or equal to 0.10；
P is less than or equal to 0.010；
S is less than or equal to 0.006；
Surplus is Fe and inevitable impurity；
And wherein the two phase stainless steel is by the austenite phase of 55~75 volume % and the ferritic phase group of 25~45 volume % At；
And wherein the product has the alternating layer of ferritic phase and austenite phase, the plane of the alternating layer and the product It is substantially parallel, and the alternating layer has the average layer thickness less than or equal to about 4.5 μm.
2. product according to claim 1, wherein the two phase stainless steel has the PRE greater than 28, and wherein PRE is fixed Justice is PRE=Cr+3.3Mo+16N.
3. product according to claim 1 or 2, wherein the two phase stainless steel by 55~70 volume % austenite phase and The ferritic phase of 30~45 volume % forms, such as by the ferrite of the austenite phase of 65~70 volume % and 30~35 volume % Phase composition.
4. product according to any one of claims 1 to 3, wherein average-ferrite or austenite are with a thickness of about 0.01 μm to about 4.5 μm, such as about 0.5 μm to about 4.5 μm, such as about 1.0 μm to about 4.5 μm, such as about 1.0 μm to about 4.2 μm.
5. product according to any one of claims 1 to 4, wherein the content of the Mn in the two phase stainless steel is 2 In the range of weight % to 5 weight %.
6. product according to any one of claims 1 to 5, wherein the content of the N in the two phase stainless steel is 0.3 In the range of weight % to 0.42 weight %.
7. the product according to any one of claims 1 to 6, wherein the content of the Mo in the two phase stainless steel is 2 In the range of weight % to 4 weight %.
8. product according to any one of claims 1 to 7, wherein the content of the Cr in the two phase stainless steel is 24 In the range of weight % to 28 weight %, such as 26 weight % to 28 weight %.
9. according to claim 1 to product described in any one of 8, wherein the content of the Ni in the two phase stainless steel exists In the range of 7.0 weight % to 9.0 weight %.
10. according to claim 1 to product described in any one of 9, wherein the product is sheet material or band or wire rod.
11. a kind of spring comprising according to claim 1 to product described in any one of 10.
12. a kind of manufacture is according to claim 1 to the method for product described in any one of 11 comprising following steps:
It provides according to claim 1 to the main body of two phase stainless steel defined in any one of 10；
One or more hot procedures are to be transformed into workpiece for the main body, and the hot procedure is at about 1050 DEG C It is executed at a temperature of to about 1300 DEG C；
One or more cold working processes, are changed into the product for the workpiece,
Wherein the final step of the method must be cold working process.
13. according to the method for claim 12, wherein the hot procedure is hot rolling.
14. according to claim 12 or claim 13 described in method, wherein the cold working process is cold rolling.
15. method described in any one of 2 to 14 according to claim 1, wherein the method also includes one or more heat Processing step, wherein one or more of heat treatment steps are annealing, the annealing is being higher than 1000 DEG C to 1250 DEG C of temperature Degree is lower to be executed.
16. method described in any one of 2 to 15 according to claim 1, the method includes in 400 DEG C to 450 DEG C of temperature Make the other step of the product aging 0.25 hour to 4 hours under degree, wherein described in executing after final cold working step Aging.
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