CN101090988A - Duplex stainless steel having excellent corrosion resistance with low nickel - Google Patents

Duplex stainless steel having excellent corrosion resistance with low nickel Download PDF

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Publication number
CN101090988A
CN101090988A CNA200580045052XA CN200580045052A CN101090988A CN 101090988 A CN101090988 A CN 101090988A CN A200580045052X A CNA200580045052X A CN A200580045052XA CN 200580045052 A CN200580045052 A CN 200580045052A CN 101090988 A CN101090988 A CN 101090988A
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steel
stainless steel
content
duplex stainless
cpt
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金光泰
李龙宪
孙元根
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Posco Holdings Inc
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Posco Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

Disclosed is duplex stainless steel that contains relatively low content of Ni, and limits constituents of Cr-Mo-Mn-N to make volume fraction of a and have about 50:50, thereby minimizing incidence of a edge crack to enhance a production yield and decrease a processing load, in which the alloy constituents includes Cr of 19.5 - 22.5%, Mo of 0.5-2.5%, Ni of 1.0-3.0%, Mn of 1.5-4.5%, N of 0.15-0.25%, Fe and unavoidable elements, and a constitution range of the alloy constituents are adjusted to make a CPT highter than 20 DEG C depending on the constitution range of the alloy constituents. Thus, the contents of Cr, Mo and Ni is decreased and the content of Mn is increased a little, so that a production cost thereof is reduced; the corrosion resistance is secured to be better than the STS 304 steel and the 316L steel; the incidence of the edge cract is decreased while being hot-rolled, thereby decreasing a load on the following process; and the surface defective is decreased, thereby improving a production yield.

Description

Low nickel duplex stainless steel with excellent corrosion resisting property
Technical field
The present invention relates to a kind of duplex stainless steel, compare with the S32205 duplex stainless steel, this duplex stainless steel has comprised Cr, Mo, N and the Ni of high-load Mn and low levels.More particularly, the present invention relates to a kind of duplex stainless steel, this duplex stainless steel has comprised Cr, Mo, N and the Ni of low levels, reduces this stainless production cost thus, has the corrosion resisting property of the excellence that is better than STS 304 steel and 316L steel, and have low limit split incidence by hot rolling the time.
Background technology
Usually, it is mother metal (base metal) that austenite (austenite) stainless steel that processability (formability) and corrosion resisting property (corrosion resistance) are excellent adopts Fe, and mainly comprises Cr and Ni.In addition, in order to reach various purposes, such as other elements such as Mo, Cu austenitic stainless steel various exploitations have been carried out by adding.
In austenitic stainless steel, the 316L steel has excellent corrosion resisting property, corrosion resistance (pittingresistance) and hot strength.Yet the 316L steel is a soft steel, and has comprised greater than the Ni of 10wt% with greater than the Mo of 2wt%, makes its cost value serious with the price volalility of Ni and Mo, thereby has reduced competitive power.
In order to enhance competitiveness, iron and steel industry by reducing Ni and Mo content and ensure that the corrosion resisting property that corrosion resisting property is better than the 316L steel makes great efforts to develop new steel.
As have austenite mutually and ferrite (ferrite phase) mix the example of the duplex stainless steel of formation mutually, S32205 duplex stainless steel (below be called " 2205 steel ") comprises Cr, the Mo of high per-cent and N ensureing excellent corrosion resisting property, and comprises Ni greater than 5wt% to ensure volume fraction.
With the STS 316L steel that comprises 10% Ni comparatively speaking, this duplex stainless steel comprises the Ni of low relatively per-cent, makes that its production cost is low, so its price has competitive power, thereby has improved added value (added value).Yet the thermoforming performance of 2205 steel is poor, therefore has 80% low-down production yield.In addition, 2205 steel have high-load Cr and Mo, make the sedimentation velocity height of σ (sigma) phase, thereby make the characteristic variation of steel, and to twining and cooling process has high capacity.Therefore, be difficult to replace the 316L steel with 2205 steel.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of duplex stainless steel, compare with 2205 steel, this duplex stainless steel has Cr, Mo, N and the Ni of low levels, reduce the production cost of steel thus, the incidence that the limit is split when reducing by hot rolling improves the production yield, and this duplex stainless steel also has the corrosion resisting property of the excellence that is better than STS304 steel and 316L steel.
The inventor has developed a kind of duplex stainless steel, and this duplex stainless steel has comprised the Ni of low relatively content, and has limited the component of Cr-Mo-Mn-N so that the volume fraction of α and γ had about 50: 50, makes production cost reduce; Ensure that CPT is higher than 20 ℃ of CPT of STS304 steel and 316L steel; Incidence is split on the limit to minimize to improve the production yield and to reduce and handle load.
In exemplary embodiment of the present invention, duplex stainless steel comprises 19.5~22.5% Cr, 0.5~2.5% Mo, 1.0~3.0% Ni, 1.5~4.5% Mn, 0.15%~0.25% N, 0.03% and less than 0.03% C, 0.03% and less than 0.03% P, 2% and less than 2% Si, Fe and inevitable element.
Description of drawings
From the description taken together with the accompanying drawings of following preferred embodiment, these and/or other purpose of the present invention and advantage will become clear and be easier to and understand, in the accompanying drawings:
Fig. 1 illustrates the photo that is split by the limit of hot rolled sample according to alloy compositions;
Fig. 2 illustrates according to the alloy compositions of steel sample of the present invention and compared steel sample and the form of volume fraction;
Fig. 3 is the form that the sample critical spot corrosion temperature (CPT) of Fig. 2 is shown;
Fig. 4 is the form that illustrates about total test result of the sample of Fig. 2 of corrosion resisting property and thermoforming performance;
Fig. 5 is the form that illustrates according to the oxidation increment of steel of the present invention and traditional steel.
Embodiment
Below, embodiments of the invention are described with reference to the accompanying drawings.Below, basal component is carried out following restriction.
Carbon (C): C is effective for come strengthening material by solution strengthening.Yet when the content of C was excessive, C was easy to combine with carbide forming element (carbide-forming element) such as Cr, and wherein, carbide forming element is influential for the corrosion resisting property on ferritic phase and the austenite border between mutually.Therefore, C has reduced the content of crystal boundary (grain boundary) Cr on every side, makes the corrosion resisting property variation.In order to make corrosion resisting property maximization, the content of C is reduced to below 0.03% and 0.03%.
Nitrogen (N): N and Ni help a kind of in the mutually stable element of austenite.When N content increased, corrosion resisting property and high strength were achieved.Yet, when the too high levels of N, the thermoforming performance variation of steel, thus reduced the production yield of steel.On the other hand, cross when low, should reduce the content of Cr and Mo, ensure the volume fraction of steel, otherwise be difficult to ensure the intensity and the phase stability of welding assembly when the content of N.Therefore, the content of N is preferably between 0.15% and 0.25%.
Manganese (Mn): Mn has about 1.5% content usually to adjust metal flow rate (metal flowrate).Simultaneously, can additionally comprise Mn and replace Ni.In this case, thermoforming performance can be improved once more.Yet when the content of Mn was excessive, Mn combined and forms MnS with S in the steel, thus the corrosion resisting property of making and thermoforming performance variation.Therefore, the upper limit of Mn content is restricted to 4.5%.Preferably, the content of Mn is between 1.5% and 4.5%.
Chromium (Cr): Cr is used as with Mo and makes the stable element of ferritic phase.Here, Cr is necessary for the ferritic phase of main guarantee duplex stainless steel not only, and also is necessary for ensureing excellent corrosion resisting property.When the content of Cr increased, corrosion resisting property improved, but the content that also should improve expensive Ni is to keep volume fraction.As a result, the content that preferably limits Cr between 19.5% and 22.5% with volume fraction that keeps duplex stainless steel and the corrosion resisting property that is better than STS 304 steel and 316L steel.
Molybdenum (Mo): as Cr, Mo not only is used for stablizing ferritic phase but also has improved corrosion resisting property widely.Yet if the content of Mo is excessive, Mo may form the σ phase when annealing, thus the corrosion resisting property of making and impact resistance variation.In the present embodiment, the just auxiliary Cr of Mo ensures ferritic volume fraction and ensures suitable corrosion resisting property, thereby the content that preferably limits Mo is between 0.5% and 2.5%.
Nickel (Ni): Ni is a stable austenite element mutually with Mn and N together, and main as the austenite phase that ensures duplex stainless steel.In order to reduce production costs,, then can replace the decrement of Ni by the content that improves the Mn that forms the austenite phase and N if reduce the content of expensive Ni.Yet, if exceedingly reduce the content of Ni, will exceedingly need Mn and N, this makes corrosion resisting property and thermoforming performance variation, perhaps reduces the content of Cr and Mo, this makes and is difficult to ensure that corrosion resisting property is better than the 316L steel.Therefore, the content of Ni is preferably located between 1.0% and 3.0%.
Phosphorus (P): P is at crystal boundary or segregation takes place at the interface, and this may make corrosion resisting property and toughness variation.Therefore, reduce the content of P as much as possible.Preferably, consider the efficient of refining treatment, be limited to 0.03% on the restriction P content.
Sulphur (S): S makes thermoforming performance variation, perhaps forms MnS with Mn, thereby makes the corrosion resisting property variation.Therefore, reduce the content of S as much as possible.Preferably, the content of S is lower than 0.03%.
Silicon (Si): add Si for deoxidation, yet Si can be used as the element that is used for stablizing ferritic phase.If the content of Si is excessive, then Si makes the mechanical characteristics variation such as impelling strength of steel.Therefore, the content of Si preferably is limited in below 2% and 2%.
Simultaneously, preparation has the two-phase stainless steel sample of component according to an embodiment of the invention, and tests about volume fraction, corrosion resisting property and thermoforming performance.Fig. 2 show with sample under 1050 ℃ temperature, anneal the back sample alloy compositions and α-volume fraction.In these alloys, their α-volume fraction about 40% to about 60% scope.In view of welding, phase stability etc., determine that the duplex stainless steel of α-volume fraction in 44% to 51% scope is excellent (O); α-volume fraction is lower than 44% or to be higher than 54% duplex stainless steel be defective (X); The duplex stainless steel of α-volume fraction in 51% to 54% scope is good (Δ).
In the sample of Fig. 2, the alloy compositions except Cr, Mo, Mn and N is unified (unify) satisfying total content range of duplex stainless steel, but for experimentally facility, the content range of Ni is limited in 2.5wt%.
Fig. 3 is the form that the sample critical spot corrosion temperature (CPT) of Fig. 2 is shown, and CPT means corrosion resisting property in form.Here, determine that CPT is that steel below 20 ℃ and 20 ℃ is defective (X); The steel of CPT in 20 ℃ to 25 ℃ scopes is good (Δ); CPT is that the steel more than 20 ℃ and 20 ℃ is outstanding (O).
Above-mentioned CPT is produced by following step: based on the G48 of American Society for testing and materials (ASTM) method, under 1050 ℃ temperature, will have being annealed of 50mm (L) * 25mm (W) * 3mm (T) size, in the acidifying ferric chloride Solution, precipitate 24 hours then by the hot rolled sample.
According to ASTM G48 method, obtain measuring the CPT of starting temperature by following equation:
CPT(℃)=(2.5×%Cr)+(7.6×%Mo)+(31.9×%N)-41.0。
The suggestion of ASTM G48 method is interval calculation CPT with 5 ℃ and selects immediate numerical value.
Yet the CPT of the measurement starting temperature of estimating by ASTM G48 method has very big deviation.The reason that deviation is very big is to consider that not Mn can the deterioration corrosion resisting property.That is to say to have high relatively Mn content, so in the CPT of the estimation that obtains by above-mentioned ASTMG48 method, produced deviation because have the duplex stainless steel of the Ni content of reduction.
In order to compensate this deviation, the inventor is by considering that Mn has calculated CPT, and the result is as follows:
CPT(℃)=-150.47+2.65Cr+11.71Mo-1.3Mn+64.58N。
According to the present invention, the CPT of estimation is approximately equal to the CPT of measurement.
Simultaneously, have the Cr and the Mo of low levels or have under the situation of high-load Mn at steel, the CPT of measurement is lower relatively than the CPT that estimates.Therefore, do not expect exceedingly to improve the content of Mn or exceedingly reduce the content of Cr and Mo for the volume fraction that ensures low Ni duplex stainless steel.
When the Ni duplex stainless steel is hanged down in production, should reduce the incidence of splitting on the limit and produce yield, and should ensure that the thermoforming performance is to minimize permanent load to improve.The steel production that will have the component of Fig. 2 is the steel ingot (ingot) of 50Kg and forges and presses to have 20mm (T) and 30mm (T), observe the incidence that their limit is split then, thus by select with 2205 steel comparatively speaking in the incidence that the limit is split the significantly improved steel of performance obtained test result as Fig. 1.
Here, determining to have the steel that splits as the limit of 2205 steel is defective (X); Have the steel that local edge splits and be good (Δ); The steel that does not almost have the limit to split is excellent (O).
Fig. 4 shows the total test result of the sample of Fig. 2 about volume fraction, corrosion resisting property and thermoforming performance.Four kinds of steel (3,4,14 and No. 15 steel) have satisfied the shaping characteristic of duplex stainless steel, have the corrosion resisting property that is better than the 316L steel, and thermoforming performance excellence.In addition, can select other steel (1,2,5,6,7,8,9,10,11,12,13,15,16,20,21 and No. 22 steel) as preferred steel, yet they are inferior to foregoing steel.Therefore, along with Mn content uprises, thermoforming performance and corrosion resisting property variation.In addition, along with N content uprises, thermoforming performance variation.Equally, the Mo that has the relative high level of steel needs of high-load Mn.
Fig. 5 show when for hot rolling with steel as steel billet (slab) when heating once more, according to an embodiment of the invention between You Yi steel and good steel and the compared steel (such as STS 304, STS 316L and 2205) in the difference aspect the high temperature oxidation.Carry out high temperature oxidation and measure by measuring certain condition oxidation increment down, described condition is as follows: under 1250 ℃ temperature heating have 10mm (L) * 10mm (W) * 3mm (T) size by the hot rolling sample, and maintenance 180 minutes in process furnace.
At this moment, under the atmosphere of process furnace, the content of S is adjusted to 200ppm.As a result, be 4 to 6 times of traditional 2205 steel according to the oxidation increment of steel of the present invention, its performance is lower than 2205 traditional steel, and is about 1/3 to 1/2 times of 316L steel, and its performance is than 316L steel height.With traditional 2205 steel comparatively speaking, by having reduced surface imperfection, so improved surface quality according to steel of the present invention owing to be formed on the surface lubrication effect that the zone of oxidation on the billet surface that is heated once more causes during by hot rolling.
With 2205 duplex stainless steels comparatively speaking, in duplex stainless steel according to the present invention, reduce the content of Cr, Mo and Ni and improve the content of Mn slightly, make the production cost of steel reduce; Ensured that corrosion resisting property is better than STS 304 steel and 316L steel; The incidence that the limit is split when having reduced by hot rolling, thus load on the ensuing process reduced; Reduce surface imperfection, thereby improved the production yield.
Though illustrated and described some embodiments of the present invention, what it will be understood by those skilled in the art that is not breaking away from principle of the present invention and spirit and not breaking away under the situation of claim and equivalent institute restricted portion thereof, can change embodiment.

Claims (2)

1, a kind of low Ni duplex stainless steel with excellent corrosion resisting property, the alloy compositions that described duplex stainless steel has comprises 19.5%~22.5% Cr, 0.5%~2.5% Mo, 1.0%~3.0% Ni, 1.5%~4.5% Mn, 0.15%~0.25% N, Fe and inevitable element, wherein
Calculate CPT by the following compositing range that utilizes described alloy compositions as the equation of function:
CPT(℃)=-150.47+2.65Cr+11.71Mo-1.3Mn+64.58N
Adjust the compositing range of described alloy compositions so that described CPT is higher than 20 ℃.
2, duplex stainless steel as claimed in claim 1 also comprises 0.03% and less than 0.03% C, 0.03% and less than 0.03% P and 2% and less than 2% Si.
CNA200580045052XA 2004-12-27 2005-12-22 Duplex stainless steel having excellent corrosion resistance with low nickel Pending CN101090988A (en)

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CN103987867A (en) * 2011-11-30 2014-08-13 Posco公司 Lean duplex stainless steel and preparation method thereof
CN105886956A (en) * 2016-07-01 2016-08-24 东北大学 Economical duplex stainless steel sheet and preparation method thereof
CN106086700A (en) * 2016-07-11 2016-11-09 无锡市锡达电子科技有限公司 A kind of cylinder jacket for Stirling engine and processing technique thereof
CN106917054A (en) * 2015-12-23 2017-07-04 Posco公司 Economizing type two phase stainless steel and the kitchen appliance being produced from it
CN116197412A (en) * 2023-01-17 2023-06-02 福州大学 Method for improving plasticity of 3D printing duplex stainless steel

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KR20130034349A (en) 2011-09-28 2013-04-05 주식회사 포스코 Lean duplex stainless steel excellent in corrosion resistance and hot workability
JP6134553B2 (en) * 2012-03-28 2017-05-24 新日鐵住金ステンレス株式会社 Duplex stainless steel with good acid resistance
KR101587700B1 (en) 2013-12-24 2016-01-21 주식회사 포스코 Lean duplex stainless steel
KR20230059938A (en) 2021-10-26 2023-05-04 주식회사 포스코 Ferritic-austenitic two-phase stainless steel and the method for manufacturing the same

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Publication number Priority date Publication date Assignee Title
CN103987867A (en) * 2011-11-30 2014-08-13 Posco公司 Lean duplex stainless steel and preparation method thereof
CN103987867B (en) * 2011-11-30 2017-03-08 Posco公司 Economizing type two phase stainless steel and preparation method thereof
CN106917054A (en) * 2015-12-23 2017-07-04 Posco公司 Economizing type two phase stainless steel and the kitchen appliance being produced from it
CN105886956A (en) * 2016-07-01 2016-08-24 东北大学 Economical duplex stainless steel sheet and preparation method thereof
CN105886956B (en) * 2016-07-01 2017-10-31 东北大学 A kind of economizing type two-phase stainless steel sheet and preparation method thereof
CN106086700A (en) * 2016-07-11 2016-11-09 无锡市锡达电子科技有限公司 A kind of cylinder jacket for Stirling engine and processing technique thereof
CN106086700B (en) * 2016-07-11 2018-01-09 无锡市锡达电子科技有限公司 A kind of cylinder jacket and its processing technology for Stirling engine
CN116197412A (en) * 2023-01-17 2023-06-02 福州大学 Method for improving plasticity of 3D printing duplex stainless steel
CN116197412B (en) * 2023-01-17 2024-04-30 福州大学 Method for improving plasticity of 3D printing duplex stainless steel

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US20080112840A1 (en) 2008-05-15
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EP1838890A1 (en) 2007-10-03
JP2008525636A (en) 2008-07-17
WO2006071027A1 (en) 2006-07-06

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